JP2001154320A - Color image forming method and color image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming method by which digital color image information nearly free from color turbidity is easily obtained in a short. time from a color film after photographing and to provide a stable image forming method in which finish quality lowers hardly even in a slack period. SOLUTION: In each of the image forming methods, a color photosensitive material is developed and image information is photoelectrically read from the resulting image and converted to electrical digital image information, (1) a developing solution used in the development comprises a developing agent- containing solution of <=pH 7 and an alkali agent-containing solution and (2) the photosensitive material is developed by supplying the developing agent- containing solution and the alkali agent-containing solution to the photosensitive material and then heating the photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for easily and quickly obtaining a color image from a photographed silver halide color light-sensitive material. It is also possible to convert color images of silver halide color light-sensitive materials used in the market into electrical digital image information and use it. And its device.

[0002]

2. Description of the Related Art In the color photographic market, a so-called color film or color film is obtained in which a photographed color light-sensitive material (hereinafter also referred to as a color film) is developed in a photo lab and the obtained image is printed on photographic paper to obtain a color print. Paper systems are usually used. Recent trends in the color photography market include (1) decentralization of development sites, that is, collecting and developing color films from stores such as photo shops,
From a conventional centralized large-scale photo lab (large lab) that passes completed color prints to customers via photo shops, to a store lab (mini-lab) that develops customer's film at stores and delivers color prints on the spot With the trend of decentralization and (2) the expansion of the use of digital photographic images, that is, the emergence of digital minilabs that handle photographic images digitally, electronic imaging of photographed film images, and print services and optical recording through electronic images The momentum for development in various image media such as magnetic recording, magneto-optical recording, and semiconductor element recording is becoming remarkable. However, with respect to the above (1), it is a fact that the time taken from receiving a color film from a customer to delivering a finished print is remarkably shortened due to the decentralization of development sites by the minilab, but it still takes at least about 30 minutes. In particular, it takes at least 10 minutes to develop a film. In addition, since the developing solution is used, maintenance is troublesome and there is little room for simplification. Regarding the above item (2), the digitalization of film information takes a long time (for example, several days) and the number of service bases is limited, which restricts the development of multimedia.

[0003] Under such circumstances, compared to the conventional color film / paper system, image access is much simpler and faster, and image information utilization is digital imaging and the use of digital imaging. It is desired to realize a new image forming system using a general-purpose color film that can be applied to various image media.

In order to meet this need, International Publication Nos. WO 98/19216 and WO 98/25399 develop a black-and-white color film, scan an obtained image with reflected light and transmitted light, and read color information from each image information. A method for constructing an image is disclosed. In this method, since the color film is brought into contact with the developing solution while being conveyed, and scanning is sequentially performed as it is, there is a problem that image reading accuracy is insufficient and noise of image information is large. In addition, processing time is required, and the fluctuation of processing performance is large.

On the other hand, JP-A-6-266066 and JP-A-6-295035 disclose improved methods for improving reading accuracy by providing a reflective layer in a color film. However, the implementation of the disclosed method has the disadvantage that general-purpose films available on the market cannot be applied, and is not practical. Also, Japanese Patent Application Laid-Open Nos. 9-146647 and 9-202031 disclose a method of obtaining digital image information by scanning and reading from an image obtained by heating and developing a film containing a developing agent. Although this method has been solved in terms of rapid and simplified development,
The disadvantage that a general-purpose film cannot be applied similarly to the above-mentioned US patent has not been solved.

On the other hand, Japanese Patent Application Laid-Open No. 11-18045 discloses that a color photosensitive material having undergone a color developing step is overlaid with a fixing material having a layer containing a fixing agent to dissolve and remove silver halide to easily form an image. A method of doing so is disclosed. This method is also a rapid and simplified development processing method, but the processing stability tends to deteriorate, especially in the off-season, when the screen is easily stained, and the finished photo quality tends to fluctuate. Is difficult to maintain.

As described above, a color print can be obtained easily and quickly from a commercially available color film for photography, and the digital information can be handled, so that it can be applied to various image media. At present, a possible color image forming system has been demanded from the market but has not sufficiently responded to it.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide means for responding to the above-mentioned market demands. That is, first, it is to present a color image forming method capable of obtaining digital color image information from a photographed color film. Second, a color image forming method capable of obtaining a color image with little color turbidity easily and in a short time is presented. Third, there is a need to provide a stable image forming method in which the quality of the finished image is less likely to be reduced even during off-peak periods.
A color image forming method that can obtain digital color image information is a method that links the use of color film images to various image recording media such as color printing, optical recording, magnetic recording, semiconductor element recording, magneto-optical recording, etc. The object of the present invention described above includes such an intention.

[0009]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies from the viewpoints of both simplification and speed of development processing and improvement of image reading accuracy. The goal was achieved. That is, the present invention is as follows.

[0010] 1. The image forming method of subjecting the photographed silver halide color light-sensitive material to development processing, photoelectrically reading image information from the obtained image, and converting the read image information into electrical digital image information. The developer used for the development processing is at least composed of a developing agent-containing solution having a pH of 7 or less and an alkali agent-containing solution,
(2) The color image, wherein the developing process is a developing process in which the developing agent-containing solution and the alkali agent-containing solution are supplied to the photosensitive material, and then the photosensitive material supplied with the developing solution is heated. Forming method.

2. 2. The color image forming method according to the above item 1, wherein the photographed silver halide color light-sensitive material has a support mainly composed of polyester.

3. After developing the color photosensitive material,
3. The color image forming method according to the above item 1 or 2, wherein a transparency process is further performed, and image information is photoelectrically read from the obtained image.

4. 4. The color image forming method as described in any one of the above items 1 to 3, wherein the digital image information obtained by photoelectrically reading and converting the image is further subjected to image processing.

5. The color image forming method according to any one of the above items 1 to 3, wherein the developing agent contained in the developing agent-containing liquid is a color developing agent.

The present invention is a simple and quick image access method in which image information is electrically extracted and used at the stage where only the development process is completed without performing all the development processes of the photographed photosensitive material. In addition, the method of heat development has been incorporated to improve the accuracy of image extraction and further speed and simplicity. It is a feature of the system. That is, (1) a developing agent solution which is stable due to a neutral pH but has a low developing activity and an alkali solution which has a developing activating ability are separately supplied to a photographed silver halide color light-sensitive material, and the both are mixed. (2) Then, the photosensitive material containing the developing solution is heated and developed. (2) Then, the image elements of the images obtained on the respective photosensitive layers are read photoelectrically by an image scanner. Various color image means by obtaining electrical image information, and (3) converting the obtained image information into an image forming method for obtaining electrical blue, green, and red digital image information by performing arithmetic processing. The data can also be output to an electronic, magnetic, or optical recording medium and stored for later use.

By adopting a developing method having two features, that is, the separation and supply of the main agent and the alkaline agent of the developing solution, and the heating of the photosensitive material containing the developing solution, firstly, the progress of the development is controlled by the time to be heated. It is easy to adjust development,
Suppressing over-development and fogging, making it less susceptible to outside temperature, and drying the image layer by heating to increase the transparency. The accuracy is improved. Thirdly, the developer is stored in a stable form until immediately before development, and since many aspects are disposable processing, the development management is simple, the development equipment is simple and the cost is low. And other advantages. The most important advantage is that this development method allows rapid heating and rapid development stoppage (by stopping heating), so that although it is wet development, which is a weak point of silver halide photosensitive materials, it is quick and solves the weakness. That is, a dry processing operation can be realized.

There are no particular restrictions on the color light-sensitive material to which the present invention can be applied, and any color film for general photography that is widely used in the market can be used. Photosensitive materials having a wide polyester support are preferred. Further, since the polyester support can reduce the thickness of the support, it is also advantageous in that reading noise due to the support is reduced. Among the polyester supports, photosensitive materials using polyethylene naphthalate as a support, for example, A
PS films are preferred.

Further, according to the present invention, the transparency of the developed film is improved by performing a transparency process following the development process to remove silver halide which may be noise of the image material and, if necessary, developed silver. Image reading accuracy can be improved.

Further, according to the image forming method of the present invention, the blue, green and red digital image information converted from the read image information can be directly or color-transferred through any image recording medium such as a magnetic, optical recording element or semiconductor element. The image is output to various color printers such as a print, an ink jet print, and a thermal transfer print. At this time, image processing is performed to further enhance image quality and image usability.

Further, according to the present invention, if a color developing agent is used, the image is a dye image, and the image can be read in accordance with the wavelength of each of the generated dyes. High quality digital image information with little turbidity can be obtained.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described in detail below, but before that, some explanations of terms used in the present invention will be added. In the following description of the image forming method of the present invention, the development usually used in the color photographic market with respect to the development used in the present invention is referred to as a standard development. In the color photographic market, each photo lab receives the products (color photosensitive materials) of each company and develops them using a substantially common developing method. For example, color negative film formulations are CN16 series (designated by Fuji Photo Film Co., Ltd.), C41 series (designated by Eastman Kodak Company, USA), and CNK4 series (Konica Corporation)
Designated prescription). These are considered to be international standard processes even though the process names (product names) are different. This is the content of the standard development.

In general, the “development process” includes a broad sense of “development process”, which refers to a series of processes for developing a photographed photosensitive material, fixing an image, and obtaining a stable image, and a development process therein. In the present invention, “development processing” refers to the latter, that is, “development processing” in a narrow sense in principle. The term "development processing" in a broad sense is described as "development processing of a color film", but when it is clear from the context, the "development processing" in a broad sense may also be referred to as "development processing". Further, in the following description, "development processing"
And "image processing", two "processing" with different contents
Are referred to as “processing”, and where there is a possibility of causing confusion, they are expressed separately from “development processing” and “image processing”.

Now, with the above as a preamble, a specific description of the present invention will be made in the following order. 1. 1. Process flow of the image forming method of the present invention Development processing 3. 3. Transparency treatment 4. Image processing including image reading and conversion to digital image information Color light-sensitive material used in the present invention and related supplementary explanations

1. First, the outline of the flow of the method of the present invention will be described with reference to the drawings. FIG. 1 is a block diagram schematically showing the flow of the steps of the method of the present invention. 1, the film processing and image reading unit 110 includes a developing unit 111 and an image information reading unit 114. The color film F is loaded into the image forming apparatus and the film processing and image reading unit 11
0, and is subjected to development processing by the development processing unit 111.
An image is formed on each of the front side, the back side, and the intermediate three photosensitive layers sandwiched therebetween. This development processing unit 111
It has a developer supply device and a heating device H, and the developer supply device is composed of a device R for supplying a developer-containing liquid having a pH of 7 or less (referred to as a developer solution) and a device A for supplying an alkaline solution. The developing agent solution and the alkaline agent solution also contain other components constituting the developing solution in one or both of them, and are supplied to the color film F at a controlled ratio from the apparatus R and the apparatus A and mixed. Then, the composition of the developer is obtained. The color film F supplied with the developing solution in the form of the developing agent solution and the alkali agent solution is heated by the heating device H to substantially start development. The developed color film F that has been subjected to the heat development is supplied to the image information reading unit 114.
The image elements constituting the image are photoelectrically read by an image scanner (not shown) to obtain image information. In FIG. 1, the image information reading unit 114 schematically illustrates a method of reading with transmitted light, but one of the preferable modes is to read an image by combining reading with reflected light and reading with transmitted light. It is.
The image information is stored in the image processing unit 1 in the form of a time-series electrical signal.
After being transmitted to a digital signal 20 and converted into a digital signal so that image processing can be performed, the digital signal is converted into electrical blue, green and red digital image information. The electrical digital image information obtained by the above steps can then be applied to any color image forming means to obtain a color image.

The color image forming means can directly output to a color printer such as a silver halide color print, an ink jet print, a thermal dye transfer print, etc., and each image information recording medium such as a disk or a tape in the form of magnetism, light, and a semiconductor device. An excellent feature of the present invention is that the digital image information can be converted between an image information recording medium and various forms of color prints (color copies). It is.

In the image forming method of the present invention, the color film can be developed only by performing the development process. Therefore, in the case of the conventional general-purpose process, the subsequent processes such as desilvering and stabilizing bath which are performed after the development process are performed. There is no need for processing, so the processing steps for color films are extremely simple and fast, and at the same time, the developing solution is supplied in the form of a developing agent solution and an alkaline solution and is not mixed until just before the start of development, and is stable to each other. It is stored in a perfect form, so there is no deterioration of the developer,
Image quality is maintained, developer management is easy,
Therefore, the object of the present invention is satisfied in terms of speed, simplicity, and image quality.

According to the present invention, since an image can be obtained in the form of digital image information, it is not necessary to save the color film after development. After image reading is completed, desilvering processing such as bleaching and fixing processing or bleach-fixing processing and stabilizing bath processing are performed, and a long-term stored developed film similar to a color film obtained by standard development processing can be obtained. it can.

2. Development Processing In the present invention, "development processing in which a developer is supplied to a photosensitive material and heated" means that development at a target speed cannot be achieved at the temperature of the supplied developer (normally, room temperature). , A development process in which substantial development is started by heating. Therefore, it is not so-called high-temperature development in which a high-temperature developer is applied to a photosensitive material. In order for this type of development to proceed, the temperature at which the photosensitive layer supplied with the developer is heated is at least 5 times lower than the temperature of the supplied developer.
Conditions higher by at least 10 ° C, preferably at least 10 ° C are selected.

First, a method of supplying a developing solution (a base solution and an alkaline solution), that is, a specific form of the developing process will be described, and then a method of heating will be described. Various known methods can be used for supplying the developing solution to the photosensitive layer of the color film. For the developing agent solution, an immersion treatment method in which the color film is immersed in the developing agent solution, and the developing agent solution is colored. Various types of coating methods for applying to the film surface, a spray method for spraying the developing agent solution onto the color film surface, and a sheet treatment (a web or sheet impregnated with the developing agent solution in contact with the color film surface to diffuse and supply the solution) Or web processing). In addition, the alkali agent solution is preferably performed by any of a coating method, a spray method, and a sheet treatment (or a web treatment). Various combinations can be selected for the combination of the above four supply systems for the developer solution and the three supply systems for the alkali agent solution.
The two supply systems may be the same or different.
The color film to which the developer has been supplied is next subjected to a heat treatment.

