JPH09146247A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color print on a photographic photosensitive material which can be used for both of projection exposure and digital processing by an easy processing method. SOLUTION: A photosensitive material having at least three kinds of photosensitive layers on a supporting body is exposed to light for an image and developed to form a color image of at least three colors. The photosensitive layers contain at least photosensitive silver halide, binder, and dye-donating coupler and these layers have different spectral sensitivity region and hue of the dye produced by the dye-donating coupler from others. Then the image information is converted into optical or electric information without removing the silver halide or developed silver remaining on the photosensitive material. Then a color image is formed on another printing material according to the converted information.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for obtaining a color print from a photographic light-sensitive material.

[0002]

2. Description of the Related Art In a method known as conventional color photography, a color photosensitive material for photographing (so-called color negative) is usually a layer for recording blue light to form a yellow image, and a layer for recording green light to form a magenta image. And a layer for recording a red light to form a cyan image, the developing agent is oxidized in the process of reducing silver halide grains containing a latent image formed by exposure to silver during development processing. Then, a dye image is formed by a reaction (coupling reaction) between the oxidant and the dye-donating coupler. Undeveloped silver halide and developed silver are removed in the bleach-fixing step following the development processing step, the resulting negative dye image is projected and exposed on a color print light-sensitive material, and the same development and bleaching is performed on the color print material. A fixing process is performed to obtain a color print. Further, in so-called color negative photosensitive materials, colloidal silver and dyes for use as filters for making spectral sensitivity difference between three types of photosensitive layers, fine silver particles or dyes for antihalation are contained in the photosensitive materials. However, among these, metallic silver such as colloidal silver is removed in the bleaching process step. There is also known a method in which after image information contained in the color negative is photoelectrically read, image processing is performed to obtain image information for recording, and a color image is obtained on another print material by the image information. In particular, the development of a digital photo printer in which the above image information is converted into a digital signal, and a photosensitive material such as color paper is scanned and exposed by a recording light modulated in accordance with the digital signal to obtain a finished print is being developed. -15593
No. etc. When converting image information into a digital signal as described above, the underlying image information need not be a dye image in principle. For example EP526,931
JP-A-6-266066 describes a system in which one layer is composed of only a silver image, and JP-A-6-266066 describes a method of reading information of residual silver halide and developed silver without containing a coloring material in all three layers. ing.

In recent years, for the purpose of accelerating the development processing and reducing the influence of the processing waste liquid on the global environment, the color developing solution containing the developing agent is not used, but the color developing agent is incorporated in the light-sensitive material to provide an activator. A method called "processing" for carrying out development with a processing solution containing no developing agent is disclosed in JP-A-57-14939.
No. 7, JP-A-7-134355, JP-B-44-1867
No. 0 is proposed. For example, Japanese Patent Laid-Open No. 5-257225
JP-A No. 2000-242242 discloses a method in which a para-phenylenediamine derivative widely used as a color developing agent is incorporated in a stable form and is used as a so-called precursor which is activated during development processing for color development. Either method is a method of utilizing a dye image by removing developed silver and undeveloped silver halide by performing bleaching and fixing steps after color development processing.

On the other hand, as a method for processing a light-sensitive material using silver halide, a simple and rapid method using heat development has been disclosed. Examples of such products include dry silver manufactured by 3M, pictrography and pictrostat manufactured by Fuji Photo Film Co., Ltd. However, the former is a black-and-white light-sensitive material, and the latter is a color print material for transferring a dye from the light-sensitive material to an image receiving material. Further, a method of incorporating a color developing agent of a sulfonylhydrazone derivative into a light-sensitive material and utilizing a color developing dye produced by thermal development together with a silver image is described in US Pat. No. 4,430,420 and the like. It is a light-sensitive material, and a color light-sensitive material for photographing by heat development is not known.

[0005]

As described above, conventional color photographic processing methods are complicated, and a simpler method is desired, and it is necessary to dispose of a chemical solution used in the bleaching step and fixing step. Also, EP 526,931,
Although the method described in Japanese Patent Laid-Open No. 6-266066 is simplified in processing, it is premised on digital image processing, and direct projection exposure to color paper or the like cannot be performed as in the conventional method. Therefore, it is an object of the present invention to provide a novel method for obtaining a color print from a photographic light-sensitive material which can be used for both projection exposure and digital processing by using a simpler processing method.

[0006]

The above object has been achieved by the following means. (1) At least three types of light-sensitive materials containing at least a photosensitive silver halide, a binder, and a dye-donating coupler on a support, and having different light-sensitive wavelength regions and the hues of dyes formed from the dye-donating coupler. A light-sensitive material having a layer is subjected to imagewise exposure and development to form a color image of at least three colors, and then the image information is converted into optical information or electrical information without removing residual silver halide and developed silver. And an image forming method for obtaining a color image on another recording material based on the information.

(2) In the above (1), the support of the light-sensitive material is a transparent support, and the transmission density of the light-sensitive material at the maximum absorption wavelength of the dyes of three colors formed from the dye-donating coupler after development is , Dmin is 2.0 or less, Dmax is 4.0 or less, and Dmax-Dmin is 1.0 or more.

(3) On the support, at least a photosensitive silver halide, a binder, a dye-donor coupler, and a developing agent capable of reacting with the dye-donor coupler to form a dye are contained. After forming a color image of at least three colors by imagewise exposing and developing a light-sensitive material having at least three types of light-sensitive layers in which the hues of the dyes formed from the dye donor are different from each other, the remaining silver halide and development are performed. An image forming method in which the image information is converted into optical information or electrical information without removing silver, and a color image is obtained on another recording material based on the information.

(4) In the above (3), the support of the light-sensitive material is a transparent support, and the transmission density at the maximum absorption wavelength of the three color dyes formed from the dye-donating coupler after development has a Dmin of 2 0.0 or less, Dmax is 4.0 or less, and Dmax-
An image forming method using a light-sensitive material characterized in that Dmin is 1.0 or more, and the density of the dye is.

(5) On the support, at least a light-sensitive silver halide, a binder, a dye-donating coupler, and a developing agent capable of reacting with the dye-donating coupler to form a dye are contained. A light-sensitive material having at least three types of light-sensitive layers having different hues of dyes formed from the dye-donor and a layer containing a dye that is decolored or removed during development is subjected to at least imagewise exposure and development. After forming a three-color image, the image information is converted into optical information or electrical information without removing the remaining silver halide and developed silver, and a color is recorded on another recording material based on the information. An image forming method for obtaining an image.

(6) In the above (5), the development processing temperature is 6
An image forming method, characterized in that the image forming method is a heat development method at 0 ° C to 150 ° C.

(7) The image forming method according to the above (3), (5) or (6), characterized in that the photosensitive material is a photosensitive material for photography in which the support is a transparent support. It was

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION There is no known method of projecting and exposing on a color paper or the like while leaving both silver halide and developed silver on the basis of a color color image obtained by exposing and developing a light-sensitive material. According to the research conducted by the present inventor, the transmission Dmin at the maximum absorption wavelength of the three color dyes after development is 2.0.
In the following, it was found that when Dmax is 4.0 or less and Dmax-Dmin is 1.0 or more, good prints having almost no problems in graininess, sharpness, and color reproduction can be obtained. When the conventional photographic light-sensitive material is not bleached or fixed, Dmin and Dmax should be the above values because the amount of coated silver halide is large and anti-halation or anti-irradiation dye, colloidal silver, filter dye, etc. remain. Therefore, the amount of light that is exposed to color paper or the like increases, and the influence of printout during exposure increases. Further, the irradiation preventing dyes, filter dyes, and antihalation dyes necessary for so-called color negative photosensitive materials unnecessarily increase the Dmin and Dmax of the image information if they remain after the processing, and therefore they are preferably removed in the development processing step.

In the present invention, the color image information including the developed silver information is converted into optical information or electrical information, but it may be photoelectrically read and converted into a digital signal. When this reading is performed by measuring the density of transmitted light, the dye density at the maximum absorption wavelength of the dye is 3 than the density of developed silver.
It is desirable that the number be twice or more. Further, it is desirable that the difference in density between the unexposed area and the exposed area is 20% or less of the original density by using silver halide in an amount 5 times or more the theoretical amount necessary for color image formation. The total concentration of silver halide and developed silver is preferably 2.0 or less. When the above conditions are satisfied, the original image can be faithfully reproduced from the read signal by image processing. When the conventional photographic light-sensitive material is not bleached and fixed, the scanner noise during reading becomes large and the image quality deteriorates significantly, so that reading is substantially impossible. The output material in this case may not be a photosensitive material, and may be, for example, a sublimation type thermal transfer material, an ink jet material, a full color direct thermal recording material, a color CRT, a color LCD, or the like, but a thermal development color print material, for example, Fuji Photo Film Co., Ltd.
When output to PICTROGRAPHY 3000, a simple and excellent print image can be obtained. Further, since the digital image signal can be arbitrarily processed and edited, the photographed image can be freely modified, transformed, processed and output.

