JP2001209157A - Method for developing silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for developing a silver halide color photographic sensitive material by which its sensitivity, graininess, color reproducibility and photographing latitude are ensured even if the layer arrangement of the sensitive material is altered and development is accelerated. SOLUTION: A photosensitive material having red-, green- and blue-sensitive silver halide photosensitive layers each comprising unit emulsion layers having the same spectral sensitivity region and different from each other in sensitivity and having layer arrangement in which the highest sensitivity red-sensitive unit emulsion layer and the highest sensitivity green-sensitive unit emulsion layer are situated farther from the base than the lowest sensitivity red-sensitive unit emulsion layer and the lowest sensitivity green-sensitive unit emulsion layer, respectively, is developed with a color developing agent containing at least 1.8×10-2 mol/l color developing agent and a gradation adjuster.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a simple and rapid development processing method for a silver halide color photographic light-sensitive material, and more particularly, to a method for maintaining high sensitivity even in a rapid processing, and having granularity and color reproducibility. The present invention relates to a method for developing a color photographic light-sensitive material capable of obtaining an excellent image.

[0002]

2. Description of the Related Art In general, the processing of silver halide photographic materials, for example, the processing of silver halide color photographic materials,
Generally, the basic steps include a color developing step (particularly a color developing step), a desilvering step, and an image stabilizing step such as washing with water. In the color development step, an image-like dye and developed silver are generated by a reaction between the color developing agent and the silver salt. In the desilvering process,
The developed silver generated in the color development step is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing action, and is removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. Alternatively, oxidation to a silver salt and its removal are performed in one step by a bleach-fix solution. The image stabilization step is a step in which the atmosphere of the image layer is adjusted to ensure long-term stability of the generated image.
Alternatively, any of a washing with water and an image stabilizing bath, or a stabilizing bath instead of washing with water is performed. Each processing step is basically a step of immersion in an aqueous solution of a chemical (referred to as a processing liquid), so that the steps are complicated and a long processing time is required.

[0003] With the practical use of non-silver salt recording materials in recent years, and in particular, with the market of magnetic recording materials such as video cassettes and electronic recording materials such as digital cameras, the processing of silver halide photographic light-sensitive materials has been simplified and accelerated. Has become a strong demand from the market. However, when the processing speed of the silver halide photographic light-sensitive material is increased, the sensitivity is lowered, and particularly, the sensitivity of the red light-sensitive layer or the lower layer (the layer close to the support) is significantly reduced, resulting in high sensitivity and high image quality. Characteristic of silver halide photography.

As a solution to this problem, a technique is employed in which the arrangement of the unit emulsion layers of the respective photosensitive emulsion layers of the light-sensitive material is changed so that the high-sensitivity emulsion layers having a slow developing speed are collected in the upper layer (far side from the support). Is disclosed. For example, in US Pat. No. 5,965,340, for each silver halide photosensitive layer sensitive to red light, green light and blue light, an arrangement in which a high-sensitivity unit emulsion layer and a low-sensitivity unit emulsion layer are separated into an upper layer side and a lower layer side, respectively. A technique is disclosed in which the color development time is reduced to 2 minutes or less by reducing the thickness of the constituent layers. U.S. Pat. No. 5,968,718 also discloses a technique in which the high-speed unit emulsion layer and the low-speed unit emulsion layer of each silver halide emulsion layer are separately arranged so that the temperature can be increased rapidly. However, when these techniques are used, the processing time can be reduced, but there is a defect that graininess and color reproducibility are deteriorated.
This defect is particularly noticeable in the high exposure area.

[0005] On the other hand, it is well known that the graininess, the color reproducibility, and the gradation reproducibility similarly decrease because the development processing surface is speeded up simply by increasing the temperature or activation. ing. JP-A-11-149144, 1
JP-A Nos. 1-212227 and 11-174463 disclose examples in which an alkylsulfonic acid, an alkylene glycol, a polyvinylpyrrolidone and a urea derivative are added to a developer. These additives are used for the purpose of thickening the developing solution or for accelerating the developing process.
It is not a technology intended to improve the graininess and color reproducibility, and there is no improvement in the graininess and color reproducibility actually associated with the rapid development process. Absent. In addition, there is a problem that the use of these compounds slightly lowers the sensitivity.

As can be seen from the above prior art, attempts to improve the photographic material or the developing process for the purpose of simplifying and speeding up the developing process of a silver halide color photographic material have been made to improve the graininess and color reproducibility. It is accompanied by the defect of deterioration, and its solution is strongly desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned deficiencies associated with the processing of a silver halide color photographic light-sensitive material and to achieve simplification and speeding up of the development processing. . Specifically, even if the development process is accelerated,
An object of the present invention is to provide a method for developing a silver halide color photographic light-sensitive material in which sensitivity, granularity, and color reproducibility are maintained, and a wide latitude characteristic of a silver halide light-sensitive material for photography is secured. More specifically, a method for developing a silver halide color photographic material that ensures sensitivity, granularity, color reproducibility and photographing latitude even when the development processing is speeded up by changing the layer arrangement of the photosensitive material. It is to present.

[0008]

In order to achieve the object of the present invention, the present inventor added a gradation adjusting agent to a developing solution even if the development processing was accelerated using a photosensitive material having a changed layer arrangement. If so, they have found that they do not adversely affect sensitivity, granularity, and color reproducibility, and based on this fact, have further studied and arrived at the present invention. That is, the present invention is as follows.

1. A photographic light-sensitive material having, on a support, a red-sensitive silver halide light-sensitive layer, a green light-sensitive silver halide light-sensitive layer and a blue light-sensitive silver halide light-sensitive layer comprising at least two emulsion layers each having the same spectral sensitivity region and different sensitivity. Wherein the photographic light-sensitive material comprises a red-sensitive unit emulsion layer having the highest sensitivity and a green-sensitive unit emulsion layer having the highest sensitivity, and a red-sensitive unit emulsion layer having the lowest sensitivity and a green-sensitive unit having the lowest sensitivity. A layer arrangement provided on a side farther from the support than any of the emulsion layers, wherein the developing process contains at least 1.8 × 10 ^-2 mol / l of a color developing agent and a gradation adjusting agent A method for developing a silver halide color photographic light-sensitive material, wherein the method is performed using a color developing solution.

[0010] 2. 2. The silver halide color photographic light-sensitive material as described in 1 above, wherein the gradation adjusting agent is bromine ion and the concentration in the color developer is at least 1.6 × 10 ^-2 mol / l. Development processing method.

3. The tone adjusting agent is an alkyl sulfonic acid,
2. The method for developing a silver halide color photographic light-sensitive material as described in 1 above, wherein the method is at least one compound selected from polyethylene glycol, polyethylene glycol alkyl ether, urea and derivatives thereof, and polyvinylpyrrolidone.

4. Wherein the image information is photoelectrically read from the image obtained by the development process, the read image information is converted into electrical digital image information, and the electrical digital image information is subjected to image processing. The method for developing a silver halide color photographic light-sensitive material according to any one of the above items.

In general, a silver halide color photographic light-sensitive material for photographing has red-sensitive, green-sensitive and blue-sensitive photosensitive layers from the side closer to the support, and each photosensitive layer secures the photographing latitude. For this reason, the spectral sensitivity region is the same and is constituted by a plurality of silver halide emulsion layers having different sensitivities (herein referred to as unit emulsion layers). Since the development speed of the high-sensitivity unit emulsion layer is low, the composition of the high-sensitivity unit emulsion layer is divided and the high-sensitivity unit emulsion layer is separated from the surface side where the action of the developing solution is strong, that is, the side farther from the support, for speeding up. However, such a layer arrangement cannot be adopted because the sensitivity, granularity, color reproducibility, and photographing latitude are deteriorated as described above. In the present invention, it has been found that by adding a gradation adjusting agent to a color developer, it is possible to suppress the occurrence of such defects regarding graininess, color reproducibility and sensitivity that are not directly related to gradation. Based on these facts, the most sensitive unit emulsion layer in each of the red and green photosensitive layers is more preferably blue than any of the least sensitive unit emulsion layers in the red and green photosensitive layers. By arranging the layer farther from the support than the unit emulsion layer having the lowest sensitivity in the photosensitive layer, rapid development can be performed by simple means without exposing the above-mentioned defects. The meaning of “the same spectral sensitivity region” of the unit emulsion layer means that even if the detailed structure of the spectral sensitivity curve is slightly different between the unit emulsion layers, the unit is actually used for color light recording in the same spectral sensitivity region. means.