The developing solution is divided into a stable developing agent solution and an alkaline solution until the start of development, and is not exposed to a high temperature unlike the high-temperature development. The handling is easy, and the means for preventing air oxidation in the developer storage container such as a stock tank may be simple.
In addition, the development progress is controlled by the supply amount of the developing solution, and the fogging of the image-receiving part is suppressed at the end of the heating. Therefore, the development progress can be easily adjusted, the image reading accuracy is high, and the image quality with little color blur is high. , And the above-mentioned advantages are obtained.

The developer can be supplied by any known method and method. Among them, the method of supplying only a processing solution in an amount capable of permeating the photosensitive material to the photosensitive material and processing the waste material is a waste liquid. No liquid is produced, and the above-mentioned immersion treatment, application treatment, spray treatment, and sheet treatment can be performed under the same conditions. For example, in the case of the new solution processing, there is a method in which a photosensitive material is immersed in a processing solution and then an excess processing solution is removed with a squeeze roller. This method is disclosed in JP-A-9-15819 and JP-A-9-15820.
And the method described in JP-A-9-15822 are preferred.

As the coating process, a known method such as a coating and developing method such as gravure coating, reverse coating, hopper coating, and slit coating can be applied. Further, one of the preferable methods is a sheet treatment in which the photosensitive material is substantially impregnated through a medium carrying a processing liquid. As this method, a method described in Japanese Patent Publication No. 2655337 can be exemplified. As the medium for supporting the treatment liquid, felt, woven fabric, metal having slits or pores, or the like can be used. Among them, JP-A-8-290088 and 8-29008
No. 7, No. 9-138493, and a method of applying a treatment liquid using a sponge or the like is preferable. Other coating methods are described in JP-A-59-18153.
Roller coating method and ear bar coating method according to,
JP-A-59-18354, a method of performing coating using a water-absorbing member, or JP-A-63-144354, JP-A-63-144355, JP-A-62-38460, JP-A-3-210555 and the like. An apparatus may be used.

In the coating process, it is often advantageous to impart viscosity to the processing solution in that a required amount of the processing solution can be reliably supplied to the photosensitive material. In that sense, the viscosity process is preferred. is there. As the viscous agent for imparting viscosity to the treatment liquid, an organic or inorganic polymer material that can be dissolved in the treatment liquid is used. Preferred viscosity-imparting agents include hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate phthalate, carboxymethyl cellulose, water-soluble cellulose derivatives such as carboxyethyl cellulose, starch and dextrin, alginic acid, peptin,
Various natural polymers such as polysaccharides, sugars such as galactose, sucrose, and glucose; vinyl alcohols such as polyvinyl alcohol and partially saponified products thereof; and water-soluble solutions such as polyacrylate, polymethacrylate, butyl methacrylate, and copolymers thereof. Synthetic polymers and the like. The preferred amount of coating in the coating process is an amount sufficient for the highest density part to be sufficiently developed,
Although it depends on the concentration of the developing solution and the amount of silver in the photosensitive material, it is usually 10 to 100 ml / m ² , preferably 15 to 50 ml / m ² .
m ² .

The spray processing, ie, the spray processing, is a method of performing processing by spraying a processing solution onto a photosensitive material.
An advantage is that it is easy to adjust the spray amount of the processing liquid to an amount that can substantially penetrate the photosensitive material. Further, the amount of the spray liquid may be set to be equal to or more than the necessary supply liquid amount, and the excess developer flowing down the application surface may be circulated and reused. Regardless of the method and method of spraying the processing liquid, the number of nozzles or counting, the spraying may be performed while moving a single movable nozzle, or may be performed using a plurality of fixed nozzles. Also,
The spray may be performed while the photosensitive material is fixed and the nozzle is moved, or the spray may be performed while the nozzle is fixed and the photosensitive material is moved. Among them, a plurality of nozzle holes for injecting a processing liquid described in JP-A-8-123001, JP-A-9-160208, and JP-A-9-179272 have a plurality of nozzle holes which are arranged at regular intervals in a conveying direction of a photosensitive material or a processing member. A method in which the processing liquid is sprayed by a processing liquid applicator having nozzles arranged linearly along the intersecting direction and an actuator for displacing the nozzles toward a photosensitive material or a processing member on a transport path is particularly preferable. . The preferred spray amount is the same as in the case of the above-described coating process. In the present invention, the liquid containing the developing agent and the liquid containing the alkaline agent can be supplied from different nozzles and spray-coated with the same head.

A developing sheet in the form of a sheet having a processing liquid carrying layer such as a polymer layer or a sponge layer containing a processing liquid on a support, or a developing web in the form of a roll can also be preferably used. Processing sheet and processing web
The processing liquid is supplied to the photosensitive layer by overlapping the processing liquid occlusion layer in contact with the photosensitive layer side of the photosensitive material. In a preferred embodiment of the present invention, heating is performed in a state where both are superimposed. The treatment layer of the treatment member (sheet or web) is preferably made of a water-soluble polymer as the treatment liquid carrying layer. An example is Research Disclosure 1.
Page 7643, page 1871, page 651, page 307
105, pages 873-874 and JP-A-64-13,5.
No. 46, pp. 71-75. Among them, gelatin and a combination of gelatin and another water-soluble material (for example, polyvinyl alcohol, denatured polyvinyl alcohol, cellulose derivative, acrylamide polymer, etc.) are preferable.

Next, a description will be given of a method of distributing the components constituting the developing solution into a developing agent solution and an alkaline solution. The distribution method is performed as follows in accordance with the principle of ensuring the storage stability of the processing solution. (1) Development of storage stability improvement by dividing into two solutions The developing agent solution contains a developing agent and a prosthetic agent, and has a pH of 7 or less, and is less susceptible to air oxidation.
The alkali solution contains an alkali agent that imparts development activity. Separate the developing agent solution and / or the alkaline agent solution in consideration of the interaction with other components and the deterioration due to chemical changes and precipitation due to air oxidation, etc. Contained.
Therefore, the storage stability is higher than that of the one-component developer. The developer solution is preferably p
H 0.1-6.0, more preferably pH 0.5-3.0.
It is. (2) Utilization of Base Precursor Since the developer has a two-part composition, the alkali in the alkali solution is not necessarily the alkali compound itself, but may be a base precursor which acts on the components in the developing agent solution to generate the alkali. Good. A particularly preferred combination is a developing agent solution containing a basic metal compound, and an alkali agent solution is a complex-forming compound that undergoes a complexing reaction with a metal ion of the basic metal compound in the presence of water to release a base. It is a method of containing. This complex forming compound is called a base precursor. By mixing the developing agent solution and the alkaline solution, the base is released and the pH of the processing solution is reduced.
And development is started with the addition of a heating effect. The pH before use is not particularly limited, but is pH 3 to
9th place is appropriate. The method using a base precursor will be further described later.

Next, the structure of the developer will be described. For the development, either black-and-white development or color development can be used, and a preferred developer can be selected according to the purpose. Since the black-and-white developer has a high developing activity, the developing time can be further reduced, and the color noise of the color image can be increased by suppressing the fog of the non-image area to reduce the image noise. And the developing solution is stable, the processing stain is small, and the management of the solution is easy. On the other hand, when a color developer is selected, an image can be read with a color image, and an image with little color mixture and high saturation can be obtained.

Hereinafter, unless otherwise specified, a description will be given of the structure of a developing solution formed by mixing a developing agent solution and an alkali solution. Conventionally known developing agents can be used for the black and white developer. Developing agents include dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate, catechol), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone,
-Phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol, N-methyl-
3-methyl-p-aminophenol, N-methyl-2-
Sulfoaminoaminophenol), ascorbic acid and erythorbic acid and isomers and derivatives thereof, p-phenylenediamines also used as a color developing agent described later, and the like.
They can be used alone or in combination. When these developing agents are used in the form of a salt, the corresponding salt is sulfate,
Forms such as hydrochloride, phosphate, p-toluenesulfonate and the like are used. The addition amount of these developing agents is preferably 1 × 10 ⁻⁵ to 2 mol / l per liter of developer.

A preservative can be used in the black-and-white developer if necessary. Sulfites and bisulfites are generally used as preservatives. The amount of these additives is 0.01 to
1 mol / l, preferably 0.1 to 0.5 mol / l.
In addition, ascorbic acid is also an effective preservative, and the preferable addition amount is 0.01 mol / liter to 0.5 mol / liter. In addition, hydroxylamines, sugars, o-hydroxyketones, hydrazines and the like can also be used.
In this case, the amount of addition is 0.1 mol / liter or less.

The pH of the black-and-white developer solution is 7 or less,
The pH is preferably 0.1 to 6, but by mixing with an alkali agent solution, the pH becomes 9 to 13, preferably 9.5 to 12.5. If necessary, various buffering agents may be used to maintain the pH after mixing. Preferred buffering agents are carbonates, phosphates, borates, 5-sulfosalicylates, hydroxybenzoates, glycines, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrate salts, valine salts, lysine salts and the like can be mentioned. In particular, the use of carbonate, borate, and 5-sulfosalicylate is preferable in that the pH range is maintained and the cost is low. The buffer is used in the form of an alkali metal such as Na or K or an ammonium salt as a counter salt. These buffering agents may be used alone or in combination of two or more. Further, an acid and / or an alkali may be added to obtain a desired pH. As the acid, an inorganic or organic water-soluble acid can be used. For example, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, propionic acid, ascorbic acid and the like. As the alkali, various hydroxides and ammonium salts can be added. For example, potassium hydroxide, sodium hydroxide, aqueous ammonia, triethanolamine, diethanolamine and the like can be mentioned.

The black and white developer preferably contains a silver halide solvent as a development accelerator. For example, thiocyanate, sulfite, thiosulfate, 2-methylimidazole, thioether compounds described in JP-A-57-63580, and the like are preferable. The amount of these compounds added is 0.00
About 5 to 0.5 mol / liter is preferable. Other development accelerators include various quaternary amines, polyethylene oxides, 1-phenyl-3-pyrazolidones, primary amines, N, N, N ', N'-tetramethyl-p-phenylenediamine, and the like. be able to.

In the black and white development step of the present invention, various antifoggants may be added for the purpose of preventing development fog. As antifoggants, alkali metal halides such as sodium chloride, potassium chloride, potassium bromide, sodium bromide and potassium iodide and organic antifoggants are preferred. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole and hydroxyazaindolizine; and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and thiosalicylic acid Such mercapto-substituted aromatic compounds can be used. These antifoggants include those that elute from the color reversal photosensitive material during processing and accumulate in these developers. Among them, the concentration of iodide added is 5 × 1
It is about 0 ^{-6 to} 5 × 10 ^-4 mol / l. Bromide is also preferable for preventing fog, and the preferred concentration is 0.001 mol / L to 0.1 mol / L, and more preferably 0.01 to 0.1 mol / L.
It is about 0.05 mol / liter.

Further, the black-and-white developer of the present invention contains a swelling inhibitor (for example, an inorganic salt such as sodium sulfate and potassium sulfate).
Alternatively, a water softener can be contained. As the water softener, those having various structures such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic inorganic phosphonic acid can be used. Specific examples are shown below, but the present invention is not limited to these. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N'N'-tetramethylenephosphonic acid,
-Hydroxyethylidene-1,1-diphosphonic acid. Two or more of these water softeners may be used in combination. A preferable addition amount is 0.1 g to 20 g / liter, more preferably 0.1 g to 20 g / l.
5 g to 10 g / liter. Also, if necessary, alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid,
Various surfactants such as aromatic carboxylic acid polyalkylenimine may be added.

When a color developing solution is used for the development in the present invention, a color developing solution is preferably used. The color developing solution is an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. As the color developing agent, a p-phenylenediamine compound is preferably used. Representative examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4 -Amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides thereof,
Phosphate, p-toluenesulfonate, tetraphenylborate, p- (t-octyl) benzenesulfonate and the like can be mentioned. If necessary, two or more of these developing agents may be used in combination. The preferred addition amount is 0.0
05 mol / l to 0.1 mol / l, preferably 0.01 mol / l
It is about mol / liter to about 0.05 mol / liter.

The pH of the color developer is preferably in the range of 8 to 13, most preferably 10.0 to 12.5. Various buffers are used to maintain this pH.
For the color developer, various buffering agents described above for the black-and-white developer can be used. In particular, 5-sulfosalicylate, tetraborate, and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH region of pH 10.0 or more,
Even when added to a color developer, it has the advantage of being inexpensive without adverse effects on photographic performance (such as stain) and is preferable as a buffer for the color developer. The amount of the buffer to be added to the color developer is suitably the amount described above in the description of the black-and-white developer.

Further, various development accelerators may be used in combination with the color developer as required. Further, examples of the development accelerator include U.S. Pat. No. 2,648,604 and JP-B-44-95.
No. 03, various pyridinium compounds represented by U.S. Pat. No. 3,171,247 and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, and JP-B-44-9304.
No. 2,533,990, U.S. Pat.
Nos. 2,950,970 and 2,577,127, nonionic compounds such as polyethylene glycol and derivatives thereof, and polythioethers; US Pat.
The thioether-based compound described in No. 42 may be used.

If necessary, benzyl alcohol and its solvent such as diethylene glycol, triethanolamine and diethanolamine can be used.
However, considering the environmental load, the solubility of the liquid, the generation of tar, and the like, it is preferable to use these as little as possible.

Further, a silver halide solvent similar to the black-and-white developer may be contained. For example, thiocyanate,
Examples thereof include 2-methylimidazole and thioether compounds described in JP-A-57-63580.