In the present invention, as the development treatment of silver halide, the exposed light-sensitive material may be passed through a base or a liquid containing a base and a reducing agent, but the development temperature is 60 ° C.
A heat development method in which the temperature is 150 ° C. or higher is preferable. In this case, when the obtained color negative image information is converted into a digital signal and printed with the above photothermographic material, the process from photographing to printing can be performed without using any processing solution used in conventional color photography. In addition, using Fuji Photo Film Co., Ltd.'s PICTROSTAT330,
Even if the image information is optically read and output by the E unit, the process from photographing to printing can be performed without using any processing liquid.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed.
No. 167,743 and No. 4-223,463, the method of mixing the monodisperse emulsion and adjusting the gradation is preferably used. The particle size is 0.1 to 2 μm, in particular 0.
2 to 1.5 μm is preferable. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,029
(1978), No. 17, 643 (December 1978)
Mon., pages 22-23, ibid. No. 18,716 (1979, 1)
(Jan.) 648, pp. 307, 105 (January 1989)
January) pages 863 to 865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkides, C.
hemie etPhisque Photographique, Paul Montel, 196
7), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, F
ocalPress, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et a
l., Making and Coating Photographic Emalusion, Foc
Any of the silver halide emulsions prepared by the method described in al Press, 1964) can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The light-sensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodidium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When incorporated, the particles may be uniformly introduced or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, and JP-A-4-126629 are preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thiourea compound or JP-B-47-11 is used as a silver halide solvent.
No. 386, or an organic thioether derivative described in
For example, a sulfur-containing compound described in 3-144,319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography," published by Paul Monte (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
(Tel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chem
istry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikm)
an et al., Making and Coating Photographic Emalusi
on, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142,329 and JP-A-55-158). 124, U.S. Pat. No. 3,650,75
No. 7). Further, the stirring method of the reaction liquid may be a known loose stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set as desired depending on the purpose. The preferred pH range is 2.2 to 7.0, more preferably 2.5 to 6.0.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,798, etc.). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to provide the photosensitive silver halide used in the present invention with green-sensitive, red-sensitive and infrared-sensitive color sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat.
617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-63-23,145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

Additives used in such steps and known photographic additives usable in the present invention are the above-mentioned RD.
No. 17, 643, No. 18, 716 and No. 3
07, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column Whitening agent Page 24 Page 648 Right column Page 868 5. Antifoggant page 24-26, page 649, right column, page 868-870, stabilizer 6. Light absorber page 25-26 page 649 right column page 873 filter dye-page 650 left column ultraviolet absorber 7. Dye image stabilizer, page 25, page 650, left column, page 872 8. 8. Hardening agent page 26 page 651 left column 874-875 Binder page 26 page 651 left column pages 873 to 874 10. Plasticizers, lubricants page 27 page 650 page right column page 876 11. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 12. Static page 27, page 650, right column, pages 876-877, inhibitor 13. Matting agent 878-879

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 1 mol per mole of the photosensitive silver halide.
10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 10 g / m ² .
4 g / m ² is suitable.

A hydrophilic binder is preferably used as the binder of the constituent layers of the photosensitive material. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also,
U.S. Pat. No. 4,960,681, JP-A-62-24
Superabsorbent polymer described in 5, 260, etc., namely-
COOM or —SO ₃ M (M is hydrogen atom or alkali metal) homopolymer of vinyl monomer or copolymer of vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical) Sumika gel L-5 manufactured by Co., Ltd.
H) is also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable, and the gelatin may be selected from lime-processed gelatin, acid-processed gelatin, so-called decalcified gelatin with a reduced content of calcium, etc., according to various purposes, and the combination should be used. Is also preferable. In the present invention, the coating amount of the binder is preferably 1 g or more and 20 g or less per 1 m ^{2, and} more preferably 2 g or more and 10 g or less.

The dye donating coupler that can be used in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler. Also,
The diffusion resistant group may form a polymer chain. An example of a coupler is TH James “The Theory of the Photogra
phic Process "4th edition pp. 291-334, and 354
Pp. 361, JP-A-58-123533, 58-1.
No. 49046, No. 58-149047, No. 59-11
1148, 59-124399, 59-174
No. 835, No. 59-231539, No. 59-2315
No. 40, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-.
No. 66249, Japanese Patent Application Nos. 6-270700 and 6-30.
7049, 6-312380 and the like.

Further, it is preferable to use the following couplers. Yellow coupler: couplers represented by formulas (I) and (II) of EP502,424A: EP513,4
No. 96A, couplers represented by the formulas (1) and (2), and a coupler represented by the general formula (I) of claim 1 of Japanese Patent Application No. 4-134523: 45 of column 1 of US Pat. No. 5,066,576; Coupler represented by general formula D on line 55, coupler represented by general formula D in paragraph 0008 of JP-A-4-274425: coupler described in claim 1 on page 40 of EP498,38A1, and coupler 4 described in EP447,969A1. Coupler represented by formula (Y) on page 4, US 4,47
Formulas (I) to (I) on lines 36 and 58 in column 7 of 6,219
A coupler represented by V). Magenta coupler: JP-A-3-39737, Japanese Patent Application No. 4
No. 234120, Japanese Patent Application No. 4-36917, and Japanese Unexamined Patent Publication No. Hei 4
A coupler described in No. 3626. Cyan coupler: JP-A-4-204843, JP-A-4
No. 43345, Japanese Patent Application No. 4-23633. Polymer coupler: JP-A-2-44345.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, GB2,12 is used.
5,570, EP 96,570, DE 3,234
No. 533 is preferred.

The light-sensitive material may also contain the following functional couplers. A coupler for correcting unnecessary absorption of a coloring dye is EP456,257A1.
Yellow-colored cyan coupler described in No. 4, yellow-colored magenta coupler described in said EP, US Pat.
33,069, a magenta colored cyan coupler, US Pat. No. 4,837,136 (2), WO92 / 11.
575. A colorless masking coupler of the formula (A) of claim 1 (especially the exemplified compound on pages 36 to 45). Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: EP378,2
36A1, page 11 of the formulas (I) to (IV), EP 436,938A2, page 7 of the formula (I), Japanese Patent Application No. 4-134523.
Represented by the formula (1) in EP No. 440,195A
2, compounds represented by formulas (I), (II) and (III) on pages 5 and 6, compounds represented by formula (I) in claim 1 of Japanese Patent Application No. 4-325564-ligand releasing compound, US
LIG-X according to claim 1 of 4,555,478
A compound represented by the formula: In the present invention, the content of the ^{coupler, 0.01g / m 2 ~10g / m} 2 are preferred,
0.1g / m ² ~2g / m ² is more preferable.

In the light-sensitive material of the present invention, the development time is shortened,
For the purpose of improving sensitivity, improving image density and the like, an embodiment in which a color developing agent capable of forming a dye by coupling an oxidant formed by silver development with the above-mentioned coupler is preferably incorporated. In this case, US Pat. No. 3,531,256
No. 3,761,270, p-phenylenediamine developing agents and phenol or active methylene couplers.
The combination of the p-aminophenol-based developing agent and the active methylene coupler of No. 1 can be used. U.S. Pat. No. 4,021,240, JP-A-60-128438 and the like.
The combination of equivalent couplers is a preferable combination because it is excellent in raw storage when incorporated in a light-sensitive material. When the color developing agent is incorporated, a precursor of the color developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599,
Research Disclosure No. 14, 850 and above
Nos. 15 and 159, Schiff base compounds, 1
Aldol compounds described in US Pat.
No. 492, JP-A-53-135628.
The urethane-based compounds described in (1) can be cited.

Further, a sulfonamidephenol-based main agent described in Japanese Patent Application No. 7-180,568, Japanese Patent Application No. 7-492.
The combinations of hydrazine-based main agents and couplers described in JP-A No. 87 and JP-A No. 7-63572 are also preferable for use in the light-sensitive material of the present invention.

When a diffusion resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Pat.
Those described in JP-A No. 9,919 and European Patent Publication No. 418,743 are used. In addition, JP-A-2-230,143,
As described in JP-A-2-235,044, a method of stably introducing into the layer is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned developing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of a diffusion-resistant developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Further, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,
040, JP-A-4-249,245, JP-A-2-46,
No. 450 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication 3-63,733
No., JP-A-1-150,135, JP-A-2-46,450
Nos. 2,64,634, 3-43,735 and EP-A-451,833 are also used.