The term "tone adjusting agent" refers to a developing solution additive capable of changing the tone of an image obtained by a development process. Often has the side effect of. In the present invention, known gradation adjusting agents can be widely applied, but bromine ions, alkyl sulfonic acids, polyethylene glycol, polyethylene glycol alkyl ether,
Urea and its derivatives, and polyvinylpyrrolidone,
Particularly effective and preferable. Further, in the aspect of the present invention in which the developed image surface is photoelectrically scanned, image information is read, and the image information is converted into digital image information, a subsequent step such as a desilvering step following the development step is not necessarily required. And an image can be obtained more simply and quickly. Also,
Since the developed image is in the form of digital image information, it can be connected to various electronic image means and image transmission means, and the applicability is expanded.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail in the order of the color photosensitive material used in the present invention and the developing method. [Color light-sensitive material] The silver halide color photographic light-sensitive material used in the present invention is the unit emulsion having the highest sensitivity among the unit emulsion layers constituting each of the red-sensitive, green-sensitive and blue-sensitive silver halide photosensitive layers. A layer is provided further from the support than the slowest unit emulsion layer,
The most sensitive red-sensitive unit emulsion layer and the most sensitive green-sensitive unit emulsion layer are both farther from the support than either the least-sensitive red-sensitive unit emulsion layer or the least-sensitive green-sensitive unit emulsion layer. Is a photosensitive material having a layer arrangement provided in the above. At present, color photosensitive materials for photography widely used in various countries are arranged in such a manner that unit emulsion layers constituting respective red-sensitive, green-sensitive and blue-sensitive silver halide photosensitive layers are laminated and integrated for each photosensitive layer. In the light-sensitive material used in the present invention, at least one of the high-sensitivity red-sensitive unit emulsion layer and the most high-sensitivity green-sensitive unit emulsion layer is
The low-sensitivity red-sensitive unit emulsion layer or the lowest-sensitivity green-sensitive unit emulsion layer is not laminated and integrated, and has a structure in which the low-sensitivity unit emulsion layer and the high-sensitivity unit emulsion layer are separated.

The preferred layer arrangement is such that the most sensitive blue-sensitive unit emulsion layer, the most sensitive red-sensitive unit emulsion layer and the most sensitive green-sensitive unit emulsion layer are the least sensitive blue-sensitive unit emulsion layer, The light-sensitive material has a layer arrangement provided farther from the support than both the red-sensitive unit emulsion layer and the green-sensitive unit emulsion layer having the lowest sensitivity. By arranging such a high-sensitivity unit emulsion layer not only on the low-sensitivity unit emulsion layer having the same spectral sensitivity region but also on the side farther from the support than on the low-sensitivity unit emulsion layer having a different spectral sensitivity region, the original development is achieved. The development of the high-sensitivity unit emulsion layer having a slow progress speed is accelerated, and rapid development becomes possible. However, such a layer arrangement was accompanied by the above-described defects such as deterioration of graininess, but in the present invention, as described later, the defects are suppressed by a color developer containing a gradation adjusting agent.

The following are specific examples of the layer arrangement of the photosensitive material preferred in the present invention, but the layer arrangement of the photosensitive material used in the present invention is not limited to these examples.
In the following examples, the yellow filter layer, the intermediate layer, the antihalation layer and the like are omitted, and the case where the protective layer is composed of a plurality of unit layers is simply described as the protective layer. (Example 1) Protective layer High speed blue-sensitive unit emulsion layer Medium speed blue-sensitive unit emulsion layer Low speed blue-sensitive unit emulsion layer High speed green-sensitive unit emulsion layer High speed red-sensitive unit emulsion layer Medium speed green-sensitive unit emulsion layer Medium speed Red-sensitive unit emulsion layer Low-speed green-sensitive unit emulsion layer Low-speed red-sensitive unit emulsion layer Support

(Example 2) Protective layer High speed blue-sensitive unit emulsion layer High speed green-sensitive unit emulsion layer High speed red-sensitive unit emulsion layer Medium speed blue-sensitive unit emulsion layer Medium speed green-sensitive unit emulsion layer Medium speed red-sensitive unit emulsion Layer Low-speed blue-sensitive unit emulsion layer Low-speed green-sensitive unit emulsion layer Low-speed red-sensitive unit emulsion layer Support

(Example 3) Protective layer High-speed blue-sensitive unit emulsion layer Medium-speed blue-sensitive unit emulsion layer High-speed green-sensitive unit emulsion layer Medium-speed green-sensitive unit emulsion layer High-speed red-sensitive unit emulsion layer Medium-speed red-sensitive unit emulsion Layer Low-speed blue-sensitive unit emulsion layer Low-speed green-sensitive unit emulsion layer Low-speed red-sensitive unit emulsion layer Support

(Example 4) Protective layer High-speed blue-sensitive unit emulsion layer Medium-speed blue-sensitive unit emulsion layer High-speed red-sensitive unit emulsion layer Medium-speed red-sensitive unit emulsion layer High-speed green-sensitive unit emulsion layer Medium-speed green-sensitive unit emulsion Layer Low-speed blue-sensitive unit emulsion layer Low-speed green-sensitive unit emulsion layer Low-speed red-sensitive unit emulsion layer Support

(Example 5) Protective layer High-speed blue-sensitive unit emulsion layer Medium-speed blue-sensitive unit emulsion layer High-speed red-sensitive unit emulsion layer High-speed green-sensitive unit emulsion layer Medium-speed red-sensitive unit emulsion layer Medium-speed green-sensitive unit emulsion Layer Slow-sensitive blue-sensitive unit emulsion layer Slow-sensitive green-sensitive unit emulsion layer Slow-sensitive red-sensitive unit emulsion layer Support Particularly preferred layer arrangements in the above examples are Examples 2, 3, and 4.
And Example 5.

The layer structure of the color light-sensitive material used in the present invention has been described above. Next, the structure of the light-sensitive material other than the layer structure will be described. Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

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

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

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

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

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

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

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

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

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

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

Polymer coupler: P-1, described in JP-A-2-44345
P-5 (page 11). US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Preference is given to colorless masking couplers of formula (A) of claim 1 of WO 92/11575 (especially the exemplary compounds on pages 36 to 45).

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

As additives other than the coupler, the following are preferred. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pp. 140-144); Latex for impregnation of oil-soluble organic compound: latex described in US Pat. (Especially I-, (1), (2), (6), (12)
(Columns 4-5), US Pat. No. 4,923,787, column 5, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1, 27 (pages 24 to 48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15,
Especially I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; hardener: JP-A 1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13-
Compounds (H-1 to 54) represented by formulas (VII) to (XII) of 23, compounds represented by formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: disclosed in JP-A-62-168139.
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, in particular, 28, 29 of column 7;
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
Page a-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Page V-1 to 23, especially V-1, EP 445627A, page 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, 17 to 28 of EP 457153A
Pages III-1 to 36, especially III-1,3, WO 88/04794
Microcrystal dispersion of Dye-1 to 124, Compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular Compounds D-1 to 87 (3) of Compound 1, EP 519306A represented by formulas (1) to (3) ~ 28 pages), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (3) represented by formula (I) of US Pat.
1) (Columns 2 to 9); UV absorber: Formula (1) of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to 9)
P.), Compounds (3) to (66) represented by formula (I) in EP 520938A.
(Pages 10 to 44) and compounds HBT-1 to 1 represented by the formula (III)
0 (page 14), compound (1) represented by formula (1) in EP 521823A
~ (31) (columns 2-9).

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

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

In the color light-sensitive material used in the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 28 μm.
Is preferably not more than 23 μm, more preferably not more than 18 μm, particularly preferably not more than 16 μm. The film swelling speed T _1/2 is preferably 30 seconds or less,
Seconds or less are more preferred. T _1/2 is 30 ° C. with a color developing solution,
When 90% of the maximum swelling film thickness reached when the treatment is performed for 3 minutes and 15 seconds is defined as the saturated film thickness, it is defined as the time required for the film thickness to reach half of that value. The film thickness is controlled at 25 ° C and 55% relative humidity (2
T1 _{/ 2} is the thickness measured in A. Green et al. (Photogr. Sci. Eng.), 19 vol.
It can be measured by using a serometer (swelling meter) of the type described on pages 2,124-129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. From the maximum swelling film thickness under the conditions described above,
It can be calculated by the formula: (maximum swollen film thickness-film thickness) / film thickness.