An antifoggant is usually added to the color developer, and the description given in the description of the black-and-white developer also applies.

Various preservatives can be used in the color developing solution according to the present invention. As typical preservatives, hydroxylamines and sulfites can be used.
These addition amounts are about 0 to 0.1 mol / liter. In some cases, it is more preferable that the color developer used in the invention contains an organic preservative in place of the hydroxylamine and the sulfite ion.

The term "organic preservative" as used herein refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution for a color photographic material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Particularly effective organic compounds are ketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines. It is a preservative. JP-A 1-1869
Nos. 39 and 1-187557, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. No. 3,746. An aromatic polyhydroxy compound described in No. 544 or the like may be used as necessary. In particular, alkanolamines such as triethanolamine, N, N-diethylhydroxylamine, N, N
-A dialkylhydroxylamine such as di (sulfoethyl) hydroxylamine, a hydrazine derivative (excluding hydrazine) such as N, N-bis (carboxymethyl) hydrazine, or an aroma represented by catechol-3,5-disulfonic acid sodium The addition of an aromatic polyhydroxy compound is preferred.

The addition amount of these organic preservatives is preferably about 0.02 mol / l to 0.5 mol / l, more preferably about 0.05 mol / l to 0.2 mol / l. Two or more kinds may be used in combination.

In addition, the color developing solution according to the present invention includes:
Organic solvents such as diethylene glycol and triethylene glycol; dye-forming couplers; citrazic acid, J acid,
Competitive couplers such as H-acid; nucleating agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; chelating agents (hard water softeners) and black-and-white development described in the section on black-and-white developers. It may contain the surfactant described in the section of the liquid.

The alkali agent solution using a base precursor will be further described. This solution can be combined with both black and white and color developer solutions. As a complex forming compound for a metal ion, a compound known as a chelating agent in analytical chemistry can be used. For example, aminopolycarboxylic acids (including salts) such as ethylenediaminetetraacetic acid, aminophosphonic acids (including salts), pyridinecarboxylic acids (salts), and picolinic acid are used. The complex-forming compound is preferably neutralized with a base and used in the form of a salt. Particularly, guanidines and amidines are preferable.
The amount of the additive is the amount of silver applied to the color film to be applied.
It is added to the alkali agent solution in an amount of 1 to 10 mol, more preferably 1 to 5 mol, per mol. The developing agent solution also contains a stoichiometrically equivalent amount of a basic metal compound. The method in which part or all of the alkali agent in the alkali agent solution is replaced with a base precursor is excellent in stability over time during storage of the processing solution, and is developed by a particularly simple operation in the case of a coating process or a sheet or web process. Is convenient.

Further, the alkaline agent solution containing the base precursor may contain a surfactant, an antifoggant, a complex-forming compound, an antifungal agent, and a bactericide. It may be composed only of a base precursor and water from the function described above.

Including the method using a base precursor,
The development processing time is 3 seconds to 1 minute, preferably 5 seconds to 60 seconds for black and white development, and 5 seconds to 2 minutes, preferably 10 seconds to 2 minutes for color development. Although the processing temperature has already been described for each embodiment, the general range of the heat development temperature of this system is 20 ° to 100 ° C., preferably 3 ° C.
3 ° to 90 ° C.

Next, the heating means will be described. As the heating means, any known method and method can be selected,
A blast heating method using warm air or steam, a heating method using infrared rays, a contact electric heating method such as heating with a heat roller, and an electromagnetic heating method such as microwave irradiation are preferable.

The blast heating method is a method in which warm air or steam is applied to the front surface and, if necessary, the back surface of the color film, and heating is preferably performed by impingement such as nozzle blowing so that fresh air is efficiently blown. In particular, a ceramic hot air heater is also preferably used. Preferably min 4m ³ to 20 m ³ as supply air volume of the case,
Particularly preferred is 6m ³ ~10m ^3. The heating prevention thermostat of the ceramic hot air heater is preferably operated by heat transfer, and the mounting position is preferably mounted on the leeward or upwind side through a radiation fin or a heat transfer portion. Further, a method of applying steam and heating is also a preferable method. The blast temperature is 40-100 ° C, preferably 5
0-90 ° C.

The infrared heating method is a method of using an electric lamp having a large amount of near infrared components such as a tungsten lamp, or performing non-contact heating with a ceramic heater or an electric heater that emits far infrared rays. The wavelength of the near infrared heater is 0.
It is in the range of 8 μm to 1.0 mm, and is preferably a far infrared heater, particularly preferably a heating by a heat ray having a wavelength of 2500 to 25000 nm. The surface temperature of the heater that emits near-infrared light or far-infrared light is about 50 to 300 ° C., and the temperature of the surface of the color film is 100 ° from room temperature.
C, preferably from room temperature to 80 ° C.
Electric heaters for infrared radiation include rod-shaped (straight) heaters that use electric heating resistors such as ceramics and nichrome wires as rods, and surface emission heaters that are bent so that the electric heating rods are in close contact with each other and arranged in a plane. Used. Further, a panel heater using an electric resistor such as a plate-shaped ceramic may be used.

In the contact heating method, a heated heat roller is pressed against the front or back surface of the color film and heated. The heat roller referred to here is capable of controlling the temperature at the center to heat the outer periphery. A heat source (for example, a metal resistance heating element, a halogen lamp, etc.) and a roller using a metal with good thermal conductivity (for example, aluminum, stainless steel, iron, copper, etc.) or a plastic material (for example, bakelite, etc.) A transport roller whose outermost peripheral portion does not adhere to the film and is covered with a material for uniformizing heat distribution, such as Teflon or silicon rubber, and whose outer periphery is appropriately heated. For example, a diameter of 12 to 80 mm and a length of 30 to 11
One having a diameter of 0 cm is preferably used. Further, the surface temperature of the heat roller is 40 to 150 ° C, more preferably 60 to 100 ° C. The heat rollers may be in a staggered arrangement or in an opposed arrangement, but the opposed arrangement is particularly preferred. Note that heating drum development in which the heat roller is replaced with a heat drum can also be applied to the present invention, but since there is no substantial difference from the heat roller heating method except that the diameter of the drum is large and that it is performed with one drum, Description is omitted.

In the electromagnetic heating method, microwave heating is exclusively used. As a microwave oscillating device, a magnetron, a klystron, a traveling wave tube that oscillates an electron, or the like is used. In particular, a magnetron is preferable for the purpose of the present invention, and an oscillation frequency of 915 or 2450 MHz (megahertz), particularly 2450 MHz (megahertz) is used. Microwave heating is suitable. In order to make the distribution of microwaves on the surface of the color film uniform, irradiation is preferably performed while rotating or moving the color film and / or the oscillation source, and the color film is sequentially irradiated by arranging a plurality of oscillation sources. It is also preferable to adopt a method in which the sheet is transported while receiving.

All of the above-mentioned heating systems are preferably used in the present invention. In particular, the blast heating system and the infrared heating system are preferable because they are non-contact type and are hardly stained and maintenance is easy. A steam heating system and an infrared heating system are preferred. It is also a preferred method to use them in combination. Each of the above-mentioned heating methods can be used in combination of two or more kinds, so that more rapid and uniform drying can be performed.

Examples of actual heat development are shown below, but the form of heat development used in the present invention is not limited to these examples. FIG. 2 is a schematic structural diagram showing an example in which the supply of a viscous developing agent solution by roller coating and the supply of an alkaline solution by web processing are combined with contact heating by a heating drum. The configuration of the apparatus and the developing action on the film in the apparatus will be described together. The color film F is bonded to the transport leader in the film bonding chamber 200, is fed through the film detection member 203, is transported in the direction of arrow A, and is filled with a viscous liquid in a liquid tank (Gieser) 20.
At 6, the developer is applied in such a manner that the photosensitive layer surface (lower side) is in contact with the roller. On the other hand, the alkaline agent web 174
Is fed from the feed roller 174 and is impregnated with an alkali agent in the alkali solution bath 204, and then stacked so that the photosensitive layer side of the color film and the alkali agent impregnated side of the web are in contact with each other and sent to the heating drum 170. In this state, the heating drum 170 goes around the heating drum 170 in the clockwise direction as shown in FIG. During this time, the film F is heated and developed, and evaporation is also prevented. Therefore, there is no heat loss due to latent heat of evaporation, so that the film F is uniformly heated in the depth direction of the photosensitive layer and development proceeds effectively.
With the peeling roller 175, the alkali agent web is taken up by the take-up roller 180, and the film F separated from the heating drum 170 is peeled off from the heating drum 170, so that the heating is completed. Drying begins. Next, the film F reaches the image information reading unit by the guide roller 177. Although the number of the image information reading device may be one, in the embodiment shown in FIG.
2 and the reading light source 211RA or 211RB
Or both and the reading sensor 209RA or 2
The reflected image is read by 09RB or both. The film F that has read the first image information is sent to the second image information reading unit 114 and is read by the reading light source 21.
The transmitted image is read by 1T and the reading sensor 209T. In the present embodiment, the surface temperature of the heat drum is 50 to 120 ° C., and the preferred temperature is 80 ° C.
１００100 ° C. The developing solution is a color or black-and-white developing solution to which a viscosity agent is added as described later and which has the composition described above.

In the present embodiment, the film F can be quickly and efficiently heated, and when the heating time ends, the film F can be quickly returned to room temperature (environmental temperature) without leaving any remaining heating time. Further, in addition to the above advantages, since the heating is performed for a short time while being performed at a high temperature, there is no increase in the unit consumption of energy consumption, and no increase in noise or cost is caused. The description of the development processing is completed above, and the transparency processing used in a preferred embodiment of the development processing of the color film of the present invention will be described next.

3. Transparency Treatment In the invention, the transparency treatment refers to a treatment for removing silver halide in an undeveloped layer in a developed photosensitive material. Therefore, although many parts are substantially common to the fixing processing of silver halide photographic materials, the fixing processing is intended to fix images to ensure long-term stability. The transparency processing of the present invention is a processing for the purpose of increasing the transmittance of the non-image portion and improving the image reading accuracy, and therefore may differ in details depending on each purpose. Various known methods and methods, such as immersion processing, application processing, and spraying processing, can be used as the method and system for the transparency treatment. The details described in the section of the development processing apply. The processing temperature and processing time are the same as those described in the section on development.

The composition of the processing solution for the clarifying process is substantially the same as the composition of the fixing solution as shown below, but when processed with a color developer, the bleaching agent is added to the clarifying solution. To remove both the same developed silver and residual silver halide as in the bleach-fix solution.

The clearing solution includes known fixing agents such as thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisthioglycolic acid, 3,6 Thioether compounds such as -dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which can be used alone or in combination of two or more. Also, Japanese Patent Laid-Open No. 55-
A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention,
The use of thiosulfates, especially ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The clarifying solution includes various known organic acids (eg, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.), organic bases (eg, imidazole, dimethylimidazole, etc.) or ,
Compounds represented by the general formula (Aa) described in JP-A-9-212819 including 2-picolinic acid, and general formulas (Bb) described in the same publication including cordiic acid include It preferably contains the compound represented. The addition amount of these compounds is 0.005 to 3.
0 mol is preferred, and more preferably 0.05 to 1.5.
Is a mole. The pH range of the clearing solution is preferably 3 to 8, and more preferably 4 to 7. When the pH is lower than the above range, the desilvering property when a silver bleaching agent is also contained is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. Conversely p
If H is higher than this, desilvering will be delayed and stain will easily occur. To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

The clarifying solution may be a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) or a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative. And sulfite ion releasing compounds such as metabisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and arylsulfines such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It preferably contains an acid or the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

As a preservative, in addition to the above, ascorbic acid, an adduct of carbonyl bisulfite, or a carbonyl compound may be added. Further, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as needed. In the present invention, the processing time of the transparency treatment is 5 to 240 seconds, preferably 10 to 60 seconds. The processing temperature is from 25C to 90C, preferably from 30C to 80C. The replenishing rate is ²⁰ ml to 250 ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 6 ml per m ² of the color film.
0 ml.

The clarifying solution can be used as it is according to the processing method or by incorporating the viscosity agent described in the section of coating development. Further, it is preferable to add a fixing accelerator from the viewpoint of increasing the transparency speed and the transparency. As the clarifying accelerator, any of known fixing accelerators such as thiocyanate, imidazoles, and thioethers are effective. Among them, fixing accelerators having a large effect are represented by the following general formulas (FI) and (FI). FII] and [FIII]
It is a compound shown by these.

[0072]

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In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group,
Represents an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an acyl group, a thioacyl group, a carbamoyl group or a thiocarbamoyl group. However, R ₁ and R ₃ are not hydrogen atoms at the same time.

[0074]

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In the formula, X and Y represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, -N (R
_{11) R 12, -N (R} 13) N (R 14) R 15, -OR 16 or -S
Representing the R _17. X and Y may form a ring. However, at least one of X and Y is substituted with at least one of a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group or an ammonium group, and a hydroxyl group. R ₁₁ , R ₁₂ , R
₁₃ , R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and R ₁₆ and R ₁₇ represent a hydrogen atom, a cation, an alkyl group,
Represents an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group.

[0076]

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In the formula, R ₄ represents a hydroxyalkyl group.

Hereinafter, the compound of the formula [FI] of the present invention will be described in more detail. R ₁ , R ₂ , and R ₃
The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group of
And preferably 10 to 10, particularly a hydrogen atom or a carbon number of 1 to 5
Is preferred. These groups may be substituted with various substituents, and preferred substituents include a hydroxyl group, an amino group, a sulfonic acid group, a carboxylic acid group, a nitro group, a phosphate group, a halogen atom, an alkoxy group, and a mercapto group. Group, cyano group, alkylthio group, sulfonyl group, carbamoyl group, carbonamido group, sulfonamido group, acyloxy group, sulfonyloxy group,
And ureido and thioureido groups. Furthermore,
More preferably, at least one of R ₁ , R ₂ and R ₃ is an alkyl group substituted with a water-soluble group. Here, the water-soluble group means a hydroxyl group, an amino group, a sulfonic acid group, a carboxylic acid group, or a phosphoric acid group, and the alkyl group preferably has 1 to 4 carbon atoms. Particularly, a case of a sulfonic acid group or a carboxylic acid group is preferable.
Further, it may have two or more substituents as required.
Hereinafter, specific examples of the compound of the general formula (I) of the present invention are shown, but the present invention is not limited thereto.