Further, in the case of a photothermographic material, it is particularly preferable that a developing agent is incorporated. In this case, as the developing agent used, those known in the field of photothermographic materials can be used. Further, a developing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used. In addition, the following reducing agents may be incorporated in the light-sensitive material. Examples of the reducing agent used in the present invention include US Pat. No. 4,500,626, columns 49 to 50, and US Pat.
39,272, 4,330,617, 4,59
0,152, 5,017,454, 5,13
No. 9,919, JP-A-60-140,335, (17)
Pp. (18), pp. 57-40, 245, and pp. 56-138,
Nos. 736, 59-178, 458, 59-53,
Nos. 831, 59-182 and 449, 59-18
No. 2,450, No. 60-119, 555, No. 60-1
28,436, 60-128,439, 60-
198,540, 60-181,742, 61
-259,253, 62-244,044, 6
2-131, 253, 62-131, 256 and 64-13,546, pages (40) to (57), JP-A-1-1
20,553 and EP 220,746 A2, pp. 78-96, and the like. Also, combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can be used. In the case of a photothermographic material, the developing agent or reducing agent may be incorporated in the processing sheet described later, or may be incorporated in the photosensitive material. In the present invention, the total amount of the developing agent and the reducing agent added is 0.
The amount is from 01 to 20 mol, particularly preferably from 0.1 to 10 mol.

Hydrophobic additives such as couplers, developing agents and diffusion resistant reducing agents can be incorporated into the layers of the light-sensitive material by known methods such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
No. 5,470, No. 4,536,466, No. 4,53
6,467, 4,587,206, 4,55
No. 5,476, No. 4,599,296, Japanese Examined Patent Publication 3-6
A high-boiling point organic solvent such as that described in No. 2,256 can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g, per 1 g of the hydrophobic additive used.
g or less, more preferably 1 g to 0.1 g. Also,
1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less, is suitable for 1 g of the binder. Tokiko Sho 51-3
9,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,242.
And the method of adding as a fine particle dispersion described in No. For compounds that are substantially insoluble in water,
In addition to the above-mentioned method, fine particles can be dispersed and contained in a binder. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157,636, Nos. (37) to (3)
On page 8), those mentioned as the surfactants described in Research Disclosure described above can be used. Further, phosphate ester type surfactants described in Japanese Patent Application Nos. 5-204325 and 6-19247 and West German Patent Application No. 1,932,299A can also be used. In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,626, Nos. 51-5.
It is described in column 2.

The light-sensitive material of the present invention contains at least three types of light-sensitive layers having different spectral sensitivities and different hues of color-forming dyes. Each photosensitive layer may be divided into a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The above-mentioned three types of photosensitive layers are preferably layers that are sensitive to any of blue light, green light, and red light. In general, the order of arrangement is from the support side to the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer. However, other arrangements may be used depending on the purpose. For example, an arrangement as described in column 162 of JP-A-7-152129 may be used. In the present invention, the silver halide, the dye donating coupler and the developing agent may be contained in the same layer, but if they are in a reactive state, they may be added separately in separate layers. For example, if the layer containing the developing agent and the layer containing silver halide are separated, the raw storage stability of the light-sensitive material can be improved. The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary, but when a cyan coupler is used for the red photosensitive layer, a magenta coupler is used for the green photosensitive layer, and a yellow coupler is used for the blue photosensitive layer, it is possible to directly add to conventional color paper and the like. Projection exposure is possible. In the light-sensitive material, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between and above the silver halide emulsion layers and the lowermost layer. Various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure as described in the above patent, the undercoat layer as described in US Pat. No. 5,051,335,
JP-A-1-167,838, JP-A-61-20,94
An intermediate layer having a solid pigment as described in JP-A-3-
120,553, 5-34,884, 2-6
An intermediate layer containing a reducing agent or a DIR compound as described in US Pat. Nos. 5,017,454 and 5,1.
39,919, an intermediate layer having an electron transfer agent as described in JP-A-2-235,044, JP-A-4-249,2.
A protective layer having a reducing agent as described in No. 45 or a layer obtained by combining them can be provided.

As the dye that can be used in the yellow filter layer and the antihalation layer, those dyes that are decolored or dissolved during development and do not contribute to the density after processing are preferable. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
The dye component may be 10 or less, and the components of the dye may be eluted from the light-sensitive material or transferred into the processing material at the time of development, or may be changed to a colorless compound by reacting at the time of development.

As the dye that can be used in the light-sensitive material of the present invention, known dyes can be used. For example, a dye that dissolves in the alkali of the developing solution, or a type of dye that decolorizes by reacting with components in the developing solution, sulfite ions, the base agent, and the alkali can be used. Specifically, dyes described in European Patent Publication EP549,489A and JP-A-7-15
No. 2129, ExF2-6 dyes. Solid-dispersed dyes as described in JP-A-8-101487 can also be used. This dye can be used when the photosensitive material is developed with a processing solution, but is particularly preferable when the photosensitive material is thermally developed using a processing sheet described later. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used.
Nos. 50,626, columns 58-59 and JP-A-61-882.
The mordants described in JP-A No. 56, pages 32 to 41, JP-A-62-244043, JP-A-62-244036 and the like can be used. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Pat. Nos. 4,559,290 and 4,783,396, European Patent 220,746A2, and JP-A-87-6119.
In addition to those described in JP-A-8-101487, it is described in paragraphs 0080 to 0081.

A decolorizable leuco dye or the like can also be used, and specifically, a silver halide containing a leuco dye previously developed with a developer of an organic acid metal salt in JP-A-1-150,132. A light sensitive material is disclosed. Since the leuco dye and the developer complex react with heat or an alkaline agent to erase the color, a combination of the leuco dye and the developer is preferred when the light-sensitive material of the present invention undergoes thermal development. Known leuco dyes can be used, and Moriga,
Yoshida, "Dyes and Chemicals", 9, 84 pages (Chemical Products Association),
"Handbook of New Dyes", p. 242 (Maruzen, 1970), R. Garn
er “Reports on the Progress of Appl.Chem” 56, 1
P. 99 (1971), "Dyes and Chemicals", p. 19, p. 230 (Chemical Products Industry Association, 1974), "Coloring Materials" 62, 288.
Page (1989), “Dyeing Industry”, 32, 208, etc. As the developer, a metal salt of an organic acid is preferably used in addition to the acid clay-based developer and phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts, metal salts of xanthogenates, and the like are useful, and zinc is particularly preferable as the metal. Among the above color developers, oil-soluble zinc salicylate is disclosed in U.S. Pat. Nos. 3,864,146 and 4,046.
No. 941 and those described in Japanese Patent Publication No. 52-1327 can be used. In the present invention, the amount of the dye, particularly the dye that is decolorized or removed during the development processing, is 1 mg / m ² to 10 so that the optical density is about 1.
g / m ² is preferable, and 10 mg / m ^{2 to 1} g / m ² is more preferable.

The light-sensitive material of the present invention is preferably hardened with a hardener. U.S. Pat.
678,739, column 41, 4,791,042,
JP-A-59-116,655 and 62-245,26.
No. 1, No. 61-18,942, JP-A-4-218,0
No. 44 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-methylol-based hardeners (such as dimethylol urea), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). 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.

Various antifoggants or photographic stabilizers and their precursors can be used in the light-sensitive material. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13,564 (7). Pages (9), (57)-(71) and (81)-(97), U.S. Patent No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No., JP-A-1-150,135 and 2-110,55
No. 7, No. 2-178,650, RD 17,643 (1978) (24) to (25) pages and the like. These compounds are used in an amount of 5 × 10 ^-6 to 1 / mol silver.
× 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 10
^-2 mol is preferably used.

As a method of developing the light-sensitive material of the present invention after exposure, heat development, an activator method of incorporating a developing agent into the light-sensitive material and developing with an alkaline processing solution, and a processing solution containing a developing agent / base are used. There is a method of developing with. In the present invention, the silver halide and the developed silver remaining after the color image is formed by the development treatment are not removed. As used herein, the term "remaining silver halide and developed silver after color image formation is not removed" means a step of additionally removing silver halide and developed silver after the development step (for example, bleaching step, fixing step, bleach-fixing step). Process).

The heat treatment of the light-sensitive material is known in the art, and the heat-developable light-sensitive material and its process are
For example, the basics of photographic engineering (Published by Corona Publishing Company in 1979)
Pages 553-555, published April 1978, video information 4
Page 0, Nebletts Handbook of Photography and Reprogra
phy 7th Ed. (Van Nostrand and Reinhold Company) 3
Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Patent 1,131,10
No. 8, No. 1,167,777 and Research Disclosure June 1978, pp. 9-15 (RD-
17029).

The activator processing is a processing method in which a color developing agent is contained in a light-sensitive material and development processing is performed with a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
It is illustrated in known documents such as 491A1 and 565,165A1.