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

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

Next, the cellulose triacetate and polyester support of the color light-sensitive material will be described. Association; 1
994.3.15.). Polyester is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, as aromatic dicarboxylic acid.
And 2,7-naphthalenedicarboxylic acid, terephthalic acid,
Examples of isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred are polyesters containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene is particularly preferable.
2,6-naphthalate. The average molecular weight range is about
5,000 to 200,000. T of the polyester of the present invention
g is 50 ° C. or higher, preferably 90 ° C. or higher. The polyester support has a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more, in order to make it difficult to form a curl
Heat treatment is performed below Tg. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The 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. Irregularities may be provided on the surface (for example, conductive inorganic fine particles such as tin oxide or antimony oxide may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing.
These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. To prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

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

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

It is preferable that the color photographic material has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the product was conveyed at 60 cm / min to a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the partner material is replaced with the photosensitive layer surface, 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.

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

Next, the color light-sensitive material used in the present invention is processed into a commonly used size standard such as a 35 mm roll 135 format, a sheet type 120 format and an APS format, and is loaded into a light-shielding packaging material such as a film cartridge. It is used. The light-shielding wrapping material 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 light-shielding packaging materials are described in JP-A 1-312537 and JP-A 1-312538. Especially 25
The resistance at 25 ° C. and 25% 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 to impart light-shielding properties.

The color photographic light-sensitive material used in the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system). In addition, an image obtained by developing the image as described later can be converted into a digital image to expand the use range. For example, by directly loading a developed APS system cartridge film or inputting image information of negative film, positive film, and print using 35 mm film scanner FE-550 or flat head scanner PE-550, the digital image obtained Data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL based on a light fixing type thermal color print system, a pictography 3000 based on a laser exposure heat development transfer system, or through an existing laboratory device through a film recorder. The Aladdin 1000 also transfers digital information directly to floppy disks and Zip disks.
Alternatively, it can be output to a CD-R via a CD writer.

Digital image information can be viewed on a TV screen, captured on a personal computer, recorded on a floppy disk, Zip disk, CD-R or hard disk, and sent to various digital printers other than silver halide color printers. Can be output.

[Development processing method]
The developing solution contains at least 1.8 × 10 ^-2
Color developer containing mol / liter and gradation adjusting agent
The development process is performed using
You. The above color developing agent concentration effectively promotes rapid development.
Concentration suitable for color development, along with a color developing agent
Directly related to gradation by adding gradation adjusting agent
There is no or graininess, sensitivity and color reproducibility
Even if the photosensitive material has the above layer arrangement,
Rapid processing is possible while maintaining usable quality. Current
General-purpose cameras supplied by photosensitive material manufacturers around the world
Color film has been accepted and accepted by
Standard processing recipes that are common to
An example of a common processing formula for film is Fuji Photo Film.
Irum Corporation's CN16 treatment, Eastman Kodak Company
Of C41). This country is common
Color development formula, which can be called standard development
The active drug concentration is about 1.6 × 10^-2Mol / l. I
However, in the present invention, the effects of the above-described invention are brought about.
To achieve this, the color developing agent concentration should be lower than this standard
Is also set high. Preferred color developing agent for the present invention
The concentration is 1.8 × 10^-2~ 15 × 10^-2Mol / liter
And more preferably 2.1 × 10^-2~ 5.2 × 10
^-2Mol / l.

Next, the gradation adjusting agent will be described. In the present invention, any known gradation adjusting agent can be used as long as it is a compound that can change the gradation by adding to a developer. Preferred gradation adjusting agents include bromine ion and alkyl sulfone. Acid, polyethylene glycol, polyethylene glycol alkyl ether, urea and its derivatives, and polyvinylpyrrolidone.

It is known that bromine ions are present as a fogging inhibitor in a developing solution and are produced as a by-product of a developing reaction from a photographic material with the development of the photographic material. In the above-mentioned general-purpose general processing formula for color negative film, the bromine ion concentration in the color developer is
This concentration is about 1.1 × 10 ^-2 mol / liter, which is also an appropriate concentration as an antifoggant for bromide ions in a standard developer, and a lower concentration or lower concentration of bromine ions in a developing replenisher. Most replenishers, which are not included, especially low replenishment systems do not contain bromide ions. In this case, the equilibrium state between the amount of bromine ions generated in the development reaction and the amount of bromine ions discharged from the developing tank It is also the concentration of When bromine ions are used as a gradation adjusting agent in the color developer used in the present invention, the bromine ion concentration should be at least 1.
6 × 10 ^-2 mol / l, preferably 1.65
× 10 ^{-2 to} 8.5 × 10 ^-2 mol / l, more preferably 1.68 × 10 ^{-2 to} 7.0 × 10 ^-2 mol / l. That is, the effect of the present invention appears at a concentration higher than the concentration generally used as an antifoggant. Therefore, the bromine ion is supplied by adding an amount exceeding the amount generated in the development reaction to the replenisher, or as a low replenishment process in which the replenishment amount is reduced, the equilibrium concentration of the bromine ion in the developer is increased to allow the development. Done. Bromine ions are added to the developer in the form of alkali metal salts and alkaline earth metal salts. Preferred salts are the alkali metal salts, especially the sodium and potassium salts, ie sodium and potassium bromide.

In the present invention, the polyethylene glycol alkyl ether used in the color developer is represented by the following general formula (I).

Formula (I) R ¹ — (OC ₂ H ₄ ) _n —OH In the formula (I), R ¹ represents an alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 50. The preferred compounds represented by the general formula (I) include the following. Among them, preferred compounds are (I-
3), (I-4), (I-5), (I-9) and (I-
11).

[0054]

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In the present invention, an alkylsulfonic acid or a salt thereof, which is a gradation adjusting agent, can also be used. Preferred alkylsulfonic acids are represented by the following general formula (II). Formula (II) R ² —SO ₃ M In Formula (II), R ² represents an alkyl group having 1 to 20 carbon atoms, and M represents a cation group. The alkyl group may be linear or branched. Preferred cationic groups are alkali metals, alkaline earth metals and Group 3 metals, particularly preferred are alkali metals, of which potassium and sodium are preferred.

The preferred compounds represented by the general formula (II) include the following. Among them, preferred compounds are (II-3), (II-4) and (II-
5), (II-9), (II-10) and (II-11).

[0057]

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The compound of the general formula (II) of the present invention
U.S. Pat.
JP-A-34161 and JP-A-11-149144 also suggest descriptions related to the technical concept of using the present compound (I) in combination with the above-mentioned photosensitive material having a unit emulsion layer structure. There is no such description.

The polyethylene glycol used in the color developer according to the present invention is represented by the following general formula (III). Formula _{(III) H (OC 2 H} 4) m -OH general formula (III), m represents an integer from about 500 or less. It can be said that the polyethylene glycol used in the above color developer is a polyethylene glycol having a number average molecular weight (hereinafter, simply referred to as an average molecular weight) of 20,000 or less.

As polyethylene glycol having an average molecular weight of 20,000 or less, diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight: 200, 300, 400, 600, 1000, 15)
40, 2000, 4000), preferably diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight: 1,000 to 20,000). The average molecular weight is preferably 100 to 50.
00.

In the present invention, ureas which are gradation adjusting agents can be used. Preferred ureas include the following compounds. Among them, (E-11) is preferable.

[0062]

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[0063]

Embedded image

In the present invention, polyvinyl pyrrolidone can be used by adding it to a developer. Preferred compounds of polyvinyl pyrrolidone include poly-N-vinyl-2-pyrrolidone and poly-N-vinyl-2-yl. A pyrrolidone / vinyl alcohol copolymer is exemplified. The average molecular weight of the polyvinylpyrrolidones is 1000 to 7000
0, preferably 1500 to 50,000. Also, poly-N-vinyl-2-pyrrolidone units in the poly-N-vinyl-2-pyrrolidone / vinyl alcohol copolymer /
Constituent ratio of vinyl alcohol unit is 99/1 to 50/5
0, preferably 90/10 to 50/50.