[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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The compound of the general formula [FI] of the present invention can be prepared by the method described in Journal of Heterocyclic Chemistry (J.
Heterocyclic Chem.) 2, 105 (1965), Journal of Organic Chemistry (J. Org. Ch.)
em.) 32, 2245 (1967), Journal of Chemical Society (J. Chem. Soc.) 3799.
(1969), JP-A-60-87322 and JP-A-60-1
No. 22936, No. 60-117240, JP-A-4-14-1
The compound can be synthesized by the method described in U.S. Pat. When the above compound is used alone as a fixing agent in a fixing solution or a bleach-fixing solution, it is preferably used in an amount of 0.03 to 3 mol / l, preferably 0.05 to 2 mol / l.

Next, the compound of the general formula [FII] of the present invention will be described in detail. X, Y, R in the general formula [FII]
_{11, R 12, R 13,} R 14, R 15, the alkyl group represented by R ₁₆ and R _17, an alkenyl group, an aralkyl group, the following examples are the aryl group and heterocyclic group. That is, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, hexyl group, isopropyl group, carboxyethyl group, sulfoethyl group, aminoethyl group, dimethylaminoethyl group, Propyl group, carboxymethyl group,
Hydroxyethyl group), substituted or unsubstituted carbon number 2
10 to 10 alkenyl groups (for example, vinyl group, propynyl group, 1-methylvinyl group), substituted or unsubstituted aralkyl groups having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-carboxyphenylmethyl group, 4-sulfophenylethyl group), substituted or unsubstituted carbon number 6
To 12 aryl groups (e.g., phenyl, naphthyl, 4-carboxyphenyl, 3-sulfophenyl), substituted or unsubstituted heterocyclic groups having 1 to 10 carbon atoms (e.g., pyridyl, furyl, A 5- or 6-membered ring such as a thienyl group, an imidazolyl group, a pyrrolyl group, a pyrazolyl group, a pyrimidinyl group, a quinolyl group, a piperidyl group and a pyrrolidyl group).

In the general formula [FII], the cation groups represented by R ₁₆ and R ₁₇ represent an alkali metal or ammonium. X
And Y may form a ring. Examples of the ring formed by X and Y include an imidazoline-2-thione ring, an imidazolidine-2-thione ring, a thiazoline-2-thione ring, a thiazolidine-2-thione ring, an oxazoline-2-thione ring, and oxazolidine- 2-thione ring, pyrrolidine-2-
A thione ring, or a respective benzo-fused ring.

However, at least one of X and Y is a carboxylic acid or a salt thereof (for example, an alkali metal salt,
Ammonium salts), sulfonic acids or salts thereof (eg, alkali metal salts, ammonium salts), phosphonic acids or salts thereof (eg, alkali metal salts, ammonium salts), amino groups (eg, unsubstituted amino groups, dimethylamino groups, Hydrochloride of methylamino group and dimethylamino group)
Alternatively, it is substituted with at least one of an ammonium group (for example, a trimethylammonium group and a dimethylbenzylammonium group) and a hydroxyl group.

The alkyl, alkenyl, aralkyl, aryl and heterocyclic groups may be substituted. Examples of the substituent include the following. Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, acylamino groups, ureido groups, urethane groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups, Sulfonyl group, sulfinyl group,
Examples thereof include an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, an alkylthio group, an arylthio group, a halogen atom, a cyano group, and a nitro group. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

A particularly preferred compound of the general formula [FII] is represented by the following general formula [FIV].

[0091]

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In the general formula [FIV], R represents a group having 1 to 10 carbon atoms.
An alkyl group, -N having 0 to 10 carbon atoms (R₂₀) R_{twenty one},carbon
-N (R_{twenty two}) N (R_{twenty three}) R_{twenty four}Represents
R_Five, R ₆, R₂₀, R_{twenty one}, R_{twenty two}, R_{twenty three}And R_{twenty four}Is hydrogen field
And an alkyl group. Where R, R_Five, R₆,
R₂₀, R_{twenty one}, R_{twenty two}, R_{twenty three}And R_{twenty four}At least one of
Rubonic acid or its salt, sulfonic acid or its salt, phos
Fonic acid or its salt, amino group or ammonium
And alkyl groups substituted with groups selected from hydroxyl groups.
You. In the general formula [FIV], more preferably, R has 0 to 0 carbon atoms.
6 -N (R₂₀) R_{twenty one}, 0 to 6 carbon atoms -N (R_{twenty two}) N
(R_{twenty three}) R_{twenty four}Represents R_Five, R₆, R₂₀, R_{twenty one}, R _{twenty two},
R_{twenty three}And R_{twenty four}Represents a hydrogen atom or an alkyl group. However,
R_Five, R₆, R₂₀, R_{twenty one}, R_{twenty two}, R_{twenty three}And R_{twenty four}Less of
One is carboxylic acid or its salt, sulfonic acid or
Represents an alkyl group substituted with a group selected from salts thereof.

Specific examples of the compound represented by formula [FII] of the present invention are shown below, but the present invention is not limited to these.

[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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The compound represented by the general formula [FII] of the present invention can be prepared by a known method, for example, the method described in Journal of Organic Chemistry (J. Org. Chem.) Vol. 24,470
-473 (1959), Journal of heterocyclic chemistry (J. Heterocycl. Chem.) Vo
l. 4,605-609 (1967), Journal of the Pharmaceutical Society of Japan, vol. 82, 36-45 (1962);
26203, JP-A-63-229449, OLS-
It can be synthesized with reference to 2,043,944.

The alkyl portion of the hydroxyalkyl group represented by R ₄ in the formula [FIII] has 1 to 9 carbon atoms.
R ₄ is preferably a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group.

The above general formulas [FI], [FII] and [FII]
When the compound [I] is used alone as a fixing accelerator in the clarifying solution, it is preferably used in an amount of 0.03 to 3 mol / l, more preferably 0.05 to 2 mol / l. Further, in the present invention, it is most preferable that the thiosulfate is used in combination with the thiosulfate.
About 0.25 is used. The specific addition amount is, of course,
0.001 mol to 0.5 mol
Mol / liter, more preferably 0.05 mol to
It is about 0.3 mol / liter. The general formula [F
Two or more compounds of the formulas I], [FII] and [FIII] may be used. Is most preferred.

In the present invention, a particularly preferred embodiment of the transparentizing treatment is a treatment using a fixing treatment sheet or a bleach-fixing treatment sheet. Hereinafter, this embodiment will be described, except that the fixing treatment sheet does not contain a bleaching agent,
Since the sheet is substantially the same as the fixing sheet, the bleach-fixing sheet will be described. Further, since the processed web in which the sheet is in the form of a roll film has no functional difference except for the difference in shape, the following description includes the fixing processed web and the bleach-fixed processed web.

In the present invention, the processing layer of the processing member of the bleach-fix processing sheet preferably uses a water-soluble polymer as a binder. Examples thereof include page 27 of Research Disclosure 17643, page 651 of JP 18716, pages 873 to 874 of JP 307105 and JP-A 64-1.
No. 3,546, pp. 71-75. Among them, gelatin and a combination of gelatin and another water-soluble binder (for example, polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivative, acrylamide polymer, etc.) are preferable. The bleach-fixed sheet is preferably hardened with a hardener.
Examples of hardeners include U.S. Pat. No. 4,678,739, column 41, 4,791,042, and JP-A-59-11.
6,655, 62-245,261, 61-1
And hardeners described in JP-A-8-942 and JP-A-4-218,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners,
Epoxy hardener, vinyl sulfone hardener (N, N '
-Ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid, or polymer hardeners (JP-A-62-234157) Described compounds). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g per 1 g of the hydrophilic binder.
g is used.

The bleach-fixing sheet may have a protective layer, an undercoat layer, a back layer, and various other auxiliary layers.
Further, the bleach-fixing processing sheet preferably has a processing layer provided on a continuous web. As used herein, the term "continuous web" means that the length of the bleach-fixing sheet is sufficiently longer than the long side of the photosensitive material to be processed by the processing member of the present invention corresponding to the bleach-fixing process, and is used for the bleach-fixing process. A form in which a part of the photosensitive material is sometimes used without being cut, and has a length capable of continuously processing a plurality of photosensitive materials. Generally, the length of the bleach-fixing sheet is not less than 5 times the width and not more than 10,000.
Means less than double. The width of the bleach-fixing sheet is optional, but is preferably equal to or greater than the width of the corresponding photosensitive material.

The thickness of the support used in the bleach-fixing sheet is not limited, but is preferably thin, particularly preferably 4 μm or more and 120 μm or less. It is particularly preferable that the thickness of the support is 40 μm or less. In this case, the amount of the bleach-fixed sheet per unit volume is increased, so that the roll of the bleach-fixed sheet can be made compact. As the support, a support that is transparent and can withstand the processing temperature is used. In general, papers and synthetic polymers (films) described on pages 223 to 240 of the Photographic Society of Japan, "Basics of Photographic Engineering-Silver salt photography-", published by Corona Co., Ltd. (1979) And photographic supports. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose).
In the case of copolymerization, those obtained by copolymerizing units such as terephthalic acid, bisphenol A, and cyclohexanedimethanol in addition to the naphthalenedicarboxylic acid unit and the ethylene glycol unit are also preferable. Preferred partners for the polymer blend include polyesters such as polyethylene terephthalate (PET), polyarylate (PAr), polycarbonate (PC), and polycyclohexanedimethanol terephthalate (PCT) from the viewpoint of compatibility.

After the bleach-fixing process, the light-sensitive material is peeled off from the bleach-fixing member of the present invention and dried directly or by drying.
Image information reading is performed. Examples of the method of superposing the bleach-fix processing sheet on the photosensitive material after the development processing are described in JP-A-62-253,159 and JP-A-61-147,2.
There is a method described in No. 44.

4. Image reading, image processing including conversion to digital image information Image reading applied to the present invention may be in any form as long as the image information of the three photosensitive layers of the film can be read. The following forms are preferred. Transmitted light reading The image information stored in each photosensitive layer of the photosensitive material is read by transmitted light, and the image information stored in each photosensitive layer is obtained based on the image information by the transmitted light. Reflection reading Image information stored in the front and back side photosensitive layers of the photosensitive material is read by reflected light, and image information stored in all photosensitive layers is obtained based on the image information by reflected light. Transmission / reflection reading This is a combination of the transmission reading and reflection reading. In this case, 1) a method of obtaining image information stored on the front and back sides of the photosensitive material by two reflection readings and obtaining image information stored in the intermediate layer of the photosensitive material by one transmission reading, 2 There is a method of obtaining image information stored on one of the front and back sides by one reflection reading and obtaining image information stored in another photosensitive layer of the photosensitive material by two transmission readings. Among them, 1) is applicable to black-and-white development and color development. In particular, in the case of color development, image information stored in the intermediate layer is read by setting the wavelength in the intermediate layer of the photosensitive material. 2) is particularly applicable to color development, and the wavelength is set such that each of the two transmission readings reads image information stored in a photosensitive layer other than the photosensitive layer obtained by reflection reading. read. In this case, in the reflection reading, when image information (for example, red) carried by the photosensitive layer on the support side of the photosensitive material is read,
In the first transmission reading, the wavelength of the light source is set so as to read the image information (blue) carried on the photosensitive layer located on the front side, and in the second transmission reading, the wavelength is held on the photosensitive layer located in the middle. The wavelength of the light source is set so as to read the image information (green). Alternatively, in reflection reading, image information carried by the photosensitive layer on the front side of the photosensitive material (for example, blue)
In the first transmission reading, the wavelength of the light source is set so as to read the image information (red) carried on the photosensitive layer located on the side of the support in the first transmission reading, and in the second transmission reading, the photosensitive position located in the middle is read. Image information carried on layer (green)
Set the wavelength of the light source to read. The above reflection reading and transmission reading can be performed by the following methods. That is, a line CCD in which light receiving elements are arranged one-dimensionally.
A line CCD-scanning method in which the density of an image is read while sub-scanning the image on the developed film and converted into an electric signal by a line CCD, and a two-dimensional image density using an area CCD is used. Read area C
An area CCD system in which electric signals are converted into electric signals rearranged in time series by electric scanning from a CD can be adopted.

Hereinafter, an example in which the image information reading unit 114 shown in FIG. 1 is transparently read and constituted by an area CCD will be described. FIG. 3 shows a schematic configuration of the image information reading unit 114. As shown in FIG. 3, the image information reading unit 114 is configured to irradiate the film F with light and detect the light transmitted through the film, so that a color image can be read photoelectrically. A light source 31 disposed on the back side, a reflection mirror 32 for reflecting light emitted from the light source 31 and transmitted through the film F, a light amount adjustment unit 34 capable of adjusting a light amount, a CCD area sensor 35 for photoelectrically detecting transmitted light, It has a lens 36 that forms an image of the transmitted light on the area sensor. In addition, the light source 31 may be arranged on the front side of the film F to detect light transmitted from the front side.

The digital image information obtained by the image information reading section 114 is supplied to the image processing section 120. The image processing unit 120 is an amplifier 3 that amplifies a generated image signal that is photoelectrically detected by the CCD area sensor 35.
7. A / D converter 38 for digitizing an image signal,
CCD for subjecting a signal digitized by the D converter 38 to correction processing for variations in sensitivity and dark current for each pixel
A correction means 39, a log converter 40 for converting image data into density data, and an interface 41,
Controlled by U46.