The method of developing with a processing solution containing a developing agent / base is described in RD. No. 17643, pp. 28-29, No. 1
No. 30710, left column to right column, and No. 30710
5, pp. 880-881. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and representative examples and preferred examples thereof are EP 556700A, pp. 28, 43-52.
The compounds mentioned in the row are mentioned. These compounds can be used in combination of two or more depending on the purpose. The color developing solution includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, trimethanolamine and catecholsulfonic acids,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-
Auxiliary developing agents such as 3-pyrazolidone, viscosity-imparting agents,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimino Diacetate, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Add ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. P of color developer
H is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area with the air in the processing tank. The processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air cm
² ] ÷ [volume of processing solution cm ³ ]). This aperture ratio is preferably 0.1 or less,
More preferably, it is 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method of providing a movable lid described in JP-A-1-82032 and JP-A-63-216
The slit developing method described in No. 050 can be mentioned. The aperture ratio is not limited to both the color development step and the black and white development step, and the subsequent steps such as bleaching, bleach-fixing,
It is preferable to reduce the amount in all steps such as fixing, washing with water and stabilizing. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color developing process is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, a high pH and using a high concentration of the color developing agent.

Next, the processing material and processing method used in the case of the activator processing in the present invention will be described in detail. In the present invention, the light-sensitive material was subjected to development (silver development / cross oxidation of built-in color developing agent) and washing with water or stabilization. After the washing or stabilizing treatment, a treatment for enhancing color development such as alkali addition may be performed.

In the present invention, when the light-sensitive material is developed using an activator processing solution, it functions as a developing agent for silver halide and / or an oxidized product of a developing agent produced by silver development is incorporated in the light-sensitive material. It is preferable to use a compound having a function of cross-oxidizing a certain color developing agent (auxiliary developing agent). Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones. These compounds may be added to the developing solution, but are preferably incorporated in the photosensitive material.

As pyrazolidones, 1-phenyl-3
-Pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4 , 4-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl -2-hydroxymethyl-5-phenyl-3-pyrazolidone, 1- (2-chlorophenyl) -4-hydroxymethyl-4-methyl-3-pyrazolidone and the like.

Examples of dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

As the reductones, N-methyl-p-
Aminophenol, N- (β-hydroxyethyl) -p
-Aminophenol, N- (4-hydroxyphenyl)
Glycine, 2-methyl-p-aminophenol and the like.

These compounds are usually used alone, but it is also preferable to use them in combination of two or more kinds in order to enhance the development and cross oxidation activities. The amount of these compounds used in the developer is from 2.5 × 10 ⁻⁴ mol / l to 0.2 mol / l, preferably from 0.0025 mol / l to 0.1 mol / l.
1 mol / l, more preferably 0.001 mol / l
Liter to 0.05 mol / liter.

Preservatives used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium formaldehyde bisulfite and hydroxylamine / sulfate, and the amount used is 0.1 mol / mol.
Liter or less, preferably 0.001 to 0.02 mol /
It may be used in the liter range. When a high silver chloride emulsion is used in the light-sensitive material, the above compound is 0.00
It may be 1 mol / liter or less, preferably not contained at all.

In the present invention, it is preferable to contain an organic preservative in place of the hydroxylamine and sulfite ion. Here, the term "organic preservative" refers to all organic compounds that reduce the rate of deterioration of the developing agent by being added to a developer.
That is, organic compounds having a function of preventing oxidation of a developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, α-hydroxyketones Aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums,
Nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235 and JP-A-63-4235.
No.-5341, No.63-30845, No.63-216
No. 47, No. 63-44655, No. 63-46454
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
657, 63-44656, U.S. Pat.
No. 5,503, No. 2,494,903, Tokubo Sho48
-30496 and the like. Other preservatives include JP-A-57-44148 and JP-A-57-537.
Various metals described in JP-A No. 49-180588
Salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. No. 3,746,54
An aromatic polyhydroxy compound described in No. 4 or the like may be contained as necessary. It is particularly preferable to contain alkanolamines described in JP-A-4-97355, pp. 631-632, and dialkylhydroxylamine described in JP-A 627-630. Further, a dialkylhydroxylamine and / or a hydrazine derivative may be used in combination with an alkanolamine, or may be a dialkylhydroxylamine and glycine represented by dialkylhydroxylamine and glycine described in EP 530,921 A1.
-It is also preferable to use amino acids in combination.

The amount of these compounds used is preferably 1 × 10 ^{-3 to} 5 × 10 ^-1 mol per liter of the developer.
More preferably, it is 1 × 10 ^-2 to 2 × 10 ^-1 mol.

In the present invention, the developer contains halogen ions such as chlorine ions, bromine ions and iodine ions. In particular, when a high silver chloride emulsion is used, it preferably contains 3.5 × 10 ^{−3 to} 3.0 × 10 ⁻¹ mol / l of chloride ions, more preferably 1 × 10 ⁻² to 2 × 10 ^−2.
× 10 ^-1 mol / l, and / or preferably contains bromide ions in an amount of 0.5 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l, more preferably 3.0 × 10 ^-3 mol / l.
^{-5 to} 5 × 10 ^-4 mol / liter. Here, the halide may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When added to the developing solution, the respective sodium salts, potassium salts, ammonium salts, lithium salts and magnesium salts can be cited as the supply substances.

When it is eluted from the light-sensitive material, it is mainly supplied from a silver halide emulsion, but it may be supplied from a source other than the emulsion.

The developer used in the present invention preferably has a pH of 8 to 13, and more preferably 9 to 12. The above p
In order to retain H, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrate salts, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxylamine methane salts, lysine salts, etc. Can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoic acid have solubility and pH 9.0 or higher.
It is preferable to use these buffers because they have excellent buffering capacity in the H region and do not adversely affect photographic performance even when added to a developer.

Specific examples of these buffers include lithium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, disodium phosphate, potassium borate, boric acid. Mention may be made of sodium, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. The amount of the buffer added to the developer is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol to 0.4 mol / l.

In addition, various chelating agents can be used as a precipitation preventing agent for calcium and magnesium in the developing solution or for improving the stability of the developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxy Phenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and alkali metal salts thereof. . These chelating agents may be used in combination of two or more as necessary. The addition amount of these chelating agents may be an amount sufficient to mask metal ions in the developer, for example, 0.1 g to 10 g per liter.
g.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. Examples of the nitrogen-containing heterocyclic compound include, for example,
Benzotriazole, 5-nitrobenzotriazole,
5-methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole, 2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, 1-phenyl-5-mercaptotetrazole or derivatives thereof are mentioned as typical examples. be able to. The addition amount of the nitrogen-containing heterocycle is 1 × 10 ⁻⁵ to 1
× 10 ^-2 mol / liter, preferably 2.5x10 ^-5 ~
It is 1 × 10 ⁻³ mol / liter.

If desired, any development accelerator can be added to the developer. As development accelerators, JP-B-37-16
No. 088, No. 37-5987, No. 38-7826,
Thioether compounds described in JP-A Nos. 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-5554, JP-A-50-137726, JP-B-44-300
No. 74, JP-A-56-156826 and JP-A-52-4
Quaternary ammonium salts described in US Pat. Nos. 2,494,903, 3,123,182, 4,230,796, and 3,253,919; No. 11431, U.S. Pat. No. 2,482,546
Nos. 2,596,926 and 3,582,34
No. 6, etc., and the amine compounds described in JP-B-37-1608.
No. 8, No. 42-25201, U.S. Pat.
No. 501, etc., polyalkylene oxides and imidazoles can be added as needed.

The developer preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4-diamino-2,2'-disulfostilbene compound. Specifically, commercially available optical brighteners such as "Dyeing Note 19th Edition"
The compounds described on pages 165 to 168 and JP-A-4-24
The compounds described in No. 2943, pages 3 to 7 can be used. The addition amount is 0.1 g to 10 g / liter, preferably 0.5 g to 5 g / liter.

The processing temperature of the developing solution applied to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishing amount is small, but 15 to ⁶ per 1 m ^{2 of} light-sensitive material
The amount is 00 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml.

The photographic material of the present invention may be washed with water and / or stabilized after development. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Soc.
iety of Motion Picture and Television Enginee rs
It can be determined by the method described in Volume 64, P. 248 to 253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but bacteria increase due to the increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this problem, JP-A-62-288,8 has been proposed.
The method of reducing calcium ions and magnesium ions described in No. 38 is extremely effective. In addition, Japanese Unexamined Patent Publication No.
7-8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) ) Sankyo Shuppan, Hygiene Society, “Microbial Sterilization, Sterilization, and Antifungal Technology” (198)
2 years) The bactericides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can also be set depending on the characteristics and use of the light-sensitive material, but generally 15 to 45 ° C. and 20 seconds to 10 minutes, preferably 25.
A range of 30 seconds to 5 minutes at -40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, JP-A-57-8543 and JP-A-58-14834.
Known methods described in No. 60-220345 can be applied. Further, there may be a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilization bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing. You can Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

Next, a processing material and a processing method used in the case of the heat development processing in the present invention will be described in detail.