The addition amount of these tone adjusting agents to the developing solution is 0.1 to 100 g / l, preferably 0.2 to 50 g / l, except for bromine ions. Further, these tone adjusting agents may be used alone or in combination of two or more. If used together,
The amount of addition is used within the above-mentioned range for each compound. The effect of the present invention cannot be obtained as long as bromine ions are generated in a developing solution in a general developing process of a general-purpose film having a general arrangement of unit emulsion layers and exist as an equilibrium concentration. Even if the other tone adjusting agent according to the present invention is present in the developer having such an amount of bromine ion concentration, it is not considered to be used in combination with bromine ion.

More preferably, the compound represented by the general formula (I) and / or (II) is combined with diethylene glycol, triethylene glycol and / or polyethylene glycol (average molecular weight: 1,000 to 5,000) to form a poly- It is preferable to use N-vinyl-2-pyrrolidone in combination.

Having described the tone adjusting agent according to the present invention, the components of the color developing solution of the present invention other than the tone adjusting agent will now be described. The color developing solution is an alkaline continuous phase liquid containing components contained in a normal color developer in a dissolved state. Among them, a color developing agent is contained, and a preferred example is a known aromatic primary
Primary amine color developing agents, especially p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. In recent years, some black-and-white photosensitive materials include:
In some cases, a coupler is added so as to form a black color and a black-and-white image is formed using a general-purpose general color developing solution. However, the color developing solution of the present invention is used for processing a photosensitive material of this type. May also be applied.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-N, N-diethyl-3-methylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline 6) 4-amino- N-ethyl-N- (3-hydroxypropyl) -3-methylaniline 7) 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline 8) 4-amino-N-ethyl- N- (β-methanesulfonamidoethyl) -3-methylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-N-ethyl-N- (β -Methoxyethyl) -3 methyl-aniline 11) 4-Amino-N- (β-ethoxyethyl) -N-
Ethyl-3-methylaniline 12) 4-amino-N- (3-carbamoylpropyl-
Nn-propyl-3-methylaniline 13) 4-amino-N- (4-carbamoylbutyl-N
-N-propyl-3-methylaniline 15) N- (4-amino-3-methylphenyl) -3-
Hydroxypyrrolidine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Among the above-mentioned p-phenylenediamine derivatives, particularly preferred are the exemplified compounds 5), 6), 7), 8) and 12), among which the compounds 5) and 8) are preferred. Also, these p-phenylenediamine derivatives are
In the state of solid material, usually sulfate, hydrochloride, sulfite,
It is in the form of a salt such as naphthalenedisulfonic acid and p-toluenesulfonic acid. The concentration of the aromatic primary amine developing agent is preferably from 18 to 150 mmol, more preferably from 20 to 10 mmol, per liter of color developer.
0 mmol, more preferably 21 mmol to 52 mmol.

The color developer used in the present invention may contain a small amount of sulfite ion or may not substantially contain it depending on the kind of the light-sensitive material to be treated. This is because sulfite ions have a remarkable preservative action, but may adversely affect the photographic performance in the color development process depending on the target photosensitive material. Hydroxylamine may or may not be included in the components of the composition depending on the type of the light-sensitive material to be treated. This is because the photographic properties can be affected because the developer itself has a silver developing activity at the same time as the function as a preservative of the developer.

The color developing solution used in the present invention contains the above inorganic preservatives such as hydroxylamine and sulfite ion,
It preferably contains an organic preservative. The organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being included in a processing solution for a photosensitive material. That is, organic compounds having a function of preventing the color developing agent from air oxidation and the like, among them, hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxyketones,
Organic preservatives particularly effective for α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused ring amines, etc. It is. These are disclosed in JP-A-63-4235, JP-A-63-30845,
-21647, 63-44655, 63-53551, 63-43140
Nos. 63-56654, 63-58346, 63-43138, 63
No.-146041, No. 63-44657, No. 63-44656, U.S. Pat.
3,615,503, 2,494,903, JP-A-52-143020,
It is disclosed in each gazette or specification such as JP-B-48-30496.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. In particular, other than the above-mentioned alkanolamines, for example, alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamine such as disulfoethylhydroxylamine and diethylhydroxylamine, or aromatic polyamines The addition of a hydroxy compound is preferred. Among the above-mentioned organic preservatives, hydroxylamine derivatives are particularly preferred, and details thereof are described in JP-A Nos. 1-97953, 1-186939 and 1-186940.
And No. 1-187557. In particular, it is more preferable to use a hydroxylamine derivative and an amine in combination in view of improving the stability of the color developer and the stability during continuous processing. Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939. Examples thereof include amines described in JP-A-1-1187557.

The color developer of the present invention may optionally contain chlorine ions. A color developer (especially a developer for color printing materials) usually uses 3.5 × chloride ions.
Although it is often contained in an amount of 10 ^{-2 to} 1.5 × 10 ^-1 mol / l, chloride ions are usually released into a developing solution as a by-product of development, and therefore, it is often unnecessary to add them to a replenishing solution. The amount of chloride ions in the replenisher, and thus in the color developer from which it is based, is set such that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is at the above-mentioned concentration level. If the chloride ion concentration is more than 1.5 × 10 ^-1 mol / liter, it has the disadvantage of delaying the development, and is unfavorable because the speed and color density are impaired. Also,
If it is less than 3.5 × 10 ^-2 mol / l, it is often not preferable in preventing fog.

If bromine ions are not used for the purposes of the present invention, their contents are the same as for chloride ions. The amount of bromine ion in the color developer is preferably about 1 to 15 × 10 ⁻³ mol / liter in the processing of a photographic material, and 1.0 × 10 ⁻³ mol / liter or less in the processing of a printing material. If necessary, bromine ions may be added to the color developing solution in the processing composition so that the bromine ion concentration falls within this range. When included in a color developer, sodium chloride, potassium chloride, ammonium chloride, lithium chloride,
Examples thereof include nickel chloride, magnesium chloride, manganese chloride and calcium chloride, and among them, preferred are sodium chloride and potassium chloride. As bromine ion supply substances, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide,
Among them, thallium bromide is preferable, and potassium bromide and sodium bromide are preferable.

The color developer used in the present invention has a pH of
It is preferably from 9.0 to 12.2, more preferably from 9.9 to 11.2, and may contain compounds of other known developer components. In order to maintain the above pH, it is preferable to use various buffers. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate,
2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Especially carbonate, phosphate, tetraborate, hydroxybenzoate,
Excellent buffering ability in the high pH range of pH 9.0 or higher. Even when added to a color developer, adverse effects on photographic performance (fog etc.)
The use of these buffers is particularly preferred because they have the advantage of being inexpensive and inexpensive. Its concentration is 0.01 to 2 mol, preferably 0.1 to 2 mol per liter of developer.
It is added to the developer so as to be 0.5 mol.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.
The amount of the buffering agent is included so that the concentration in the color developer is 0.1 mol / L or more, especially 0.1 mol / L to 0.4 mol / L.

Further, in the present invention, it is preferable to use potassium hydroxide in addition to potassium carbonate as the alkali agent, and it is particularly preferable to use a part of potassium hydroxide by replacing it with lithium hydroxide. Thereby, the kit deposition preventing effect is improved.

The color developer used in the present invention may contain other color developer components, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium, or which also improve the stability of the color developer. Can also. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ',
N'-tetramethylene sulfonic acid, trans siloxane diamine tetraacetic acid, 1,2-diaminopropane tetraacetic acid,
Glycol ether diamine tetraacetic acid, ethylene diamine orthohydroxyphenyl acetic acid, ethylene diamine disuccinic acid (SS form), N- (2-carboxylate ethyl)
-L-aspartic acid, β-alaninediacetate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine- N,
N'-diacetic acid, 1,2-dihydroxybenzene-4,6
-Disulfonic acid and the like. These chelating agents may be used in combination of two or more as necessary. The amount of these chelating agents may be an amount sufficient to block metal ions in the color developer. For example, 0.1 g per liter
Add about 10 g.

The color developer of the present invention can optionally contain an optional development accelerator. As development accelerators, JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, and JP-B-44-123
No. 80, No. 45-9019 and U.S. Pat.No. 3,813,247, etc. and thioether compounds described in the specification and JP-A Nos. 52-49829 and 50-15554.
Phenylenediamine compounds, quaternary ammonium salts disclosed in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
No. 2,494,903, No. 3,128,182, No. 4,230,796, No. 3,
No. 253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc.
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat.No.3,532,501.Polyalkylene oxides other than those described in each publication or specification, and other 1-phenyl-3-pyrazolidones,
Imidazoles and the like can be added as needed.