In the area CCD in the image information reading section 114, a plurality of pixels for detecting light are arranged in a plane along the longitudinal direction and the width direction of the film F, and all pixels are charged according to the light received. Has the function of storing frame images, and can electrically read a frame image (two-dimensional). Although the description has been mainly focused on the area CCD, the area CCD can be replaced with a line CCD instead of the area CCD. Line CCD
A plurality of pixels for detecting light are linearly arranged along the width direction of the film F, and have a function of accumulating electric charges in accordance with light received by the line pixels. Is read electrically.

The light source applicable to the image information reading section 114 is preferably infrared light or laser light. The wavelength of the infrared light is from 800 nm to 1200 nm, preferably from 850 nm to 1100 nm.

The image information read by the image information reading unit 114 is input to the image generation unit. Although the detailed description of the image generation unit is omitted, based on the obtained image information,
The image information (R, G, B) stored in the photosensitive material is individually generated by weighting with a predetermined coefficient by a known linear conversion and then adding them together. The digital image data of each color obtained by the image generation unit is output to the digital image processing unit 70.

FIG. 4 shows a schematic configuration of the digital image processing section 70. The digital image processing unit 70 is capable of inputting image data obtained by photographing with a digital camera 71 or the like. The digital image processing unit 70 is capable of inputting image data obtained by reading a transparent original, a reflective original, or the like with a scanner 72, or a computer or the like. Thereafter, the floppy disk drive 73, the MO drive or the CD drive 74 is stored in the recording medium.
And image data (image file data) input through communication via the modem 75 and the like.

The digital image processing section 70 stores the input digital image data in the memory 76, and performs image processing such as various corrections in the color gradation processing section 77, the hyper processing section 78, the hyper sharpness processing section 79, and the like. Then, the image data is output to a printer (not shown) as recording image data. Even if the image quality of the original image developed by this image operation or the read image is inferior, the image correction of gradation and saturation is performed. The digital image processing unit 70 stores the image data on which the digital image processing has been performed as image file data in a storage medium (for example, FD, MO, CD) and outputs the same to the outside, or to the outside via a communication line. It is also possible to output.

Further, a keyboard 70K is used as an input device.
And a monitor 70M. While viewing the display on the monitor 70M, an image can be captured by the key operation of the keyboard 70K and various image processing can be performed.

5. Photosensitive Material Used in the Present Invention and Supplementary Explanation Related thereto (1) Photosensitive Material The photosensitive material used in the present invention is a color photograph for photography generally used in the photographic market as described above in relation to the object and background of the invention. This is a photosensitive material having at least one photosensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting the above-mentioned silver halide light-sensitive layer comprise two layers, a high-speed emulsion layer and a low-speed emulsion layer, which are directed toward a support. It is preferable to arrange them so that the sensitivities become lower sequentially. Also, JP-A-57-112751, 62-200350, and
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support and a high-sensitivity emulsion layer may be provided on the side near the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokuaki Akira
As described in JP-A-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support. Others
High-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification of JP-A-63-89850, adjacent to or adjacent to the main photosensitive layer. .

A preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

Examples of the silver halide photographic emulsion usable in the present invention include, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 18716 (November 1979), p. 648, pp. 307105 (1989
Nov., pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimi)
e et Phisique Photographiques, Paul Montel, 1967)
, Duffin, Photographic Emulsion Chemistry, Published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, F
ocal Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman, et.
al., Making and Coating Photographic Emulsion, Fo
cal Press, 1964). US 3,574,628, US 3,655,394 and GB
Monodisperse emulsions described in 1,413,748 are also preferred.

Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
ngineering), Vol. 14, pp. 248-257 (1970); US 4,43.
It can be easily prepared by the methods described in 4,226, 4,414,310, 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. Although the thickness of the shell of this emulsion varies depending on the development processing and the like, it is preferably 3 to 40 nm, and 5 to 40 nm.
-20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the color photographic light-sensitive material used in the present invention, two or more kinds of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are contained in the same layer. Can be used as a mixture. U.S. Pat.No.4,082,553.
98. Applying internally fogged silver halide grains and colloidal silver described in JP-A-59-214852 to a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer Is preferred. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of the unexposed portions and exposed portions of the photosensitive material. , Its preparation method is US
4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. The average grain size of these fogged silver halide grains is 0.
It is preferably from 01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. Also,
The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferred that

It is preferable to use non-light-sensitive fine grain silver halide for the color light-sensitive material. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . Fine grain silver halide
The content of silver bromide is from 0 to 100 mol%, and it may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.
Is more preferred. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains.

[0130] The silver coating amount of the color light-sensitive material used in the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred. Photographic additives that can be used in color photographic materials are also RD
And the relevant places in the following table are shown.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column pages 876-877 Inhibitors 10. Matsuto 878-879.

Various dye-forming couplers can be used in the color light-sensitive material, and the following couplers are particularly preferred. Yellow couplers: couplers represented by formulas (I) and (II) in EP 502,424A; couplers represented by formulas (1) and (2) in EP 513,496A (especially Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the general formula (I) in column 1, lines 45 to 55 of US 5,066,576; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); Couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) in columns 7, 36 to 58 of column 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257, A-4 -63 (p. 134), A-4 -73, -75 (p. 139); EP 486,
965 M-4, -6 (p. 26), M-7 (p. 27); EP 571, 959A M-45 (19
(M page) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-36631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); JP-A-4-43345, C-7,10 (page 35), 3
4, 35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1.

Polymer coupler: P-1, described in JP-A-2-44345
P-5 (page 11). As couplers in which the coloring dye has an appropriate diffusivity, US
4,366,237, GB 2,125,570, EP 96,873B, DE 3,234,533
Are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are represented by the formula (C) described on page 5 of EP 456,257A1.
I), (CII), (CIII), (CIV) represented by yellow colored cyan coupler (especially YC-86 on page 84), yellow colored magenta coupler ExM-7 (page 202) described in the EP, EX- 1 (2
49), EX-7 (page 251), Magenta colored cyan coupler CC-9 (column 8) and CC-13 (column 10) described in US 4,833,069, (2) (column 8) of US 4,837,136, WO92 / Colorless masking couplers of formula (A) of claim 1 of 11575 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of the coupler releasing a photographically useful group include the following. Development inhibitor releasing compound:
Compounds of the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 4
Compounds represented by formula (I) described on page 7 of 36,938A2 (especially D-49 (page 51)), compounds represented by formula (1) of EP 568,037A (especially (23) (page 11)), Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly, (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; fluorescent dye releasing compound: of claim 1 of US 4,774,181
Compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
Compounds represented by the formulas (1), (2) and (3) in column 3 of 4,656,123 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only after leaving: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

The following are preferred as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex according to No. 363; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 2, 54 to 62 of US Pat. No. 4,978,606 (especially I-, (1), (2), (6), (12 ) (Column 4 ~
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; formalin scavenger: SCV-1 to 28 on pages 24 to 29 of EP 477932A, especially SCV-8; hardener: JP-A 1-214845
Formula of columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
Compound represented by the formula (6) at the lower right of page 8 of 214852 (H-1 to 7
6), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursor: P-2 of JP-A-62-168139
No. 4,37,39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
3 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13), U
Compounds 1-65 of columns 25-32 of S 4,952,483, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
Page a-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Page V-1 to 23, especially V-1, EP 445627A, page 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, 17 to 28 of EP 457153A
Pages III-1 to 36, especially III-1,3, WO 88/04794
Microcrystal dispersion of Dye-1 to 124, Compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular Compounds D-1 to 87 (3) of Compound 1, EP 519306A represented by formulas (1) to (3) ~ 28 pages), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, and color positive films. Is suitable for the purpose of the invention. Further, application to a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784 is also suitable.

Suitable supports that can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, RD. No. 18716, page 647 right column to page 648 left column, and RD. No. 307105, page 879. It is described in.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and more preferably 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach half when 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes 15 seconds is the saturated film thickness. Is defined.
The film thickness refers to a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days), and T _1/2 is a value obtained by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129, which can be used for measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness.

The color light-sensitive material used in the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) of m. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The development processing of the color light-sensitive material is described above. In addition, see RD.
No. 18716, 651 left column to right column, and No. 307105, 880
88881.

In the present invention, the desilvering process is not necessary. However, when the developed film is to be preserved, the developed color negative is developed by carrying out ordinary desilvering and washing or stabilization after reading the second image. A film can be obtained. The desilvering process is performed using a bleaching solution and a fixing solution, or a bleach-fixing solution. The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 are applied to the processing solution having bleaching ability (bleaching solution or bleach-fixing solution). Can be. The bleach has a redox potential of 1
Although those having 50 mV or more are preferable, specific examples thereof include those described in JP-A-5-72694 and JP-A-5-73312, and in particular, 1,3-diaminopropanetetraacetic acid, JP-A-5-133313, page 7 Ferric complex salts of the compounds of Example 1 are preferred.

In order to improve the biodegradability of the bleaching agent, JP-A-4-218845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a solution having bleaching ability.
It is preferred to design with a mole to 0.15 mole. When the bleaching liquid is a bleaching liquid, 0.2 mol to 1 mol / L is used.
It is preferred to contain mole bromide, especially 0.3 to
It is preferable to contain 0.8 mol.

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat. Compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of JP-A-4-125558 can be applied to a processing solution having a fixing ability. In addition to the use of p-toluenesulfinic acid salts, the use of sulfinic acids described in JP-A-1-224762 is also preferable from the viewpoint of improving the preservation. It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property, but it is more preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .

In the bleach-fixing solution and the fixing solution, it is preferable to use a free chelating agent which is not a metal complex from the viewpoint of improvement of preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used. Regarding the washing and stabilizing steps, the contents described in JP-A-4-125558, page 12, right lower column, line 6 to page 13, right lower column, line 16 can be preferably applied. In particular, EP instead of formaldehyde is used in the stabilizer.
Use of azolylmethylamines described in 504,609 and 519,190 and N-methylolazoles described in JP-A-4-362943, and use of an interface free from image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment.

In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used. As the treating agent used in the present invention, those described in the right column of page 3, line 15 to the left column of page 4, line 32 of Hatsumei Kyokai Kokai Giho No. 94-4992 are preferable. As a developing machine used for this, a film processor described in the above-mentioned published technical report on page 3, right column, lines 22 to 28 is preferable. A preferred treating agent for practicing the present invention,
Specific examples of the automatic developing machine and the evaporation correction method are described in the above-mentioned published technical report from page 5, right column, line 11 to page 7, right column, last line.

The supply form of the developer, the clarifying processing agent, and the processing agent for desilvering and stabilizing used as needed in the present invention may be in the form of a liquid in a used liquid state or in a concentrated form, or in the form of granules. , Powders, tablets, pastes, emulsions and the like. Examples of such treating agents include JP-A-63-17453, Japanese Patent Application Laid-Open No. 4-19655, JP-A-4-19748, and Vacuum-packaged powder or granules, JP-A-4-230748. 221951 discloses a granule containing a water-soluble polymer, JP-A-51-61837 and JP-A-6-102628 disclose a tablet, and JP-A-57-500485 discloses a paste-like treating agent. Although it can be used, it is preferable to use a liquid which has been prepared in advance in a concentration in a used state from the viewpoint of simplicity at the time of use.

The containers for storing these treating agents are made of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, or the like, alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 200 mL / m ² · 24 hrs.

The color light-sensitive material used in the present invention often has a magnetic recording layer. The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support. The magnetic particles include ferromagnetic iron oxide such as γFe ₂ O ₃ , Co-coated γFe ₂ O ₃ , Co
Deposited magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. The magnetic recording layer and other backing layers may have functions such as improvement of lubricity, curl control, antistatic, antiadhesion, and head polishing. It is preferable to add non-spherical inorganic particles to the composition. Suitable particle compositions include oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, silicon carbide, silicon carbide, carbides such as titanium carbide, and diamond. And the like are preferred. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US 5,336,589, US 5,250,404, US 5,229,2
59, 5,215,874 and EP 466,130.

Next, a polyester support, which is a preferred support used in the color light-sensitive material of the present invention, will be described. For details including photosensitive materials, treatments, cartridges and examples to be described later, refer to published technical bulletins and official publications. Technique number 94-6023
(Invention Society; March 15, 1994.). In the present invention, heating and drying are performed after the first image is read upward. However, since rapid and strong drying is desirable, a polyester support sufficiently stable to the heating temperature is preferable. Polyester is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, as aromatic dicarboxylic acid.
1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A as a diol;
Bisphenol is mentioned. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 50 mol% of 2,6-naphthalenedicarboxylic acid to 1 mol%.
It is a polyester containing 00 mol%. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher. The polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours or more 15
The time is 00 hours or less, more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Irregularities may be provided on the surface (for example, conductive inorganic fine particles such as tin oxide or antimony oxide may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping, Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku
The purpose can be achieved by kneading a commercially available dye or pigment for polyester.

In the present invention, in order to adhere the support and the light-sensitive material constituting layer, it is preferable to perform a surface treatment after applying an undercoat layer or directly. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, preferred are ultraviolet irradiation treatments,
Flame treatment, corona treatment and glow treatment. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, and active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) And the like, epichlorohydrin resin, active vinyl sulfone compound and the like. Silicon dioxide,
Inorganic fine particles such as titanium dioxide and alumina or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent. In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds.

The most preferred antistatic agent is at least one type of volume resistance selected from zinc oxide, silicon dioxide, titanium dioxide, alumina, indium oxide, magnesium oxide, barium oxide, manganese oxide and vanadium oxide. Rate is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω
-Cm1 or less particle size 0.001-1.0 μm crystalline metal oxides or their composite oxides (Sb, P, B, In, S, Si,
C) and fine particles of a sol-shaped metal oxide or a composite oxide thereof. The addition amount to the photographic material, 5 to 500 mg / m ² is preferably particularly preferably 10 to 35
It is 0mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide and the binder is preferably from 1/300 to 100/1,
More preferably, it is 1/100 to 100/5.