A base or a base precursor is preferably used in the light-sensitive material of the present invention for the purpose of promoting silver development and dye formation reaction. As base precursors, salts of organic acids and bases that decarboxylate by heat, intramolecular nucleophilic substitution,
There are compounds that release amines by Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat. Nos. 4,514,493 and 4,657,848 and Known Technology No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86. Have been.
Further, as described in European Patent Publication No. 210,660 and U.S. Pat. No. 4,740,445, which will be described later, a basic metal compound which is poorly soluble in water and a metal ion which constitutes the basic metal compound, A method in which a base is generated by a combination of compounds capable of a complex formation reaction (referred to as a complex formation compound) using water as a medium may be used. The amount of the base or base precursor used is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² .

A heat solvent may be added to the light-sensitive material of the present invention for the purpose of promoting heat development. Examples include U.S. Pat. Nos. 3,347,675 and 3,667,9.
Organic compounds having a polarity as described in JP-A No. 59-59 are exemplified. Specifically, amide derivatives (benzamide etc.), urea derivatives (methyl urea, ethylene urea etc.), sulfonamide derivatives (compounds described in JP-B-1-40974 and JP-B-4-13701, etc.), polyol compounds Sorbitols), and polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose. The amount of the hot solvent added is 10% of the binder of the layer to be added.
Wt% to 500 wt%, preferably 20 wt% to 300
% By weight.

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
The temperature is 50 ° C., but especially 60 ° C. to 150 ° C. is useful.

In the heat development step, air is blocked during heat development, volatilization of the material from the light-sensitive material is prevented, material for processing is supplied to the light-sensitive material, In order to remove the material (YF dye, AH dye, etc.) or unnecessary components generated during development, a material different from the photosensitive material may be superposed on the photosensitive surface of the photosensitive material and heated. As the support and binder of the processing sheet used in this case, the same materials as those for the light-sensitive material can be used. A mordant may be added to the treatment sheet for the purpose of removing the above-mentioned dye and other purposes. As the mordant, those known in the photographic field can be used, and US Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-88256, 32 to 4 can be used.
Page 1, JP-A-62-244043, JP-A-62-24
The mordants described in No. 4036 and the like can be mentioned. Further, a dye-receptive polymer compound described in US Pat. No. 4,463,079 may be used.

When the processing sheet is used, it is preferable that the base or the base precursor is contained in a separate sheet in order to improve the raw storability of the light-sensitive material. The hot solvent may be put in either the light-sensitive material or the processed sheet, or both, depending on the purpose.

In the case of heat development using a treatment sheet,
A solvent may be used for the purpose of accelerating development, accelerating transfer of the processing material, and accelerating diffusion of unnecessary substances. Specifically, U.S. Pat. Nos. 4,704,245 and 4,470,445.
And JP-A-61-238056.
In this method, the heating temperature is preferably equal to or lower than the boiling point of the solvent used. For example, when the solvent is water, 50 ° C. to 10
0 ° C. is preferred. Examples of the solvent used for accelerating the development and / or for the diffusion transfer of the processing material include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include an image forming accelerator). Those described in the section (1) are used), a low boiling point solvent or a mixed solution of a low boiling point solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as the solvent used in these heat development steps, but any commonly used water may be used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the light-sensitive material and the image receiving element of the present invention, water may be used up, or may be circulated for repeated use. In the latter case, water containing components eluted from the material will be used. In addition, JP-A-63-14
4,354, 63-144,355, 62-3.
The apparatus and water described in JP-A No. 8,460, JP-A-3-210,555 and the like may be used. These solvents can be applied to the photosensitive material, the processing sheet, or both. In this case, it may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of applying this water, for example, the methods described in JP-A-62-253,159, page (5) and JP-A-63-85,544 are preferably used. Further, the solvent may be enclosed in microcapsules, or may be incorporated in advance in the form of a hydrate in the light-sensitive material or the processed sheet or both. The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85,544.

When heat development is carried out in the presence of a small amount of water or a solvent, as described in European Patent Publication No. 210,660 and US Pat. No. 4,740,445, a basic substance which is poorly soluble in water is used. It is effective to employ a method in which a base is generated by a combination of a metal compound and a metal ion constituting the basic metal compound and a compound capable of complexing reaction with water as a medium (referred to as complex forming compound). In this case, it is desirable from the viewpoint of raw storability that the basic metal compound which is hardly soluble in water is added to the light-sensitive material and the complex-forming compound is added to the processing sheet.

As the heating method in the developing step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared or far infrared lamp heater or the like is brought into contact therewith. Alternatively, there is a method of passing through a high temperature atmosphere.
A method for superposing a light-sensitive material and a processing sheet is disclosed in JP-A-62-62.
-253,159, JP-A-61-147,244 (2
7) The method described on page can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application Nos. 4-277,517 and 4
-243,072, 4-244,693, 6-
Devices described in JP-A-164,421 and JP-A-6-164,422 are preferably used. As a commercially available device, there can be used Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrostat 330, Pictrostat 50, Pictrograph 3000, Pictograph 2000, etc., manufactured by Fuji Photo Film Co., Ltd. .

The light-sensitive material and / or the processed sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of the present invention, those described in JP-A-61-145544 can be used.

Various surface active agents may be used in the light-sensitive material for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, JP-A-62-17.
3,463 and 62-183,457. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57
No. 9053, columns 8 to 17, JP-A-61-20944
No. 62-135826 and hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

It is preferable that the light-sensitive material has slipperiness. 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 stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when 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.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O ₂ , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
A particle size of at least one selected from MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less; Metal oxides or their composite oxides (Sb, P, B, In, S,
Fine particles of Si, C, etc., and fine particles of sol-like metal oxides or composite oxides thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or the composite oxide to the binder is from 1/300 to
100/1 is preferable, and 1/100 to 1 is more preferable.
00/5.

The composition of the light-sensitive material or the processing sheet (including the back layer) includes dimensional stabilization, curl prevention, adhesion prevention,
Various polymer latexes can be contained for the purpose of improving film physical properties such as prevention of cracking of the film and prevention of pressure increase / decrease sensation. Specifically, JP-A Nos. 62-245258 and 62
Any of the polymer latexes described in JP-B-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but is 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 narrow, and 90% or more of the total number of particles may be contained within 0.9 to 1.1 times the average particle size. preferable. It is also preferable to add fine particles of 0.8 μm or less at the same time 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
.mu.m) and colloidal silica (0.03 .mu.m). Specifically, it is described in JP-A-61-88256 (page 29). Others, benzoguanamine resin beads,
There are compounds described in JP-A Nos. 63-274944 and 63-274952, such as polycarbonate resin beads and AS resin beads. In addition, the compounds described in the above Research Disclosure can be used.

In the present invention, as the support for the light-sensitive material and the processing sheet, those capable of withstanding the processing temperature are used. In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-", published by Corona Co., Ltd. (Showa 54)
(Years) (223) to (240) pages, photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate,
Examples include polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (eg, triacetyl cellulose). These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, Japanese Patent Laid-Open No. 62-253,15
No. 9, pages 29-31, JP-A-1-161,236 (14)-
(17), JP-A-63-316,848, JP-A-2-2
No. 2,651, No. 3-56,955, U.S. Pat.
The support described in 001,033 or the like can be used.

Particularly when heat resistance and curl characteristics are severely demanded, it is used as a support for a photosensitive material.
No. 6-43581, No. 6-51426, No. 6-
No. 51437, No. 6-51442, Japanese Patent Application No. 4-251
No. 845, No. 4-231825, No. 4-253545
Nos. 4-258828, 4-240122, 4-221538, 5-21625, 5-15
No. 926, 4-331919, 5-199704
And the support described in JP-A-6-13455 and JP-A-6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

Further, in order to bond the support and the light-sensitive material constituting layer, it is preferable to carry out a surface treatment. 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, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
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 resorcin and p-chlorophenol. In the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates,
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), epichlorohydrin resin,
Examples thereof include active vinyl sulfone compounds.
SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Further, as the support, for example, Japanese Patent Laid-Open No. 4-1
24645, 5-40321, 6-35092
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in Japanese Patent Application Nos. 5-58221 and 5-106979.

The magnetic recording layer is formed by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite,
Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co
Co-deposited ferromagnetic iron oxides such as complexed γFe ₂ O ₂ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0.
× 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁴ to
2.5 × 100 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-1610.
As described in No. 32, the surface thereof may be treated with a silane coupling agent or a titanium coupling agent. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binder used in the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, reaction products of these isocyanates with polyalcohols (for example, reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and condensation products of these isocyanates. Examples of the polyisocyanate include, for example, JP-A-6-5935.
No. 7.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable as in the method described in JP-A-6-35092, and the combined use is also preferable. JP-A-5-088283
The dispersants described in No. 1 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
It is 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01.
~ ² g / m ² , more preferably 0.02-0.5 g / m ²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. 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. Photosensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874 and EP466,130. .