An optional antifoggant can be added to the color developer according to the present invention, if necessary. As the antifoggant, an organic antifoggant other than the above-mentioned alkali metal halides such as sodium chloride, potassium bromide and potassium iodide can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples. Further, a surfactant, for example, various surfactants such as arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developer as needed.

The processing temperature of color development in the present invention is as follows.
In the case of color development of a color negative or color reversal film, the development temperature is from 30 to 80C, preferably from 35 to 70C, more preferably from 40 to 65C. The development processing time is 20 seconds to 6 minutes, preferably 25 to 200 seconds, more preferably 30 to 150 seconds. Also, in the case of a color negative, it is preferably 30 to 140 seconds. It is preferable that the replenishment amount is small, but 1 m ²
20 to 1000 ml is suitable, and preferably 5 to 1000 ml.
0-600 ml, particularly preferably 100-40
0 ml. This replenishing amount is the total amount of the replenisher composition and water when the concentrated replenisher composition and water are separately added to the developing tank. The present invention is particularly preferably applied to color negative processing.

After the development step using a color developer, a desilvering step is performed, and processing is performed using a bleaching solution and a fixing solution or a bleach-fixing solution. In a preferred embodiment of the present invention, an image obtained by color development is photoelectrically read, and digital image information obtained by digitally converting the read value is used. In this case, a development step is essential. However, a subsequent step such as a desilvering step may not be required. However, in the following description, a case where a subsequent step is also performed to obtain a developed photosensitive material will be described.

The desilvering process is performed using a bleaching solution and a fixing solution, or a bleach-fixing solution. A processing solution having a bleaching ability (bleach solution or bleach-fix solution) is described in JP-A-4-125558, page 4, lower left column.
The compounds and processing conditions described in line 16 to page 7, lower left column, line 6 can be applied. The bleach has a redox potential of 150
mV or more is preferable, but as a specific example,
Preferred are those described in 5-72694 and 5-73312, and particularly preferred are 1,3-diaminopropanetetraacetic acid and a ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A-5-73312.

Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a solution having bleaching ability.
It is preferred to design with a mole to 0.15 mole. When the bleaching liquid is a bleaching liquid, 0.2 mol to 1 mol / L is used.
It is preferred to contain mole bromide, especially 0.3 to
It is preferable to contain 0.8 mol. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, a known bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids) or citric acid, tartaric acid, malic acid Organic acids, such as persulfates and hydrogen peroxide, are preferred.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Aminopolycarboxylic acids or salts thereof useful for forming an organic complex salt of the following are listed: biodegradable ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L-asparagine Acid, beta-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3
-Diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
Iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl)
-L-aspartic acid, β-alanine diacetate, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because their iron (III) complex salts have good photographic properties. These ferric ion complex salts may be used in the form of a complex salt, or a ferric salt such as ferric sulfate,
A ferric ion complex salt may be formed in a solution using ferric chloride, ferric nitrate, ammonium ferric sulfate, ferric phosphate and a chelating agent such as aminopolycarboxylic acid. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, iron aminopolycarboxylate complexes are preferred, and the amount added is 0.01 to
1.0 mol / liter, preferably 0.05 to 0.50
Mol / l, more preferably 0.10 to 0.50 mol / l, even more preferably 0.15 to 0.40 mol / l.

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat.

The bleaching time is usually from 20 seconds to 6 minutes and 30 seconds, preferably from 30 seconds to 4 minutes and 30 seconds. Various known organic acids (eg, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.) and organic bases (eg, imidazole, dimethylimidazole, etc.) are used in the bleaching solution, bleach-fixing solution or fixing solution. Or a compound represented by the general formula (Aa) such as 2-picolinic acid described in JP-A-9-212819 and a general formula (B- It preferably contains the compound represented by b). The addition amount of these compounds is preferably from 0.005 to 3.0 mol, more preferably from 0.05 to 1.5 mol, per liter of the treatment liquid.

The fixing agent used in the bleach-fixing solution or the fixing solution includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. When the pH is lower than this, the desilvering property is improved,
The deterioration of the solution and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used in the present invention is 8
It is the following, 2-7 are preferred, and 2-6 are especially preferred. If the pH is lower than this, the deterioration of the solution and the leuco-formation of the cyan dye are promoted. To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. Also p-
It is also preferable to use the sulfinic acid described in JP-A-1-224762 in addition to the toluenesulfinic acid salt in order to improve the preservation. It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property, but it is more preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .

The bleach-fixing solution and the fixing solution preferably contain a free chelating agent which is not in the form of a metal complex from the viewpoint of improving the preservability. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, Sulfite ion releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and arylsulfinic acids such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It is preferable to contain the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. The bleach-fixing process and the fixing process according to the present invention have a processing time of 5 to 240 seconds, preferably 10 to 100 seconds. The processing temperature is 25 ° C to 80 ° C, preferably 30 ° C to
65 ° C. The replenishment rate is ² per m ² of photosensitive material.
0 ml to 250 ml, preferably 30 ml to 100 m
1, particularly preferably 15 to 60 ml.

After desilvering processing such as fixing or bleach-fixing, washing and / or stabilizing processing are generally performed. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture).
and Television Engineers) Vol. 64, pp. 248-253 (1955
May issue). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and the increase in the residence time of water in the tank causes the bacteria to propagate and the resulting suspended matter to adhere to the photosensitive material. Occurs. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively.
Further, chlorinated fungicides such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, copper ion, and others described in the official gazette.
1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) Can be used.

Also, aldehydes such as formaldehyde, acetaldehyde, pyruvaldehyde and the like which inactivate the remaining magenta coupler to prevent fading of the dye and generation of stain, methylol compounds described in US Pat. No. 4,786,583 and hexamethylentetramine Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seized patent publication 504609.
And azolylmethylamines described in JP-A Nos. 519190 and 519190 are added.

Regarding the washing and stabilizing steps, see JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, the treatment can be performed directly with the stabilizing solution without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin, a buffering agent for adjusting a membrane pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener can be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly performed without going through a washing step, a known method described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can be used. Can be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C.

Following the washing and / or stabilizing step, drying is performed. From the viewpoint of reducing the amount of water carried into the image film, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, it is possible to speed up the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in Japanese Patent Application Laid-Open No. 3-157650, it is possible to adjust the angle at which dry air is blown to the photosensitive material,
Drying can be accelerated by the method of removing the exhaust air.

In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used. The development process of the color light-sensitive material has been described above.
No. 18716, No. 18716, 651 left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development.

As the treating agent used in the present invention, those described in Hatsumei Kyokai Disclosure No. 94-4992, page 3, right column, line 15 to page 4, left column, line 32 are preferred. Further, as a developing machine to be used for this, as described in the right column of page 3
The film processor described in lines 22 to 28 is preferred.
Specific examples of preferred processing agents, automatic developing machines, and evaporation correction systems for carrying out the present invention are described in the above-mentioned published technical report from page 5, right column, line 11 to page 7, right column, last line. .

The supply form of the developer used in the present invention and the processing agent for desilvering and stabilizing used as required may be a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, It may be in any form such as a paste or an emulsion. As an example of such a treating agent, see JP-A-63-174.
53 is a liquid agent stored in a container with low oxygen permeability,
655, 4-230748 include vacuum-packed powders or granules,
No. 4-221951, granules containing a water-soluble polymer, JP-A-51-61837, JP-A-6-102628, tablets, JP-T-57-50048
No. 5 discloses a paste-like treating agent, and any of them can be preferably used. However, from the viewpoint of simplicity at the time of use, it is preferable to use a liquid which has been prepared in advance in a concentration in a state of use.

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

Since the present invention aims at a simple and rapid development process, as a public mode particularly suitable for this purpose, image information is photoelectrically read from an image obtained through a development process, and the read image information is converted into a digital image. There is a method to use it as information. Since the image information can be obtained only by the development step, an image can be obtained very quickly, and it is not always necessary to perform a subsequent step such as a desilvering step. it can. In the present invention, this embodiment will be referred to as a "digital imaging system", and this system will be described below.