It is preferable that the color light-sensitive material has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the product was conveyed at 60 cm / min to a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane. And polymethylphenylsiloxane. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The color photographic material preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
Methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrower.
It is preferable that 90% or more of the total number of particles be contained between 0.9 and 1.1 times. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)),
Polystyrene particles (0.25 μm), colloidal silica (0.
03 μm).

Next, the film cartridge of the color photographic material used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, carbon black, metal oxide particles,
Nonionic, anionic, cationic and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537 and JP-A 1-312537.
312538. Especially resistance at 25 ℃ and 25% RH
It is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties. The size of the patrone may be the same as the current 135 size, and it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g. Further, the patrone may be a patrone that rotates a spool and sends out a film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613.
The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, the raw film and the developed photographic film may be stored in the same new cartridge or different cartridges.

The color photographic light-sensitive material used in the present invention is also suitable as a negative film for an advanced photo system (hereinafter, referred to as an APS system), and is processed into an APS system format and stored in a special cartridge. Can be. These APS system cartridge films are used by loading them into APS system cameras. Further, the color photographic light-sensitive material of the present invention,
This is a Fujicolor photo run made by Fujifilm. It is also suitable for films with lenses such as Super Slim.

As these print systems, for example, Fujifilm Digital Lab System Frontier Series is preferable. In the frontier system, scanner & image processor SP-1000 and laser printer & paper processor LP-1000P or laser printer LP-1000 are used.

The APS system can also be enjoyed on a digital image workstation. For example, you can directly load a developed APS system cartridge film into a digital image workstation, or transfer image information from negative film, positive film, and print to a 35 mm film scanner FE-550 or flat head scanner PE-550.
And the obtained digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL based on a light fixing type thermal color print system, a pictography 3000 based on a laser exposure heat development transfer system, or through an existing laboratory device through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is transferred to a Fujifilm photo player AP.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To enter a film, print, or three-dimensional object into a computer, use Fujifilm PhotoVision FV-10 / FV.
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable. To store the developed AP system cartridge film, use Fuji Color Pocket Album AP-5 POP L,
AP-1 POP L, AP-1 POP KG or cartridge file 16 is preferred.

[0160]

[Example 1]

1. Tested color negative film <Preparation of emulsion> (Preparation of Em-A) An aqueous solution 120 containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, 1.0 g of KBr and 1.0 g of KBr
0 milliliters (hereinafter referred to as “mL”) is 35
C. and stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of AgNO ₃ , 1.5 g of KBr and a molecular weight of 15,000
30 g of an aqueous solution containing 0.7 g of low-molecular-weight gelatin was added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. KBr
Was added, and the mixture was heated to 75 ° C. and aged. After aging,
35 g of succinated gelatin was added. The pH was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was -2 with respect to the saturated calomel electrode.
It was kept at 5 mV. Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added over a period of 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, Ag with a size of 0.03 μm
The I fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at -25 mV. 132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by the double jet method. KBr so that the potential at the end of the addition becomes -20 mV.
The addition of the aqueous solution was adjusted. After the temperature was adjusted to 40 ° C., 5.6 g of Compound 1 in terms of KI was added, and 64 cc of a 0.8 M aqueous sodium sulfite solution was further added. Furthermore, Na
The pH was raised to 9.0 by adding an aqueous OH solution and maintained for 4 minutes to rapidly generate iodide ions.
Returned to 5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of the addition, an aqueous solution 25 containing 70 g of AgNO ₃
0 mL and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the mixture was adjusted to pH 5.8 and pAg 8.7 at 40 ° C.

[0161]

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The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively.

The temperature of the above emulsion was raised to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added thereto in terms of Ag and shelled. Next, sensitizing dyes 1, 2, 3
In the form of a solid fine dispersion,
5.85 × 10 ^-4 mol, 3.06 × 10 ^-4 mol, 9.0
0 × 10 ^-6 mol was added. As shown in Table 1, the inorganic salt was dissolved in ion-exchanged water, and then a sensitizing dye was added.
By dispersing at 0 rpm for 20 minutes, sensitizing dye 1,
A few solid fine dispersions were made. When the sensitizing dye is added and the adsorption of the sensitizing dye reaches 90% of the adsorption amount in the equilibrium state, the calcium nitrate is reduced to a calcium concentration of 250 ppm.
Was added so that The amount of sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation, measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and adsorbing the sensitizing dye. The amount of dye was determined. After addition of calcium nitrate, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N,
N-dimethylselenourea and Compound 4 were added for optimal chemical sensitization. N, N-dimethylselenourea was added in an amount of 3.40 × 10 ⁻⁶ mol per mol of silver. At the end of the chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-A.

[0164]

[Table 1]

[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g, and the succinated gelatin was converted to a trimellitization ratio of 98,000 having a molecular weight of 100,000 containing 35 μmol methionine per gram.
% Of trimellitated gelatin, compound 1 is replaced with compound 6, and the amount of compound 6 added is 8.
The amount of the sensitizing dye added before chemical sensitization was changed to 6.50 × 10 ^-4 mol, 3.40 × 10 ^-4 mol, and 1.40 × 10 ^-4 mol, respectively, with respect to sensitizing dyes 1, 2, and 3, respectively. Em-B in the same manner as Em-A except that the amount was changed to 00 × 10 ⁻⁵ mol and the amount of N, N-dimethylselenourea added during chemical sensitization was changed to 4.00 × 10 ⁻⁶ mol. Was prepared.

[0172]

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g, and the succinated gelatin was converted to a phthalated phthalate having a molecular weight of 100,000 containing 35 μmol methionine per gram. 97
% Phthalated gelatin and compound 1 was replaced with compound 7
And the amount of compound 7 added was changed to 7.1 g in terms of KI, and the amount of sensitizing dye added before chemical sensitization was 7.80 × 10 ^{− with} respect to sensitizing dyes 1, 2, and 3, respectively. ⁴ moles,
Except that the amounts were changed to 4.08 × 10 ⁻⁴ mol and 1.20 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization was changed to 5.00 × 10 ⁻⁶ mol. Is E
Em-C was prepared in the same manner as mA.

[0174]

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(Preparation of Em-E)
Water containing 1.0 g of low molecular weight gelatin and 1.0 g of KBr
The liquid (1200 mL) was kept at 35 ° C. and stirred vigorously. Ag
NO _Three30 mL of an aqueous solution containing 1.9 g, 1.5 g of KBr
And 0.7 g of low molecular weight gelatin having a molecular weight of 15,000
30 mL of the aqueous solution is applied for 30 seconds by the double jet method.
Nucleation was performed by addition. At this time, the excess concentration of KBr is reduced to one.
Kept constant. Add 6 g of KBr, heat to 75 ° C and ripen
did. After aging, 15 g of succinated gelatin, and
20 g of the above-mentioned trimellitated gelatin was added. pH
Was adjusted to 5.5. AgNO_ThreeAqueous solution 1 containing 30 g
50mL and KBr aqueous solution for 16 minutes by double jet method
Over a period of time. At this time, the silver potential is changed to a saturated calomel electrode.
-25 mV. Furthermore, AgNO_Three11
Aqueous solution containing 0 g and KBr aqueous solution by double jet method
Accelerate the flow rate so that the final flow rate is 1.2 times the initial flow rate
For 15 minutes. At this time, the size is 0.0
A 3 μm AgI fine grain emulsion was prepared with a silver iodide content of 3.8%.
At the same time to accelerate the addition and the silver potential
It was kept at -25 mV. AgNO_ThreeAqueous solution 1 containing 35 g
32mL and KBr aqueous solution in 7 minutes by double jet method
Added throughout. The potential at the end of the addition becomes -20 mV
The addition of the aqueous KBr solution was adjusted as described above. Add KBr
After adjusting the potential to -60 mV, the benzenethiosulfone
1 mg of sodium acid was added,
13 g of 1 ppm lime-processed gelatin was added. End of addition
After that, a low molecular weight gelatin aqueous solution having a molecular weight of 15,000 and A
gNO_ThreeAn aqueous solution and a KI aqueous solution are disclosed in JP-A-10-43570.
Having a magnetic coupling induction stirrer as described in
Particle size prepared by premixing just before addition in the chamber
(Equivalent sphere diameter) 0.008 μm AgI fine grain emulsion
While continuously adding 8.0 g in conversion, AgNO_Three70g
250 mL of an aqueous solution containing
It was added over 20 minutes while maintaining 0 mV. This and
And the yellow blood salt was added in an amount of 1.0 × 10 ^-FiveMolar addition
did. After washing with water, lime treatment with calcium concentration of 1 ppm
Add 80 g of gelatin, pH 5.8 at 40 ° C., pAg
Adjusted to 8.7.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy, and was 15 ppm, 2 ppm and 1 ppm, respectively.
ppm.

In the chemical sensitization, sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount was 7.73.
× 10 ^-4 mol, 1.65 × 10 ^-4 mol, 6.20 × 10
Em-E was prepared by performing chemical sensitization in the same manner as Em-A except that the amount was changed to ^-5 mol.

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[0179]

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[0180]

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(Preparation of Em-F)
Water containing 1.0 g of low molecular weight gelatin and 1.0 g of KBr
The liquid (1200 mL) was kept at 35 ° C. and stirred vigorously. Ag
NO _Three30 mL of an aqueous solution containing 1.9 g, 1.5 g of KBr
And 0.7 g of low molecular weight gelatin having a molecular weight of 15,000
30 mL of the aqueous solution is applied for 30 seconds by the double jet method.
Nucleation was performed by addition. At this time, the excess concentration of KBr is reduced to one.
Kept constant. Add 5 g of KBr, heat to 75 ° C and ripen
did. After ripening, succinated gelatin 20g and phthalated
15 g of gelatin was added. The pH was adjusted to 5.5.
AgNO_Three150mL aqueous solution containing 30g and KBr aqueous solution
The liquid was added by the double jet method over 16 minutes. This
, The silver potential is set to -25 mV with respect to the saturated calomel electrode.
Kept. Furthermore, AgNO_ThreeAn aqueous solution containing 110 g and K
The final flow rate of Br aqueous solution is the initial flow rate by the double jet method.
Accelerate the flow rate to 1.2 times and add for 15 minutes
Added. At this time, AgI fine particles having a size of 0.03 μm
The emulsion was simultaneously run so that the silver iodide content was 3.8%.
The amount was accelerated and the silver potential was kept at -25 mV.
AgNO_Three132mL of aqueous solution containing 35g and KBr aqueous solution
The liquid was added by the double jet method over 7 minutes. KB
After adjusting the potential to −60 mV by adding an aqueous solution of
AgI fine grain emulsion with a size of 0.03 μm
9.2 g were added. Sodium benzenethiosulfonate
1 mg, and a calcium concentration of 1 ppm
13 g of ash-processed gelatin was added. After the addition is completed, AgN
O_Three250 mL of aqueous solution containing 70 g and KBr aqueous solution
Add over 20 minutes while maintaining the potential at 60 mV
Was. At this time, yellow blood salt was added in an amount of 1.0 × 10
^-FiveMole was added. After washing with water, calcium concentration 1ppm
80 g of lime-processed gelatin were added at 40 ° C. and pH5.
8, pAg was adjusted to 8.7.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy.
ppm.

For chemical sensitization, sensitizing dyes 1, 2, and 3 were replaced by sensitizing dyes 4, 5, and 6, and the added amount was 8.50 ×
10 ^-4 mol, 1.82 x 10 ^-4 mol, 6.82 x 10 ^-5
Chemical sensitization was carried out in the same manner as in Em-B except for using mol, to prepare Em-F.

(Preparation of Em-G)
Water containing 1.0 g of low molecular weight gelatin and 1.0 g of KBr
The liquid (1200 mL) was kept at 35 ° C. and stirred vigorously. Ag
NO _Three30 mL of an aqueous solution containing 1.9 g, 1.5 g of KBr
And 0.7 g of low molecular weight gelatin having a molecular weight of 15,000
30 mL of the aqueous solution is applied for 30 seconds by the double jet method.
Nucleation was performed by addition. At this time, the excess concentration of KBr is reduced to one.
Kept constant. 1.5 g of KBr was added, and the temperature was raised to 75 ° C.
Matured. After ripening, the above-mentioned trimellitized gelatin
15 g and 20 g of the above-mentioned phthalated gelatin were added. p
H was adjusted to 5.5. AgNO_ThreeWater containing 30g
150mL of KBr solution and 16 mL of KBr aqueous solution by double jet method
Added over minutes. At this time, the silver potential becomes saturated calomel.
It was kept at -25 mV with respect to the electrode. Furthermore, AgNO_Three
Double jet of aqueous solution containing 110 g and KBr aqueous solution
Flow rate so that the final flow rate is 1.2 times the initial flow rate.
Added rapidly over 15 minutes. At this time, the size
A 0.03 μm AgI fine grain emulsion having a silver iodide content of
At the same time, accelerate the flow rate so that it becomes 3.8% and add it.
The silver potential was kept at -25 mV. AgNO_Three, Including 35g
132mL aqueous solution and KBr aqueous solution by double jet method
For 7 minutes. The potential will be -60mV
The addition of the aqueous KBr solution was adjusted as described above. Size 0.03
7.1 g of a μm AgI fine grain emulsion was added in terms of KI.
Was. Add 1 mg of sodium benzenethiosulfonate
Lime-treated gelatin with a calcium concentration of 1 ppm
13 g was added. After the addition is completed, AgNO_Three70 g
Potential of 60 mL of aqueous solution containing 250 mL and KBr aqueous solution
V over 20 minutes. At this time,
1.0 × 10 5 per 1 mol of silver^-FiveMole added
Was. After washing with water, lime treatment
80 g of ratine was added, pH 5.8 at 40 ° C., pAg
Adjusted to 8.7.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy, and was 15 ppm, 2 ppm and 1 ppm, respectively.
ppm.

Sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6
Was changed to 1.00 × 10 ^-3 mol,
Em-G was prepared in the same manner as Em-C except that 2.15 × 10 ⁻⁴ mol and 8.06 × 10 ⁻⁵ mol were used.

(Preparation of Em-J) In the preparation of Em-B, sensitizing dyes added before chemical sensitization were sensitizing dyes 7 and 8.
Was changed to 7.65 × 10 ^-4 mol,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

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[0189]

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(Preparation of Em-L) (Preparation of Silver Bromide Emulsion) Average sphere equivalent diameter: 0.6 μm, aspect ratio: 9.
0, 1.16 mol of silver per kg of emulsion, gelatin 66
A silver bromide tabular emulsion containing g was prepared.

(Growth Process 1) Aqueous solution 1 containing 1.2 g of potassium bromide and succinated gelatin having a succinating rate of 98%
0.3 g of modified silicone oil was added to 250 g.
After the silver bromide tabular emulsion containing 0.086 mol of silver was added, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and the silver iodide fine particles having a particle size of 0.037 μm were added so as to be 5.4 mol with respect to silver to be added. Further, at this time, the pAg was 8.1 by double jetting the aqueous potassium bromide solution.
It was added while adjusting to be.

(Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and 2.5 mg of thiourea dioxide were added.

Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous solution of potassium bromide were accelerated by a double jet to obtain 66
Added over minutes. At this time, the silver iodide fine particles of 0.037 μm were added in a molar amount of 7.0 mol with respect to the added silver. At this time, the amount of potassium bromide in the double jet was adjusted so that the pAg became 8.1. After the addition,
2 mg of sodium benzenethiosulfonate were added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous solution of potassium bromide were added to each other by a double jet.
Added over 6 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9.

(Addition of sparingly soluble silver halide emulsion 4)
After adjusting the host grains to 9.3 with an aqueous potassium bromide solution, 25 g of the 0.037 μm silver iodide fine grain emulsion was used.
Was rapidly added within 20 seconds.

(Formation 5 of outermost shell layer)
An aqueous solution containing 9 g was added over 22 minutes.

This emulsion was tabular grains having an average aspect ratio of 9.8, an average equivalent sphere diameter of 1.4 μm, and an average silver iodide content of 5.5 mol.

[Chemical sensitization] After rinsing with water, the succination ratio was 9
Add 8% succinated gelatin and calcium nitrate and add 40%
PH was adjusted to 5.8 and pAg to 8.7 at ℃. The temperature was raised to 60 ° C., 5 × 10 ⁻³ mol of a 0.07 μm silver bromide fine grain emulsion was added, and sensitizing dyes 9, 10 and 11 were added 20 minutes later. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, compound 4
Was added for optimal chemical sensitization. Compound 3 was added 20 minutes before the end of the chemical sensitization, and Compound 5 was added at the end of the chemical sensitization. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are added in an amount of 10 ^-1 to 10 ^-8 per mol of silver halide so that the sensitivity at the time of exposure at 1/100 is maximized.
It means that it was selected from the range of addition amount of mol.

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[0202]

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was charged into a reaction vessel equipped with a stirrer, and the temperature of the solution was kept at 70 ° C. To this solution was added 276 mL of an aqueous solution of AgNO ₃ (containing 12.0 g of AgNO ₃ ) and an aqueous solution of KBr having an equimolar concentration while maintaining the pAg at 7.26 over 7 minutes by a controlled double jet addition method. Then, the temperature was reduced to 68 ° C, and thiourea dioxide (0.05
wt%) was added to 7.6 mL.

Subsequently, 592.9 mL of an AgNO ₃ aqueous solution
(Including 108.0 g of AgNO ₃ )
A mixed aqueous solution of r and KI (2.0 mol% KI) was added over 18 minutes and 30 seconds by a controlled double jet addition method while maintaining the pAg at 7.30. Five minutes before the end of the addition, 18.0 m of thiosulfonic acid (0.1 wt%) was added.
L was added.

The obtained grains were cubic grains having an equivalent sphere diameter of 0.19 μm and an average silver iodide content of 1.8 mol%.

Em-O was re-dispersed by subjecting it to desalting and washing with a usual flocculation method,
It adjusted to 6.2 and pAg7.6.

Subsequently, Em-O was subjected to the following spectral and chemical sensitization.

First, sensitizing dye 10, sensitizing dye 11, and sensitizing dye 12 were each added in an amount of 3.37 × 10 ^-4 per mol of silver.
Mol / mol, KBr 8.82 × 10 ^-4 mol / mol, sodium thiosulfate 8.83 × 10 ^-5 mol / mol, aqueous potassium thiocyanate 5.95 × 10 ^-4 mol / mol and potassium chloroaurate 3. Aging was performed at 68 ° C. by adding 07 × 10 ⁻⁵ mol / mol. The aging time is 1/10
The sensitivity was adjusted so that the 0 second exposure sensitivity was the highest.

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(Em-D, H, I, K, M, N) For the preparation of tabular grains, low molecular weight gelatin was used according to the examples of JP-A-1-158426. According to the examples of JP-A-3-237450, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dyes and sodium thiocyanate shown in Table 2. Emulsion D,
H, I, and K contain the optimum amounts of Ir and Fe. Emulsions M and N were prepared according to the examples in JP-A-2-191938.
Reduction sensitization has been performed at the time of grain preparation using thiourea dioxide and thiosulfonic acid.

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[Table 2]

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[0214]

[Table 3]

In Table 3, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

1) Support The support used in this example was:
Created by the following method.

1) First layer and undercoat layer: 90 μm thick
For the polyethylene naphthalate support, each of
On both sides, process atmosphere pressure 0.2 Torr, in atmosphere gas
H _TwoO partial pressure 75%, discharge frequency 30kHz, output 25
00W, processing intensity 0.5 kV · A · min / m^TwoGlow release
Electric treatment was performed. On this support, as a first layer, the following set
Bar coating method disclosed in JP-B-58-4589.
Using 5mL / m ^TwoWas applied at the application amount.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by weight 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene 0.1 parts by weight Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and was heat-treated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, heat-treated, and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method.

Gelatin 1.01 parts by weight Salicylic acid 0.30 parts by weight Resorcin 0.40 parts by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer, which will be described later, are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side to form a silver halide emulsion. A transparent magnetic recording medium with a layer was produced.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length:
0.25 μm, S _BET : 39 m ² / g, Hc: 831
Oe, σs: 77.1 emu / g, σr: 37.4 em
u / g) 1100 parts by weight, 220 parts by weight of water and 165 parts by weight of a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] are added, and the mixture is sufficiently treated with an open kneader for 3 hours. Kneaded. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again in an open kneader for 4 hours according to the following formulation.

The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2,000 rpm for 4 hours. did. As the medium, glass beads having a diameter of 1 mm were used.

The above kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, The mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion used in the present invention was prepared according to the following formulation.

(A) Sumicorundum AA-1.5 (average primary particle diameter 1.5 μm, specific surface area 1.3 m ² / g).

Preparation of Particle Dispersion Liquid Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / Cyclohexanone = 1/1).

With the above formulation, a ceramic-coated sand mill (1/4 G sand mill) was used at 800 rpm.
m for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used.

(B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used.

This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and has a solid content of 30%.

Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industries, Ltd.) Diluent 203 g (solid content 20%, diluent solvent: methyl ethyl ketone) / Cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g.

The coating solution obtained by mixing and stirring the above was applied by a wire bar so as to have an application amount of 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the dried magnetic layer was 1.0 μm.

3) Third layer (layer containing higher fatty acid ester slipping agent) Preparation of a stock solution of slipping agent
The mixture was heated and dissolved at ℃, added to the solution A, and dispersed with a high-pressure homogenizer to prepare a stock solution of a slip agent.

Solution A The following compound 399 parts by weight C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by weight nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 Parts by weight.

Liquid A Cyclohexanone 8600 parts by weight.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by weight Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by weight Compound 2-1 2.93 parts by weight

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Sea hosta KEP50 88.00 parts by weight (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring for 10 minutes with the above formulation, the following is further added.

252.93 parts by weight of diacetone alcohol.

While the above solution was cooled with ice and stirred, an ultrasonic homogenizer “SONIFIER450 (BRANSON) was used.
(Manufactured by Co., Ltd.) for 3 hours to obtain a spherical inorganic particle dispersion c1.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

XC99-A8808 (Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by weight Methyl ethyl ketone 120 parts by weight Cyclohexanone 120 parts by weight (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone) = 1/1).

While cooling with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
(2) for 2 hours to obtain a dispersion liquid c2 of spherical organic polymer particles.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%).

The above third layer coating solution was coated on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of photosensitive layer Next, on the side opposite to the back layer obtained above, layers having the following compositions were applied in a multilayer manner.
A color negative film was made.

(Composition of Photosensitive Layer) Main materials used for each layer are classified as follows; ExC:
Cyan coupler UV: UV absorber
ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H
: Gelatin hardener (specific compounds are described below, a numerical value is added after a symbol, and a chemical formula is listed after the symbol).

The number corresponding to each component indicates the coating amount in g / m ² , and the amount of silver halide indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver iodobromide emulsion Silver 0.01 Gelatin 0.919 ExC-1 0.002 ExC-3 0.002 Cpd -2 0.001 HBS-1 0.005 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 Solid Disperse Dye ExF-9 0.120 HBS-1 0.074.

Third layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-40 .121 ExC-5 0.010 ExC-6 0.007 Cpd-2 0.025 Cpd-4 0.025 Cpd-7 0.050 Cpd-8 0.050 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474.

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 Cpd-2 0.036 Cpd-4 0.028 Cpd-7 0.010 Cpd-8 0.010 HBS-1 0.129 Gelatin 1.086.

Fifth layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 Cpd-2 0.064 Cpd-40 077 Cpd-7 0.040 Cpd-8 0.040 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245.

Sixth layer (intermediate layer) Cpd-1 0.094 Cpd-9 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886.

Seventh Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Em-J Silver 0.293 Em-K Silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExY -1 0.016 ExY-6 0.036 Cpd-6 0.011 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610.

Eighth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Cpd-6 0.007 Gelatin 1.470.

Ninth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-1 0.007 ExC-6 010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Cpd-6 0.011 Cpd-7 0.010 Gelatin 0.446.

Tenth Layer (High Sensitive Green Sensitive Emulsion Layer) Em-E Silver 0.794 ExC-6 0.002 ExM-1 0.013 ExM-2 0.011 ExM-3 0.030 ExM-40 017 ExY-5 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 Cpd-7 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939.

Eleventh layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-7 0.010 HBS-1 0.049 Gelatin 0.630.

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExY-1 0.027 ExY-2 0.890 ExY-6 0.120 Cpd-2 0.100 Cpd-3 0.004 Cpd-6 0.009 HBS-1 0.222 HBS-5 0.074 Gelatin 2.058.

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.071 gelatin 0.678.

Fourteenth Layer (First Protective Layer) 0.07 μm Silver Iodobromide Emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 gelatin 1.984.

Fifteenth layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S- 10.20 Gelatin 0.750.

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-17, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye No. 11
The layer ExF-2 was dispersed in the following manner.

ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 011 kg Water 4.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition was roughly dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-9
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

The compounds used for forming each layer are shown below.

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[0281]

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[0282]

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[0283]

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[0284]

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The color negative photosensitive material prepared as described above is used as a sample 101.

The color negative film sample 101 prepared as described above was subjected to 240-25 according to the ISO1007 standard.
It was processed into the form of Ex (with 25 cartridges of patrone) APS and used.

[0288] 2. Development processing A. Test with Newly Prepared Processing Solution (1) Development Processing of Present Invention Example-1 As a development processing and image information reading apparatus of the present invention, application of a developing agent solution of a roller coat type shown in FIG. 2 and impregnation with an alkali agent were performed. A developing device combining the processed web and contact heating of a heating drum type was used. The rotation speed of the heating drum is 1 revolution per minute, so that the heating time during which the color film is in contact with the drum is 45 minutes.
Seconds. The surface temperature of the drum is 8
It has been adjusted to 5 ° C.

Therefore, the flow of the color film in this device is as follows. That is, the color film is sent out from the film loading chamber 200 in the direction of arrow A, and the photosensitive layer surface is indirectly connected to the roller for 5 seconds via the application roller half-immersed in the developing agent solution in the developing agent solution application section 206. After smear application is performed,
Heat is applied while rotating clockwise around the heating drum so that the surface of the impregnated layer of the alkali agent impregnated web and the surface of the photosensitive layer of the color film are in contact with each other. The film separated from the processing web by the peeling roller 175 is sent to the image reading unit along the transport path by the guide roller 177, and the image information is read. The apparatus shown in FIG. 2 can perform both reading with reflected light and reading with transmitted light, but in the present embodiment, the light source 211T
The reading was performed using a reading device 114 based on transmitted light, which is composed of a sensor 209T and a sensor 209T.

The developing agent solution and the alkaline agent solution of Example 1 of the present invention are viscous developers having the following compositions. (Developing agent solution) Prescription amount (g) Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 Sodium sulfite 3.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline Sulfate 20.0 Hydroxymethylcellulose 3.0 Add water 0.5 liter pH (adjusted with potassium hydroxide and sulfuric acid) 1.0 (Alkaline solution) Formulation amount (g) Diethylenetriaminepentaacetic acid 4.0 Hydroxylamine 7.0 Diethylene glycol 17.0 Potassium carbonate 59.0 Ethylene urea 5.5 Odor Potassium iodide 1.4 Hydroxymethylcellulose 3.0 Add water 0.5 liters pH (adjusted with potassium hydroxide and sulfuric acid) 12.0 Note that hydroxymethylcellulose is formulated in 10 ml of 10% NaOH aqueous solution for both the developing agent solution and alkaline solution. Do you mix well Was added.