The polyester support preferably used in the above-mentioned magnetic material having the magnetic recording layer will be further described. For details including the light-sensitive material, processing, cartridge, and examples, refer to Kokai Giho, JP-A-94-6023. (Invention Society; 1994. 3.15). Polyester is formed by using diol and aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5.
-, 1,4-, and 2,7-naphthalenedicarboxylic acid,
Terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 100.
It is a polyester containing 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 is 50 ° C. or higher, and 9
0 ° C. or higher is preferred.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. 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 and 1500 hours or less, and 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. The surface is provided with irregularities (for example,
Conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ) may be applied) to improve the surface condition. 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. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, a film cartridge in which a light-sensitive material can be loaded 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 may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537 and 1-
No. 312538. 25 ° C, 25%
The resistance at RH 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 in order to impart light shielding properties. The size of the cartridge may be the same as the current 135 size, and it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to miniaturize the camera. The volume of the cartridge case is 30 cm ³
It is preferably 25 cm ³ or less. The weight of the plastic used for the cartridge and patrote case is preferably 5 to 15 g.

Further, a patrone that rotates the spool to feed the film may be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are U
S4, 834, 306 and 5, 226, 613.

As a method for producing a print on a color paper or a photothermographic material using this color photographic material,
JP-A-5-241251, 5,19364, 5
-19363 can be used.

[0095]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 An aqueous solution of 30 g of inert gelatin, 6 g of potassium bromide and 1 liter of distilled water was stirred at 75 ° C., and 35 cc of an aqueous solution of 5.0 g of silver nitrate and 3.2 g of potassium bromide were added thereto. A seed emulsion was prepared by adding 35 cc of an aqueous solution of 0.98 g of potassium iodide at a flow rate of 70 cc / min for 30 seconds each and then raising the pAg to 10 and ripening for 30 minutes.

Subsequently, a predetermined amount of 1 liter of an aqueous solution containing 145 g of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide are added in equimolar amounts at a predetermined temperature and a predetermined pAg at a rate close to the critical growth rate. It was added at a rate to prepare a tabular core emulsion. Furthermore, the remaining silver nitrate aqueous solution and a mixture of potassium bromide and potassium iodide having a composition different from that in the preparation of the core emulsion were added to the aqueous solution in equimolar amounts at an addition rate near the critical growth rate to coat the core. Thus, the core / shell type silver iodobromide tabular emulsion 1 shown in Table 1 was prepared.

[0097]

[Table 1]

Using the prepared emulsion 1, the following samples were prepared. On the undercoated cellulose triacetate film support, each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 S-1 0.15 S-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion K Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.20 Silver iodobromide emulsion B Silver 0.20 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.11 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 S-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.60 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.095 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 S-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion 1 Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.70 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 ExC-9 0.040 Cpd-2 0.050 S-1 0.022 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 S-1 0.050 polyethyl acrylate latex 0.15 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion D Silver 0.15 Silver iodobromide emulsion E Silver 0.10 Silver iodobromide emulsion F Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExC-10 5.0 × 10 ^-3 ExM-2 0.20 ExM-3 0.050 ExM-6 0.040 ExM-7 0.12 ExY-1 0.010 S-1 0.30 Gelatin 1.40

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion G Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-3 0.015 ExM-4 0.030 ExM-5 0.035 ExM-6 0.015 ExM-8 0.035 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 S-1 0.100 Gelatin 0.80

Ninth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Emulsion 1 Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExC-10 5.0 × 10 ^-3 ExM-1 0.020 ExM-9 0.040 Cpd-3 0.040 S-1 0.200 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 ExC-11 0.050 Cpd-1 0.10 Oil-soluble dye ExF-2 0.010 S-1 0.30 Gelatin 0.80

11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion H Silver 0.09 Silver iodobromide emulsion I Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.55 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 S-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.11 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 S-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.15 UV-2 0.075 UV-3 0.065 UV-4 0.080 S-1 5.0 × 10 ^-2 S-2 5.0 × 10 ^-2 Gelatin 1.4

14th layer (second protective layer) Silver iodobromide emulsion K Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 HS-1 0.25 gelatin 0.70

Further, W-1 to W-4 and B-4 to B- are added to each layer to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property. 6, F-1 to F-
17 and iron salt, lead salt, gold salt, platinum salt, palladium salt,
Contains iridium and rhodium salts.

[0114]

[Table 2]

In Table 2, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared 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 dye and sodium thiocyanate described in each photosensitive layer. (3) Emulsion J is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

[Chemical 6]

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

The prepared light-sensitive material (101) was used as a standard 35
The film was cut into a mm negative film size, punched, and loaded into a camera to photograph a person and Macbeth chart. This sample was subjected to readal processing in the following color processing steps.

<Processing step> Process Processing time Processing temperature Color development 3 minutes 5 seconds 38.0 ℃ Stop 30 seconds 38.0 ℃ Water wash 1 minute 38.0 ℃ Dry 1 minute 30 seconds 60 ℃

The composition of the processing liquid is shown below. (Color developer) Diethylenetriamine pentaacetic acid 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 3.9 g Potassium carbonate 37.5 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate Salt 2.4 g 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) -amino) aniline sulfate 4.5 g Water was added to 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid ) 10.05 (stop solution) 30g acetic acid Add water 1.0 liter

After the development processing, a negative image of the photographed image was obtained on the photosensitive material 101. This negative film is exposed to Fuji Photo Film Co., Ltd. Fuji Color Paper SUPER FAV with Fuji Photo Film Co., Ltd. automatic color printer 12C4510 in the same manner as normal negative film, and Fuji Photo Film Co., Ltd. minilab champion FA120. CPFAII, a treatment chemical for color paper
Standard treatment was performed. Despite the fact that silver halide and developed silver remained on the negative film, a good print was obtained, and the human skin color and each color on the Macbeth chart could be reproduced.

Further, the obtained negative film was processed in the same manner as a normal negative film by using PICTROST manufactured by Fuji Photo Film Co., Ltd.
Using the AT330, the NSE unit optically read the image information and output it. Also in this case, a good print was obtained, and the skin color of the person and each color on the Macbeth chart could be reproduced even though the silver halide and the developed silver remained on the negative film.

The image information of the processed light-sensitive material is read by the negative film scanner, Topaz manufactured by Rhinotype Hell, which uses diffused light, and read by Apple Computer.
The digital information obtained was transferred to a Macintosh Quadra 840AV manufactured by Macintosh, and after the image processing, it was output with a Pictrography 3000, and a good portrait print was obtained.

Example 2 A photosensitive material (Sample 102) having the same constitution was prepared, except that the compositions of the first layer, the sixth layer and the tenth layer of the photosensitive material 101 were changed as follows. The number corresponding to each component indicates the coating amount expressed in g / m ² . (1st layer) Gelatin 1.60 Solid disperse dye ExF-3 0.080 ExF-4 0.070 ExF-5 0.030 ExF-6 0.120 (6th layer) Gelatin 1.10 Cpd-1 0. 090 S-2 0.050 Polyethyl acrylate latex 0.15 Solid disperse dye ExF-5 0.050 (10th layer) Gelatin 0.80 Cpd-1 0.10 S-2 0.10 Solid disperse dye ExF-6 0.090 ExF-7 0.090

(Preparation of Dispersion of Organic Solid Disperse Dye) The above ExF-3 was dispersed by the following method. That is, 21.7 ml of water, 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate, and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) and 700 ml of 700 ml were added. The mixture was placed in a pot mill, 5.0 g of dye ExF-3 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, take out the contents, 1
8 g of 2.5% gelatin aqueous solution was added and the beads were filtered off to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-4, ExF-6 and ExF-7 were obtained. The average particle size of the fine dye particles is 0.24 μm, 0.45 μm and 0.52 μm, respectively.
Met. ExF-6 is European Patent Application Publication (EP) No. 5
Dispersion was carried out by the microprecipitation dispersion method described in Example 1 of the specification of No. 49,498A. The average particle size was 0.06 μm.

[0142]

Embedded image

The processing 102 was used as a color negative film in the same manner as the sample 101, and was cut, perforated, loaded into a camera and used as a photographic material. This negative film is exposed to Fuji Photo Film Co., Ltd. Fuji Color Paper SUPER FAV with Fuji Photo Film Co., Ltd. automatic color printer 12C4510 in the same manner as normal negative film, and Fuji Photo Film Co., Ltd. minilab champion FA120. Was used for standard treatment with CP40FAII, a treatment chemical for color paper. Good prints were obtained despite the residual silver halide and developed silver on the negative film,
I was able to reproduce the skin color of a person and each color on the Macbeth chart.
A more saturated print was obtained than when using Sample 101.

Further, the obtained negative film was processed in the same manner as a normal negative film by PICTROST manufactured by Fuji Photo Film Co., Ltd.
Using the AT330, the NSE unit optically read the image information and output it. Also in this case, a good print was obtained, and the skin color of the person and each color on the Macbeth chart could be reproduced even though the silver halide and the developed silver remained on the negative film. A more saturated print was obtained than when using Sample 101.