In the method of the present invention in this embodiment, (1) a photographed silver halide color light-sensitive material is first subjected to a development process to form an image on each of the photosensitive layers (R, G, and B photosensitive layers). (2) Then, an image reading device (most practically an image scanner, hereinafter referred to as an image scanner) photoelectrically reads the image elements of the image of each photosensitive layer to obtain electrical image information, and (3) Then, the obtained image information is subjected to arithmetic processing to remove silver image and silver halide noise information and the like, thereby obtaining electrical blue, green, and red digital image information, and forming an image. Using the color light-sensitive material of the present invention for the color light-sensitive material,
This is an embodiment of the present invention comprising providing a color developing solution with a color developing agent concentration and a gradation adjusting agent according to the present invention. In the above method, in a further preferred embodiment, the image reading by the image scanner is performed by electrically reading the image element of the image of the one or more photosensitive layers by reflected light photoelectrically (referred to as first image information). )
The image elements of the image of one or more photosensitive layers including another photosensitive layer are read photoelectrically to obtain electrical image information (referred to as second image information), and obtain the obtained first and second image information. This is a method of obtaining electrical blue, green, and red digital image information by performing arithmetic processing on the second image information, and increasing the accuracy of image processing to obtain digital image information to improve color reproducibility and gradation reproducibility. Can be. At that time, when the developed photosensitive material is heated and dried to increase the transparency of the film in the middle of the reading operation of the first image information and the reading operation of the second image information, the reading accuracy of the second image information is improved. Particularly preferred. Therefore, the following description will be made in accordance with the mode of the separation reading method.

(Process Flow of Digital Imaging System) First, the outline of the process flow of this system will be described with reference to the drawings. FIG. 1 is a block diagram schematically showing the flow of the steps of the method of the present invention. In FIG. 1, a film processing and image reading unit 110 includes a developing unit 111, a first image information reading unit 112 using reflected light, and a heating / drying unit 113.
And a second image information reading unit 114 using transmitted light. The color film F is loaded into the image forming apparatus and transported to the film processing and image reading unit 110, where the development processing is performed in the development processing unit 111, and the respective photosensitive layers (R, R,
(G, B photosensitive layers). Next, in the first image information reading unit 112, a reflected light type image scanner (not shown) photoelectrically reads an image element of at least one of the images on the front side and the back side photosensitive layer to obtain first image information. After the reading of the first image information, the color film F is dried in the heating and drying unit 113 to make the non-image part transparent, thereby reducing the transmission density. In the color film F in which the image contrast of the transmission density is improved by making the non-image portion transparent, the image of the remaining photosensitive layer is photoelectrically read by the transmitted light type image scanner (not shown) in the second image information reading portion 114. To obtain second image information. The obtained first and second image information is in the form of a time-series electric signal,
After being transmitted to the image processing unit 120 and converted into a digital signal so that image processing can be performed, it is converted into electrical blue, green, and red digital image information. The electrical digital image information obtained by the above steps can then be applied to any color image forming means to obtain a color image.

Examples of the color image forming means include time-series electrical image signals such as color print using color photographic paper, ink jet, thermal dye transfer, and images recorded on magnetic recording media and optical recording media in the form of disks and tapes. Any known means that can convert a digital print image into an image can be used, and it is an excellent feature of the present invention that the digital print image can be freely converted.

(Form of Developing Process) The developing process can be performed by any known method and method such as immersion development, coating development, and spray development. Above all, a method in which only a processing solution that can permeate the photosensitive material and is supplied to the photosensitive material for processing is preferable because no waste liquid is generated. As a method for supplying a small amount of liquid, there is a method in which a photosensitive material is immersed in a processing liquid, and then an excess processing liquid is removed with a squeeze roller. As this method, the methods described in JP-A Nos. 9-15819, 9-15820 and 9-15822 are preferable. There is no particular limitation on the method of supplying the treatment liquid, but it is preferable to apply a coating treatment or a spray treatment.

(Reading of Image) An embodiment included in the present invention in which reading by reflected light and reading by transmitted light are applied to each photosensitive layer with the heating and drying process interposed therebetween will be described.
The image content may be read in any form as long as the image information of the three photosensitive layers can be read. Among them, the following forms are preferable. As the first image information, the image information recorded on the front side photosensitive layer obtained by reading from the front side of the photosensitive material is read with a blue filter light density, and the image information contained in all the photosensitive layers is transmitted light as the second image information. Read simultaneously. This system utilizes the fact that image information recorded on the front side photosensitive layer of the photosensitive material has high accuracy in reading by reflected light. A method in which image information of all photosensitive layers is obtained by a sensor for transmission density, that is, a sensor for reading second image information. The image reading sensor may be a transmission density reading sensor only. Further, the first image information is read only with the blue-sensitive highest sensitivity unit emulsion layer, and the blue-sensitive intermediate or low-sensitivity unit emulsion layer is read with a second image information reading device using a blue filter light density. A method for obtaining yellow image information of the entire blue photosensitive layer by calculation.

Hereinafter, the first image reading unit 112 and the second image reading unit 114 shown in FIG. 1 will be described by way of an example of reading an image of a black-and-white developed film. The first image reading unit 112 reads an image with an image scanner using reflected light (reflective image reading), and the second image reading unit 114 reads an image with an image scanner using transmitted light ( Transmission image reading). The reflection type image reading and the transmission type image reading can be performed by the following method. That is, a line CCD that reads the density of an image while sub-scanning the image on the developed film using a line CCD in which light receiving elements are arranged one-dimensionally and converts the density into an electric signal by the line CCD.
A scanning method and an area CCD method in which the density of an image is read two-dimensionally using an area CCD and converted into electric signals rearranged in chronological order by electric scanning from the area CCD can be adopted. .

FIG. 2 shows a schematic configuration of the first image information reading unit 112. As shown in FIG. 2, the first image information reading unit 112 photoelectrically converts the color image by irradiating light on the back side (support side) and the front side (emulsion side) of the film F and detecting the reflected light. The first image information is thereby obtained. The first image information reading unit 112 includes a light source 11, a mirror 12 that reflects light emitted from the light source 11 and reflected on the surface of the film F, a light amount adjustment unit 14 that can adjust the light amount, and a reflected light And a lens 16 for forming an image of the reflected light on the area sensor. Similarly, on the emulsion side, a light source 81, a reflecting mirror 82, a light amount adjusting unit 84,
It has a CCD area sensor 85 and a lens 86.

In the case of a general color negative film, the film F has red, green and blue photosensitive layers from the support side, and the light source 11 irradiates the red photosensitive layer.
The light source 21 irradiates the blue photosensitive layer. The CCD area sensor 15 receives reflected light from the red photosensitive layer, and the CCD area sensor 25 receives reflected light from the blue photosensitive layer. Therefore, the first image information mainly includes red and blue image information. Here, “mainly” is used because the reflected light may include not only monochromatic image information but also image information of an adjacent layer depending on the light intensity and the layer thickness.

The first image information obtained by the first image information reading section 112 is supplied to the image processing section 120 shown in FIG. The image processing unit 120 includes an image processing unit 120a that digitally converts one of the first image information, an image processing unit 120b that digitally converts the other, and an image processing unit 120c that converts second image information described later into a digital signal. You. The image processing unit 120a includes an amplifier 17 that photoelectrically detects the CCD area sensor 15 and amplifies the generated image signal, and an A / D converter 1 that digitizes the image signal.
8. CCD correction means 19 for performing a process of correcting variations in sensitivity and dark current for each pixel with respect to a signal digitized by the A / D converter 18; a log converter 20 for converting image data into density data; It has an interface 21 and is controlled by the CPU 26. Image processing unit 120b
Similarly, the amplifier 27 that photoelectrically detects by the CCD area sensor 85 and amplifies the generated image signal, A / A
D converter 88, CCD correction means 89, log converter 90,
It has an interface 91 and is controlled by the CPU 96. The image processing unit 120b is also controlled in the same manner as 120a.

FIG. 3 shows the operation timings of the light sources 11 and 81 and the CCD area sensors 15 and 85. A control circuit (not shown) controls the light sources 11 and 81 to be turned on alternately. And alternately irradiate light to the front side. The CCD area sensors 15 and 85 operate in synchronization with the lighting of the light sources 11 and 81 and operate so as not to receive the light of the opposite light source.