(2) Comparative Example-1 The developer prepared by mixing the above-mentioned developer solution and alkali solution was filled in the developer solution application section 203 in FIG. A developing process was performed in the same manner as in Example 1 of the present invention except that a cover film was sent in place of the web and development was performed with a heating drum while covering a color film containing a developing solution to obtain digital image information. A color print was prepared, and this was designated as Comparative Example-1. (3) Comparative Example 2 Development processing was performed in the same manner as in Example 1 of the present invention, but instead of reading and using image information, a printer processor (PP-1257V, Fuji Photo Film Co., Ltd.) of a normal uniform surface exposure system was used. A color print was prepared using Comparative Example 2). (4) Reference Example (Example of Standard Development) Reference was made to show that the image quality obtained by the image forming method of the present invention is equivalent to the image quality obtained by general processing (standard processing) performed in the market. Development by the standard processing described above was also performed as an example. In the standard processing, development processing was performed according to the following color negative developing machine and processing specifications. That is, Fuji Photo Film Co., Ltd.
Using an automatic developing machine FP-363SC, the processing steps and the composition of the processing solution are as follows. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 10.3 liter Bleaching 50 seconds 38.0 ° C 5 ml 3.6 liters Fixed (1) 50 seconds 38.0 ° C-3.6 liters Fixed (2) 50 seconds 38.0 ° C 7.5 ml 3.6 liters Stable (1) 20 seconds 38.0 ° C-1.9 liters Stable (2) 20 seconds 38.0 ° C-1.9 liters Stable (3) 20 seconds 38.0 ° C 30 ml 1.9 liters Drying 1 min 30 sec 60 ° C. * the replenishing amount is the light-sensitive material 0.039M ² per.

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developer brought into the bleaching process,
The amount of the bleaching solution brought into the fixing step and the amount of the fixing solution brought into the washing step were 2.5 ml, 2.0 ml, and 2.0 ml, respectively, per 35 mm width 1.1 m of the light-sensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.4 0.5 Hydroxylamine 10.0 15.0 Sodium sulfite 4.0 9.0 Diethylene glycol 10.0 17.0 Potassium carbonate 39.0 59.0 Ethylene urea 3.0 5.5 Potassium bromide 1.4-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 11.4 Add water and add 1.0 liter 1.0 liter pH (with potassium hydroxide Adjusted with sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (g) Replenisher (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 128 180 Ammonium bromide 50 70 Succinic acid 30 50 Imidazole 20 30 Maleic acid 40 60 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.4 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium bisulfite (72% solution) 20 80 Aqueous ammonium thiosulfate (750 g / liter) 280 ml 1000 ml imidazole 5 45 2- (N, N-dimethyl) ) Ethylaminomercaptotetrazole 1.0 3.0 Ethylenediaminetetraacetic acid 8 12 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.0 7.0

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 p-Nonylphenoxypolyglycidol (Average degree of polymerization of glycidol 10) 0.4 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-Benzoisothiazolin-3-one 0.10 1.0 liter with water pH 8.5 Test with Processing Solution Aged In the above-mentioned present invention-1 and comparative example-1, after the development processing, the development processing apparatus was left for 5 days with the processing liquid filled, and the above-described test was performed using the same processing liquid. Repeated. This was designated as Invention-1 'and Comparative Example-1'. 3. Image Reading and Image Processing For the samples of the present invention example-1 and comparative example-1, image information obtained by performing image information reading is converted into a positive image by the digital image processing unit 70 described in FIG. Output.

In Example 1 of the present invention and Comparative example 1, the input image produced by the above-described configuration is converted into an electric image signal.
A high-speed scanner / image processing workstation SP-1500 (Fuji Photo Film Co., Ltd.) is an example of a commercially available input device that can generate a positive image by inputting the signal.
Laser Printer / Paper Processor LP-1500SC (Frontier 350, manufactured by Fuji Photo Film Co., Ltd.) was used as an example of a commercially available output device. Also, S
As for P-1500, the program software was changed so that the image processing could be performed. For the standard processing and Comparative Example-2, a minilab PP-1257V manufactured by Fuji Photo Film Co., Ltd., which is a general surface exposure method at present, was used. This system is equipped with a simultaneous full-exposure printer that prints through a processed color negative and prints on color paper, and is commonly used in the current market where color balance and print exposure are adjusted by controlling filters. It is a printer processor of the known type.

For printing of the developed films of Invention Examples-1 and 1 ', Comparative Examples-1 and 1' and 2, and Reference Example (standard processing), all were commercially available Fuji Color Paper SUPER FA Type D as color paper. The development was carried out using a general-purpose color paper processing prescription CP-48S and a processing agent (both manufactured by Fuji Photo Film Co., Ltd.).

[0299] 4. Method of photographic characteristics test Each test film was exposed to a standard C light source described in ISO 5800 (sensitivity measuring method for color negative film) and illuminated with standard exposure, half under exposure and four times over standard exposure. At three levels of exposure, a person was snap shot against a gray wall background, and the development processing conditions were changed as in the above-described examples of the present invention and each comparative example, using the above-described color paper and the printer processor. To obtain an image for evaluation. The overall image quality was evaluated by the five-point scale given below by 10 persons specializing in photographic evaluation, with an emphasis on the granular smoothness of the image for evaluation.

Very poor and unacceptable. ... 1 point Slightly inferior and unacceptable. ······ 2 points Relatively inferior, but acceptable. ··· 3 points Relatively excellent and preferable.・ ・ ・ ・ ・ 4 points Very good. ... 5 points

[0301] 5. Test Results Test with Newly Prepared Processing Solution As can be seen from Table 4, the development treatment is the method of the present invention, but the image of the color print of Comparative Example-2 obtained with the surface exposure type PP-1257V has low contrast. Was a poor image with low color density. Although the developing solution was not divided into a developing agent solution and an alkaline solution, it was used as a one-solution developer. In Comparative Example 1 in which image processing was added, good results were obtained with a fresh solution, but in Comparative Example 1, The image of Comparative Example-1 ′ developed with the solution after aging had a reduced density and deteriorated image. Inventive Example-1 in which the developing agent solution was supplied, and the resultant was superimposed on the alkali agent-impregnated processing web, heated and developed with a heating drum, and the image information was read to perform image processing was almost equivalent to the reference example of the standard processing. It was shown to have an image quality of
Further, the performance was maintained in Example 1 of the present invention treated with the developing agent solution and the alkali agent solution after 5 days of aging, and it was found that the ability could be sufficiently exerted even during light processing. The test results are shown in Table 4.

[0302]

[Table 4]

Example 2 (1) Invention Example-2 The color developing agent solution of Invention Example-1 in Example 1
Except that the alkaline agent solution processing / heating step was changed to the following black-and-white developing agent solution, alkali agent solution processing / heating step,
A test was conducted using the same color negative film sample, apparatus and method as in Inventive Example-1. The development treatment formula, temperature and time are as follows. (Black-and-white development step) Step Processing time Processing temperature Black-and-white development 20 seconds 90.0 ° C. The surface temperature of the heating drum is set to 90 ° C., and the rotation speed is set to 3 rotations per minute, so that the contact heating time of the film is 10 seconds. Set to. [Black-and-white developing agent solution] Prescription value Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g Sodium bisulfite 15 g Hydroquinone / potassium monosulfonate 30 g 1-phenyl-4-methyl-4-hydroxy Methyl-3-pyrazolidone 1.5 g Hydroxymethylcellulose 3.0 g Water was added to 0.5 liter pH (adjusted with potassium hydroxide and sulfuric acid) 2.0

[Alkaline agent solution] Prescription value Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g Potassium carbonate 20 g Potassium bicarbonate 12 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Hydroxymethyl cellulose 3.0 g Water was added and 0.5 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.60 In each of the above solutions, hydroxymethylcellulose was added after the formulation amount was sufficiently mixed with 10 ml of a 10% aqueous NaOH solution.

(2) Comparative Example-3 A black-and-white developing solution was prepared by mixing the black-and-white developing agent solution of the present invention example 2 and an alkaline solution (pH 10.0). Processed. (3) Comparative Example-4 The heating drum of the developing device with a heating drum in FIG.
And the rotation speed was set to one rotation in three minutes, the contact time of the film with the heating drum was 90 seconds, and the developing solution was a black-and-white developing solution. Developing, image reading and color printing were performed to obtain Comparative Example-4. Further, Invention-2 and Comparative Example-3
After being left for 3 days, it was reprocessed in the same manner as in Example-1.

After the processing is completed, the present invention example-2 and comparative example-3
Each of the samples 4 and 4 was evaluated for image quality in the same manner as in Example 1. The test results are shown in Table 5.

[0307]

[Table 5]

As shown in Table 5, the sample of Inventive Example-2 had sufficient image quality even with the passage of time with the same liquid as the reference example described in Table 4, while Comparative Example-3 Even when treated with the aged treatment liquid and in Comparative Example-4 with the new liquid, the evaluation results were unsatisfactory. Also, from the comparison between Inventive Example-1 using the color developing solution shown in Table 4 and Inventive Example-2 using the black-and-white developing solution in Table 5, the developing process is quicker when using the black-and-white developing solution. The use of the color developer for reading the dye image of Inventive Example-1 has higher image quality.

Example 3 (1) Invention Examples -3 to 12 In the invention example 1 of the example 1, the heat development time was set to 30.
After heat development, the following transparency treatment was performed before image reading.

[0310] The image layer of the color film and the transparentizing sheet were overlapped and heated at 70 ° C for 40 seconds. The sheet is provided with a gelatin layer obtained by adding 0.5% of a gelatin weight of 2,4-dichloro-6-hydroxy-1,3,5-triazine having a thickness of 20 μm to a PET film having a thickness of 80 μm so that the thickness at the time of swelling is increased. It is made to be a liquid film of 80 microns, and is previously impregnated with a clearing solution having the following composition to a saturated amount (immersion time: 6 minutes at 28 ° C.).

(Clearing treatment solution) (g) Ammonium methanesulfinate 20 Ammonium methanethiosulfonate 4 Aqueous solution of ammonium thiosulfate (700 g / L) 280 mL Fixing accelerator (see Table 5) 5 Ethylenediaminetetraacetic acid 15 Carboxymethylcellulose 2 Water 1.0 liter pH [adjusted with ammonia water and acetic acid] 7.4 Table 6 shows the test results.

[0312]

[Table 6]

As shown in Table 6, each of the samples of the present invention examples 4 to 13 which had been subjected to the clearing treatment was evaluated to be superior to the sample of the present invention example 3 and promoted the fixing to the clearing solution. The aspect of the present invention in which the agent is added contributes to speeding up of the clarifying process,
This shows that even when the speed is increased, a preferable result of preventing or improving the image quality is provided. From comparison with the reference examples in Table 4, it can be seen that each sample of Inventive Examples-4 to 13 has substantially the same image quality as when standard development is performed. The color prints obtained in this test were substantially equal to or more than the present invention example 1 even though the development time of the negative film was short.

[0314]

According to the present invention, a developing agent solution and an alkali agent solution are separately supplied to a photographed color film, heating is performed, image information is read after heat development, and red, blue, and green are read based on the read image information. 2) The method of the present invention for obtaining digital image information makes it possible to stabilize the development process over time, and at the same time, to obtain satisfactory image quality in terms of saturation (no color turbidity) and gradation. Images can be obtained. Further, by adding a transparency treatment after the heat development, the image quality is further improved. Further, the processing step is a development step only, and no processing agent for desilvering or stabilizing bath is required, which contributes to resource saving and environmental load reduction.

[Brief description of the drawings]

FIG. 1 is a block diagram schematically showing a flow of steps of a method of the present invention.

FIG. 2 is a schematic diagram of an image forming apparatus using a heating drum used in one embodiment of the image forming method of the present invention.

FIG. 3 is a block diagram schematically showing a configuration of an image information reading unit 114 shown in FIG.

FIG. 4 is a block diagram illustrating a configuration of a digital image processing unit.

[Explanation of symbols]

 F film 31 light source 32 mirror 34 light intensity adjustment unit 36 lens 35 CCD area sensor 37 amplifier 38 A / D converter 39 CCD correction means 40 log converter 41 interface 70 digital image processing unit 71 digital camera 72 scanner 73 floppy drive 74 MO ( CD) 75 Modem 76 Image memory 77 Color gradation processing unit 78 Hypertone processing unit 79 Hyper sharpness processing unit 110 Film processing and image reading unit 111 Developing unit 112 First image information reading unit 114 Second image information reading unit 177 Guide roller Reference Signs List 120 Image processing unit 170 Heating drum 175 Treated web peeling roller 178 Delivery roller 180 Treated web take-up roller 200 Film loading chamber 202 Fill Feed roller 203 film detector 206 developer solution applying unit 208 heat-development section 209T, 209RA, 209RB reading sensor 211T, 211RA, 211RB reading light sources

Claims (5)

[Claims] An image forming method for developing a photographed silver halide color photosensitive material, photoelectrically reading image information from an obtained image, and converting the read image information into electrical digital image information. (1) the developing solution used in the developing process is at least composed of a developing agent-containing solution having a pH of 7 or less and an alkali agent-containing solution;
A color image forming method, wherein the developing process is a developing process in which the developing agent-containing solution and the alkaline agent-containing solution are supplied to the photosensitive material, and then the photosensitive material supplied with the developing solution is heated. 2. The color image forming method according to claim 1, wherein the photographed silver halide color light-sensitive material has a support containing polyester as a main component. 3. The color image according to claim 1, wherein after the color light-sensitive material is developed, a transparency process is further performed, and image information is photoelectrically read from the obtained image. Forming method. 4. The color image forming method according to claim 1, wherein digital image information obtained by photoelectrically reading and converting the image is further subjected to image processing. 5. The color image forming method according to claim 1, wherein the developing agent contained in the developing agent-containing liquid is a color developing agent.