The image information of the processed light-sensitive material is read by a negative film scanner using a diffused light, Topaz manufactured by Rhinotype Hell, and read by Apple Computer.
The digital information obtained was transferred to a Macintosh Quadra 840AV manufactured by Macintosh, and after the image processing, it was output with a Pictrography 3000, and a good portrait print was obtained. Sample 10
Prints with higher saturation, sharpness and graininess were obtained as compared with the case of using No. 1.

Example 3 (Preparation of Photosensitive Material) A multilayer color photosensitive material having the layer structure shown below was prepared. This is designated as a sample (301). The coating solution was prepared as described below.

Preparation of coating liquid for the first layer 27.8 g of yellow color coupler (Y-1), ETA
-1 4.0 g, color-forming reducing agent (I-1) 20.5 g were dissolved in solvent (Solv-1) 52 g and ethyl acetate 73 cc, and this solution was added with 10% sodium dodecylbenzenesulfonate and citric acid. % Emulsion L was prepared by emulsifying and dispersing in 420 cc of gelatin aqueous solution.

[0148]

Embedded image

On the other hand, silver chlorobromide emulsion L (cubic, 3: 7 mixture of large size emulsion having an average grain size of 0.88 μm and small size emulsion of 0.70 μm (silver molar ratio). Coefficient of variation of grain size distribution. Of 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride in each size emulsion). In this emulsion, blue-sensitive sensitizing dyes-1, 2 and 3 shown below were composed of silver 1
1.4 x 1 for large emulsions per mole
^0-4 mol, and for small emulsions 1.
7 × 10 ^-4 mol is added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion L and this silver chlorobromide emulsion L were mixed and dissolved to prepare a coating solution for the first layer.

[0150]

Embedded image

The coating solutions for the third and fifth layers are also the coating solutions for the first layer.
Was prepared in the same manner as in. That is, silver chloride for the third layer
Emulsion M (cubic, large grain size 0.50 μm average grain size)
1: 4 mixture of small emulsion and 0.41 μm small size emulsion
(Silver molar ratio). The coefficient of variation of the particle size distribution is
0.09 and 0.11, silver bromide 0.8 m
Exists in a part of the surface of silver chloride based grains.
Was prepared). This emulsion has the following green sensitization
Dye-1 per mole of silver
3.0 × 10^-Four3.6 × for moles and small emulsions
10^-Four1 mole of silver and 2 moles of green sensitizing dye-2
4.0 × 10 for large emulsions ^-FiveMole, small
7.0 × 10 for Izu emulsion^-FiveMole added
You. Further, the green-sensitizing sensitizing dye-3 is added in a large amount per mol of silver.
2.0 × 10 for Izu emulsion^-FourMole, also small size
2.8 × 10 for emulsion^-FourMole is added. This
Of silver chlorobromide emulsion M and emulsion L prepared in the same manner
And an emulsion M containing a color coupler (M-1)
Mixed and dissolved to prepare a third layer coating liquid.

[0152]

Embedded image

Silver chloride emulsion for the fifth layer (cubic, 1: 4 mixture of large size emulsion with average grain size 0.50 μm and small size emulsion with 0.41 μm (silver mole ratio). Coefficient of variation of grain size distribution is , 0.09 and 0.11, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride for each size emulsion). In this emulsion, the red sensitizing dye-1 shown below was used per mol of silver, 5.0 × 10 ^-5 mol for large size emulsion and 6.0 × 10 ^-5 mol for small size emulsion. Mol, and red sensitive sensitizing dye-2 per mol of silver, 5.0 × 10 ⁻⁵ mol for large size emulsion and 6.0 × for small size emulsion.
10 ^-5 mol is added.

[0154]

Embedded image

Further, compound A was added in an amount of 2.6 × 1 per mol of silver.
0 ^-3 mol was added. This silver chlorobromide emulsion N and emulsion N containing cyan color coupler (C-1) prepared in the same manner as emulsion L were mixed and dissolved to prepare a fifth layer coating solution.

[0156]

Embedded image

The second, sixth and seventh layers are also given in Table 3,
It was prepared so as to have the composition shown in Table 4. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-
Triazine sodium salt was used. In addition, each layer has Cpd
Total volume -4 and Cpd-5, respectively, was added such that 25 mg / m ² and 50 mg / m ^2.

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ^-5 mol, 9.0 × 10 ^-4 mol per mol,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. An anti-irradiation dye was added to the emulsion layer to prevent irradiation. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). It represents the amount of silver halide emulsion and silver equivalent.

[0159]

[Table 3]

[0160]

[Table 4]

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

<Activator Development> The photosensitive material 301 was cut into a size of a normal color negative film of 35 mm, perforated and loaded into a camera to photograph a person. The exposed light-sensitive material was processed as follows. <Processing step> Activator development 40 ℃ 1 minute Stop 40 ℃ 30 seconds Water wash 40 ℃ 1 second Dry 60 ℃ 2 minutes Activator solution tested both (1) and (2) below. However, the result was not so different.

Activator solution (1) Tetramethylammonium hydroxide (25%) 0.15 mol / l N, N′-dimethylguanidine 0.10 mol / l Sodium bicarbonate was added to pH 12.5 (25 ° C.) Activator Liquid (2) Water 80 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-disulfonic acid (30%) 40 ml Water was added to 1000 ml pH (25 ℃, with potassium hydroxide) 12.5

Stopping solution 30 g acetic acid Water added to 1 liter

After the development processing, a negative image of the photographed image was obtained on the photosensitive material 201. This negative film is exposed to Fuji Photo Film Co., Ltd. Fuji Color Paper SUPER FAV with Fuji Photo Film Co., Ltd. automatic color printer 12C4510 in the same manner as normal negative film, and Fuji Photo Film Co., Ltd. minilab champion FA120. CP40F, a treatment chemical for color paper
Standard treatment was performed with AII. Despite the fact that silver halide and developed silver remained on the negative film, a good print was obtained, and the human skin color and each color on the Macbeth chart could be reproduced.

Further, the obtained negative film was used in the same manner as a normal negative film, and PICTROST manufactured by Fuji Photo Film Co., Ltd.
Using the AT330, the NSE unit optically read the image information and output it. Also in this case, a good print was obtained, and the skin color of the person and each color on the Macbeth chart could be reproduced even though the silver halide and the developed silver remained on the negative film.

The image information of the processed light-sensitive material is read by a negative film scanner, Topaz manufactured by Rhinotype Hell, which uses diffused light, and read by Apple Computer.
The digital information obtained was transferred to a Macintosh Quadra 840AV manufactured by Macintosh, and after the image processing, it was output with a Pictrography 3000, and a good portrait print was obtained.

Example 4 A dye composition was prepared and added as an emulsified dispersion as follows. Leuco dye and developer and optionally oil
(1) was weighed, ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C to form a uniform solution, and 100 g of this solution was added with 1.0 g of the surfactant (1) and lime-processed gelatin heated to about 60 ° C. Of 6.6% aqueous solution (190 cc) was added, and the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. As shown in Table 5,
Two types of dye dispersions were made.

[0171]

[Table 5]

[0172]

Embedded image

A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For Red-sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and the following chemicals) (A) Add 15mg and 42 ℃
The solution (I) and the solution (II) shown in Table 6 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 8 minutes. Then, 8 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of a dye (water 1) was added.
1.9 g of gelatin in 60 ml, the following pigment (a) 127
mg, the following pigment (b) 253 mg, the following pigment (c) 8 mg
Containing 35 ° C. and kept at 35 ° C.). After 2 minutes, solution (III) and solution (IV) in Table 6 were simultaneously added at the same flow rate for 32 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene was added, followed by sodium thiosulfate and chloroauric acid for optimum chemical sensitization at 68 ° C, and then the following antifoggant
(1), 80 mg of the chemical (C) and 3 g of the chemical (D) were added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.21 μm was obtained.

[0176]

[Table 6]

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

Photosensitive Silver Halide Emulsion (2) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 700 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 53 ° C.), the solutions (I) and (II) in Table 7 were simultaneously added at an equal flow rate for 10 minutes. Then, 6 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of the dye (115 ml of water) was added.
Then, 1.2 g of gelatin, 77 mg of the above dye (a), 153 mg of the above dye (b), and 5 mg of the above dye (c) and kept at 45 ° C.) were added. After 4 minutes, (I
Solution (II) and solution (IV) were added simultaneously at the same flow rate for 30 minutes.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin and 50 mg of the above-mentioned chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6-. Methyl-1,3,3a, 7-tetrazaindene was added, followed by sodium thiosulfate and chloroauric acid for optimum chemical sensitization at 68 ° C., and then the antifoggant described above.
(1), 80 mg of the chemical (C) and 3 g of the chemical (D) were added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0182]

[Table 7]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 5 in 690 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 41 ° C.), the solutions (I) and (II) in Table 8 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 8 were simultaneously added at the same flow rate for 32 minutes. (II
1 minute after the addition of the solutions (I) and (IV) was completed, the dye solution in methanol (47 ml of methanol was mixed with the following dye (d-1) 2810).
mg and (d-2) 57.3 mg which were kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B), 3 of chemical (D)
g to adjust pH to 6.2 and pAg to 7.8
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, followed by sodium thiosulfate to give 6
Optimum chemical sensitization at 0 ℃, then the following antifoggant (1)
And then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.23 μm was obtained.