In the illustrated example, the light sources 11, 81 and C
The CD area sensors 15 and 85 are arranged so as to read the image of the film F at the same position, respectively.
Images of the film F at different positions (for example, positions shifted by one frame) may be read. That is, the irradiation positions of the light sources 11 and 81 are made different, and the focal positions of the CCD area sensors 15 and 85 are made different so as to image the film F having different irradiation positions.

The wavelengths of the light sources 11 and 81 may be different from each other, and the CCD area sensors 15 and 85 may be made to respond to the wavelength of the corresponding light source. In this case, CC
Since the D area sensor does not respond to the light on the opposite side, it is possible to turn on the light sources 11 and 81 at the same time and image the film F.

FIG. 4 shows a schematic configuration of the second image information reading unit 114. As shown in FIG. 4, the second image information reading unit 114 is provided downstream of the first image information reading unit 112 and the transparency processing unit 113, and irradiates light to the film F that has been subjected to the transparency processing, and By detecting transmitted light, a color image can be read photoelectrically, and a light source 31 disposed on the front side of the film F, and a reflection reflecting light emitted from the light source 31 and transmitted through the film F are reflected. It has a mirror 32, a light amount adjustment unit 34 capable of adjusting the light amount, a CCD area sensor 35 for photoelectrically detecting transmitted light, and a lens 36 for forming an image of the transmitted light on the area sensor. Note that the light source 31 may be arranged on the back side of the film F, and light transmitted from the back side may be detected. When the light source 31 irradiates the film F from the back side, the CCD area sensor 35 receives the transmitted light of the photosensitive layer of each color. Therefore, red, green, and blue image information are superimposed on the second image information.

[0120] The second image information obtained by the second image information reading unit 114 is supplied to the image processing unit 120c. The image processing unit 120c includes an amplifier 37 that photoelectrically detects and is generated by the CCD area sensor 35, amplifies the generated image signal, and an A / D converter 38 that digitizes the image signal.
For the signal digitized by the / D converter 38,
CC for correcting sensitivity variation and dark current for each pixel
D correction means 39, a log converter 40 for converting image data into density data, and an interface 41,
Controlled by the PU 46.

The first and second image information reading units 112,
At 114, the film F is conveyed so that the film surface is perpendicular to the optical axis, stops at a predetermined position, and is conveyed by an image frame pitch when a frame image is read.

The first and second image information reading units 112,
In the area CCD 114, a plurality of pixels for detecting light are arranged in a plane along the longitudinal direction and the width direction of the film F, and have a function of accumulating charges according to light received by all pixels. The frame image (two-dimensional) can be read electrically. Although the description has been mainly focused on the area CCD, a line CCD can be used instead of the area CCD. Line CC
When D is used, the film F need not be transported at the image frame pitch, but may be transported continuously. Line CC
D has a function in which a plurality of pixels for detecting light are linearly arranged along the width direction of the film F, and has a function of accumulating electric charges in accordance with the light received by the line pixels. (1D) is read electrically.

The first and second image information reading units 112,
Light sources applicable at 114 include tungsten, fluorescent lamps, light emitting diodes, and laser light.
In particular, the light sources 11 and 21 used in the first image information reading unit 112 are preferably infrared light, and the light sources 31 used in the second image information reading unit 114 are preferably infrared light or laser light. The wavelength of the infrared light is 80
0 nm to 1200 nm, preferably 850 nm to 1
100 nm.

The first and second image information reading units 112,
The first and second image information read at 114 are input to the image generator 60.

FIG. 5 shows the structure of the image generation unit 60, which includes memories 61 and 62 for storing first image information, a memory 63 for storing second image information, and red and black included in the first image information.
The linear conversion unit 64 that weights the red, green, and blue image information included in the blue image information and the second image information with a predetermined coefficient by a known linear conversion, performs an addition process based on the weighted result, and outputs red, green, An adder 65 is provided for separately deriving blue monochromatic image information. The digital image data of each color obtained by the image generation unit 60 is output to the digital image processing unit 70.

FIG. 6 shows a schematic configuration of the digital image processing section 70. The digital image processing unit 70 is capable of inputting image data obtained by photographing with a digital camera 71 or the like. The digital image processing unit 70 is capable of inputting image data obtained by reading a transparent original, a reflective original, or the like with a scanner 72, or a computer or the like. Thereafter, the floppy disk drive 73, the MO drive or the CD drive 74 is stored in the recording medium.
And image data (image file data) input through communication via the modem 75 and the like.

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

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

In the above image reading, the first image information reading unit 112 reads the image from the front and back sides twice, and the second image information reading unit 114 reads the image once. It is not always necessary to separate the information into transmission reading, and image information of three image layers may be read by any one of them. In such a case, the image of the color-developed film is read by the first or second image information reading unit (112 or 114) so as to obtain density information of the photosensitive layer of a desired color.
By controlling the wavelength of the color image, a color image recorded on a desired image layer can be selectively extracted.

[0130]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
Although described, the present invention is not limited to these.
No. Example 1 Preparation of Color Negative Film (1) Preparation of Comparative Sample A For comparison with the present invention, a general-purpose color negative film was prepared.
Comparative sample A having a layer configuration was prepared according to the following specifications. <Preparation of Emulsion> (Preparation of Em-A) Low molecular weight gelatin having a molecular weight of 15,000
Aqueous solution containing 1.0 g of tin and 1.0 g of KBr
Literature (hereinafter referred to as “mL”) at 35 ° C.
Keep and stir vigorously. AgNO_ThreeWater containing 1.9g
30 mL of liquid, 1.5 g of KBr and low molecular weight of 15,000
30 mL of an aqueous solution containing 0.7 g of gelatin
It was added for 30 seconds by the jet method to form nuclei. this
At that time, the excess concentration of KBr was kept constant. Add 6g of KBr
The mixture was heated to 75 ° C. and aged. After aging, succulent
35 g of gelatin was added. The pH was adjusted to 5.5.
AgNO_Three150mL aqueous solution containing 30g and KBr aqueous solution
The liquid was added by the double jet method over 16 minutes. this
The silver potential at -25 mV with respect to the saturated calomel electrode.
Was. Furthermore, AgNO_ThreeAqueous solution containing 110 g and KB
The final flow rate of the aqueous solution is doubled by the double jet method.
Accelerate the flow rate to 1.2 times and add over 15 minutes
did. At this time, AgI fine particle milk having a size of 0.03 μm
At the same time so that the silver iodide content is 3.8%
The addition was accelerated and the silver potential was kept at -25 mV. A
gNO_Three132mL aqueous solution containing 35g and KBr aqueous solution
The liquid was added by the double jet method over 7 minutes. End of addition
The KBr aqueous solution was added so that the potential at the end was -20 mV.
Was adjusted. After bringing the temperature to 40 ° C.,
5.6 g in terms of conversion and 0.8 M sodium sulfite
64 cc of the aqueous solution was added. NaOH aqueous solution
To raise the pH to 9.0 and hold for 4 minutes.
After a rapid on formation, the pH was returned to 5.5.
After returning the temperature to 55 ° C, sodium benzenethiosulfonate
Lium, 1mg, and calcium concentration 1p
13 g of lime-treated gelatin at pm were added. End of addition
Later, AgNO_Three, 70 mL of an aqueous solution containing 70 g and K
Bring the aqueous solution of Br for 20 minutes while maintaining the potential at 60 mV.
Was added. At this time, the yellow blood salt was added in an amount of 1. mol per mol of silver.
0x10 ^-FiveMole was added. After washing with water, calcium concentration
Add 80 g of 1 ppm lime-processed gelatin, and at 40 ° C
The pH was adjusted to 5.8 and pAg to 8.7.