[0185]

[Table 8]

[0186]

Embedded image

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 710 ml of water).
g and the above-mentioned chemical (A) 7.5 mg were added and kept at 63 ° C.) at the same time with the solutions (I) and (II) in Table 9
It was added at an equal flow rate for 0 minutes. After 10 minutes, (III) in Table 9
The solution and the solution (IV) were simultaneously added at an equal flow rate for 20 minutes. Also
One minute after the addition of the liquids (III) and (IV) was completed, the dye solution in methanol (35 ml of the above-mentioned dye (d-1) 210
mg and (d-2) 42.7 mg and kept at 46 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.2. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 60 ° C, and then the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0189]

[Table 9]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 5 parts of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 46 ° C.), the liquid (I) and the liquid (II) shown in Table 10 are simultaneously added to 8 parts.
Add at an equal flow rate for minutes. After 10 minutes, (III) in Table 10
Solution and (IV) solution were added simultaneously at the same flow rate for 18 minutes. Also
One minute after the addition of the solutions (III) and (IV) was completed, the following dye (e) 225 was added to an aqueous solution of the dye (in 95 ml of water and 5 ml of methanol:
mg, and 225 mg of the following dye (f) were kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 65 ° C., and then the following antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.27 μm was obtained.
g was obtained.

[0192]

[Table 10]

[0193]

Embedded image

Photosensitive Silver Halide Emulsion (6) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 710 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 59 ° C.), the liquids (I) and (II) in Table 11 are simultaneously added to 8 parts.
Add at an equal flow rate for minutes. 10 minutes later (III) in Table 11
Solution and (IV) solution were added simultaneously at the same flow rate for 18 minutes. Also
One minute after the addition of the solutions (III) and (IV) was completed, the dye (e) 113 was added to an aqueous solution of the dye (82 ml of water and 6 ml of methanol).
mg and the above-mentioned dye (f) (113 mg, kept at 40 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 65 ° C, and then the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.

[0196]

[Table 11]

<Preparation Method of Zinc Hydroxide Dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Preparation Method of Emulsified Dispersion of Coupler> Table 1
Dissolve the oil phase component and the water phase component of the composition shown in 2, respectively,
Make a uniform solution at 60 ° C. The oil phase component and the water phase component were combined and dispersed in 1 liter of a stainless steel solution at 10,000 rpm for 20 minutes by a dissolver equipped with a disperser having a diameter of 5 cm. To this, warm water in the amount shown in Table 12 was added as post-water and mixed at 2000 rpm for 10 minutes.
Thus, a coupler emulsified dispersion of three colors of cyan, magenta and yellow was prepared.

[0199]

[Table 12]

[0200]

Embedded image

[0201]

Embedded image

Using the materials thus obtained, a heat-developable color photosensitive material 401 having a multilayer structure shown in Tables 13, 14, and 15 was produced.

[0203]

[Table 13]

[0204]

[Table 14]

[0205]

[Table 15]

[0206]

Embedded image

The prepared light-sensitive material (401) was used as a standard 35
A film and a Macbeth chart were photographed by cutting, perforating, and loading in a camera to a mm negative film size. This sample was processed using Pictrostat 300. That is, the exposed light-sensitive material 101 is attached to the photosensitive material surface of the donor film of the pictrostat 300 so that the emulsion surface of the light-sensitive material 101 faces upward, and is loaded into the cassette of the donor film to be placed in the magazine D of the pictrostat 300. set. Stop the exposure function of the pictrostat. The magazine R of the Pictrostat 300 was loaded with the treatment sheets R101 shown in Table 16 and Table A. 1. Donor film with exposed light-sensitive material attached to water kept at 40 ℃ 2.
After soaking for 5 seconds, it was squeezed with a roller and immediately superposed so that the treated sheet and the film surface were in contact with each other. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface temperature is 80 ° C., it is heated for 17 seconds and the processing sheet is peeled off from the photosensitive material to obtain a negative image of the photographed person on the photosensitive material. It was

The structure of R101 of the processing sheet used is shown in the table below.

[0209]

[Table 16]

[0210]

[Table 17]

[0211]

Embedded image

[0212]

Embedded image

[0213]

Embedded image

[0214]

Embedded image

After the development processing, a negative image of the photographed image was obtained on the photosensitive material 401. This negative film is exposed to Fuji Photo Film Co., Ltd. Fuji Color Paper SUPER FAV with Fuji Photo Film Co., Ltd. automatic color printer 12C4510 in the same manner as normal negative film, and Fuji Photo Film Co., Ltd. minilab champion FA120. CP40F, a treatment chemical for color paper
Standard treatment was performed with AII. Despite the fact that silver halide and developed silver remain on the negative film, good prints such as sharpness and graininess can be obtained, and human skin color,
Each color on the Macbeth chart could be reproduced.

Further, the obtained negative film was used in the same manner as a normal negative film, and was manufactured by Fuji Photo Film Co., Ltd. PICTROST.
Using the AT330, the NSE unit optically read the image information and output it. In this case as well, although the silver halide and the developed silver remained on the negative film, good prints such as sharpness and graininess were obtained, and human skin color and each color on the Macbeth chart could be reproduced. In this example, the process from photographing to printing could be performed without using any processing liquid used in conventional color photography.

The image information of the processed light-sensitive material is read by a negative film scanner, Topaz made by Rhinotype Hell, which uses diffused light as reading light, and read by Apple Computer
When transferred to a Macintosh Quadra 840AV (manufactured by Macintosh), the resulting digital information was image-processed and then output by a Pictography 3000, a print of a good human image such as sharpness and graininess was obtained.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/30 G03C 7/30 7/46 7/46 G06T 1/00 H04N 1/00 GH 04N 1/00 1 / 04 107Z 1/04 107 G06F 15/62 310A

Claims (7)

[Claims] 1. A support comprising at least a photosensitive silver halide, a binder, and a dye-donating coupler,
After forming a color image of at least 3 colors by imagewise exposing and developing a light-sensitive material having at least 3 types of light-sensitive layers in which the light-sensitive wavelength region and the hue of the dye formed from the dye-providing coupler are different from each other, they remain. Silver halide,
An image forming method in which image information is converted into optical information or electrical information without removing developed silver, and a color image is obtained on another recording material based on the information. 2. The support of a light-sensitive material according to claim 1, wherein the support is a transparent support, and the transmission density of the light-sensitive material is Dmin at the maximum absorption wavelength of the dyes of three colors formed from the dye-donor coupler after development. Is 2.0 or less, Dmax is 4.0 or less, and Dmax-Dmin is 1.0 or more. An image forming method using a light-sensitive material. 3. A support containing at least a light-sensitive silver halide, a binder, a dye-donor coupler, and a developing agent capable of reacting with the dye-donor coupler to form a dye. Silver halide remaining after forming a color image of at least three colors by imagewise exposing and developing a light-sensitive material having at least three types of light-sensitive layers having different hues of dyes formed from a dye-donor,
An image forming method in which image information is converted into optical information or electrical information without removing developed silver, and a color image is obtained on another recording material based on the information. 4. The support according to claim 3, wherein the support of the light-sensitive material is a transparent support, and the transmission density at the maximum absorption wavelength of the dyes of three colors formed from the dye-donor coupler after development has a Dmin of 2.0. Below, Dmax is below 4.0, and Dmax-
An image forming method using a light-sensitive material characterized in that Dmin is 1.0 or more, and the density of the dye is. 5. A support containing at least a light-sensitive silver halide, a binder, a dye-donor coupler, and a developing agent capable of reacting with the dye-donor coupler to form a dye. A light-sensitive material having at least three types of light-sensitive layers having different hues of dyes formed from a dye-donor and a layer containing a dye that is decolored or removed during development is subjected to at least 3 by imagewise exposure and development. After forming a color image of color, the image information is converted into optical information or electrical information without removing the remaining silver halide and developed silver, and a color image is formed on another recording material based on the information. Image forming method for obtaining 6. The development processing temperature according to claim 5,
An image forming method, characterized in that the image forming method is a heat development method at a temperature of from 150 ° C to 150 ° C. 7. The image forming method according to claim 3, 5 or 6, wherein the photosensitive material is a photographic photosensitive material whose support is a transparent support.