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

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

[0134]

[Table 1]

[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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

[0142]

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

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

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

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[0147]

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[0148]

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(Preparation of Em-G)
Water containing 1.0 g of low molecular weight gelatin and 1.0 g of KBr
The liquid (1200 mL) was kept at 35 ° C. and stirred vigorously. Ag
NO _Three30 mL of an aqueous solution containing 1.9 g, 1.5 g of KBr
And 0.7 g of low molecular weight gelatin having a molecular weight of 15,000
30 mL of the aqueous solution is applied for 30 seconds by the double jet method.
Nucleation was performed by addition. At this time, the excess concentration of KBr is reduced to one.
Kept constant. 1.5 g of KBr was added, and the temperature was raised to 75 ° C.
Matured. After ripening, the above-mentioned trimellitized gelatin
15 g and 20 g of the above-mentioned phthalated gelatin were added. p
H was adjusted to 5.5. AgNO_ThreeWater containing 30g
150mL of KBr solution and 16 mL of KBr aqueous solution by double jet method
Added over minutes. At this time, the silver potential becomes saturated calomel.
It was kept at -25 mV with respect to the electrode. Furthermore, AgNO_Three
Double jet of aqueous solution containing 110 g and KBr aqueous solution
Flow rate so that the final flow rate is 1.2 times the initial flow rate.
Added rapidly over 15 minutes. At this time, the size
A 0.03 μm AgI fine grain emulsion having a silver iodide content of
At the same time, accelerate the flow rate so that it becomes 3.8% and add it.
The silver potential was kept at -25 mV. AgNO_ThreeIncluding 35g
132mL aqueous solution and KBr aqueous solution by double jet method
Added over 7 minutes. Set the potential to -60 mV
The addition of the aqueous KBr solution was adjusted. 0.03μ size
m of AgI fine grain emulsion was added in an amount of 7.1 g in terms of KI.
Add 1 mg of sodium benzenethiosulfonate and add
Lime-treated gelatin with a calcium concentration of 1 ppm
3 g were added. After the addition is completed, AgNO_ThreeWater containing 70g
The potential of 250 mL of the solution and the aqueous KBr solution was maintained at 60 mV.
Over a period of 20 minutes. At this time, yellow blood salt
Of 1.0 × 10^-FiveMole was added. Washing
After that, lime-treated gelatin 8 with a calcium concentration of 1 ppm
0 g and adjusted to pH 5.8 and pAg 8.7 at 40 ° C.
It was adjusted.

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

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

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

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

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

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

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

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

(Formation of Outer Shell Layer 5) Silver nitrate 34.9
g was added over 22 minutes. This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and the average silver iodide content was 5.5 mol.

[Chemical sensitization] After rinsing with water, the succination ratio was 9
Add 8% succinated gelatin and calcium nitrate and add 40%
PH was adjusted to 5.8 and pAg to 8.7 at ℃. Rise to 60 ° C
Then, a 0.07 μm silver bromide fine grain emulsion was added to 5 × 10^-3Mo
After 20 minutes, sensitizing dyes 9, 10, and 11 were added.
Was. Then potassium thiocyanate, chloroauric acid, thiosulfuric acid
Sodium, N, N-dimethylselenourea, compound 4
Was added for optimal chemical sensitization. 20 minutes before the end of chemical sensitization
Compound 3 was added, and compound 5 was added at the end of chemical sensitization.
Was. Here, the optimal chemical sensitization means that the exposure is 1/100.
Sensitizing dyes and each to maximize sensitivity when illuminated
The compound was added in an amount of 10 ^-1From 10^-8
It means that it was selected from the range of addition amount of mol.

[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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

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

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

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

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

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

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(Em-D, H, I, M, N) For the preparation of tabular grains, low molecular weight gelatin was used according to the examples of JP-A-1-158426. Also, Japanese Patent Application Laid-Open
Gold sensitization, sulfur sensitization, and selenium sensitization were performed in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate according to the examples of -237450. Emulsions D, H, and I contain optimum amounts of Ir and Fe. Emulsions M and N were subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

[0173]

[Table 2]

[0174]

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[0175]

[Table 3]

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

<Coating of Constituent Layer on Support> The photosensitive material used in this example was prepared by the following method.

1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 0.2 Torr, a partial pressure of H ₂ O in an atmosphere gas of 75%, a discharge frequency of 30 kHz were applied to both surfaces of the support. , Output 25
Glow discharge treatment was performed at 00 W and a treatment intensity of 0.5 kV · A · min / m ² . A coating solution having the following composition was applied as a first layer on the support at a coating amount of 5 mL / m ² using a bar coating method described in Japanese Patent Publication No. 58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration) 50 parts by mass 10% aqueous dispersion. A secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) gelatin 0.5 part by mass water 49 parts by mass polyglycerol polyglycidyl ether 0.16 parts by mass poly (degree of polymerization 20) oxyethylene 0.1 parts by weight sorbitan monolaurate

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

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

After the support with the backing first layer and the undercoat layer is prepared as described above, further, the second and third layers described later are sequentially applied on the first layer, and finally, described later. A transparent magnetic recording medium having a silver halide emulsion layer was prepared by coating a color negative photosensitive material having the composition on the opposite side in a multilayer manner.

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

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

The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the mixture was finely dispersed in a sand mill (1/4 G sand mill) at 2000 rpm for 4 hours according to the following formulation. did. As the medium, glass beads having a diameter of 1 mm were used.

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

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

With the following formulation, an α-alumina abrasive dispersion used in the present invention was prepared.

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

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

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

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

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

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

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

3) Third Layer (High Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Stock Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, dispersed with a high-pressure homogenizer, and dispersed Was prepared.

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

Solution A Cyclohexanone 8600 parts by mass

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

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

[0201]

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

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

Diacetone alcohol 252.93 parts by mass

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

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

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

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

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

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

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

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

(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 hardener (specific compounds are described below with numerical values following symbols and chemical formulas after).

The numbers corresponding to the respective components indicate coating amounts in units of g / m ² , and silver halide indicates the coating amount in terms of silver.

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

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

Third layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.809 Em-C silver 0.486 ExC-1 0.263 ExC-2 0.015 ExC-3 0.105 ExC-40 .169 ExC-5 0.014 ExC-6 0.011 Cpd-2 0.035 Cpd-4 0.035 Cpd-7 0.070 Cpd-8 0.070 HBS-1 0.160 HBS-5 0.053 Gelatin 2.064

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

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

Sixth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.428 Em-G silver 0.433 Em-I silver 0.114 ExM-2 0.491 ExM-3 0.061 ExY-1 0.022 HBS-1 0.139 HBS-3 0.013 HBS-4 0.100 HBS-5 0.712 Cpd-5 0.013 Cpd-6 0.091 Gelatin 1.911

Seventh layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.794 ExC-6 0.002 ExM-1 0.013 ExM-2 0.011 ExM-3 0.030 ExM-40 017 ExY-5 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 Cpd-7 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939

Eighth Layer (Yellow Filter Layer) Cpd-1 0.094 Solid Disperse Dye ExF-2 0.150 Solid Disperse Dye ExF-5 0.010 Oil-soluble Dye ExF-7 0.010 HBS-1 0.049 Gelatin 0.630

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

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

Eleventh layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 Gelatin 1.984

Twelfth layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S- 1 0.200 Gelatin 0.750

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

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the eighth layer was dispersed by the following method.

ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0. 011 kg water 4.020 kg total 7.210 kg (adjusted to pH = 7.2 with NaOH)

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

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

The compounds used for forming each layer are shown below.

[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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As described above, a color negative photosensitive material sample A for comparison was prepared. This comparative sample A was subjected to ISO 1007
135-24Ex (standard 35mm, 24
(With patrone), and used in the following tests.

(2) Sample 101 of Example of the Present Invention The same support as that of Comparative Sample A described above, which had the first to third backing layers and the undercoat layer coated thereon, an emulsion and additives were used, and the layer constitution was as follows. The sample 101 of the example of the present invention was manufactured by changing the above.

[Layer arrangement order (from support side)] [Contents of layer] First layer (first antihalation layer): same as first layer of comparative sample A Second layer (second antihalation layer): Same as the second layer Same as the second layer Third layer (low-sensitivity red-sensitive emulsion layer): Same as the third layer Fourth layer (intermediate layer): Same as the sixth layer (intermediate layer) Emulsion layer): Same as the eighth layer (low-sensitivity green-sensitive emulsion layer) Sixth layer (intermediate layer): Same as the sixth layer (intermediate layer) Seventh layer (low-sensitivity blue-sensitive emulsion layer): Same Same as 12 layers (low-sensitivity blue-sensitive emulsion layer) 8th layer (intermediate layer): Same as 6th layer (intermediate layer) 9th layer (high-sensitivity red-sensitive emulsion layer): Same as 4th layer (high-sensitivity red) Same as the 10th layer (intermediate layer): Same as the sixth layer (intermediate layer) Same as the 11th layer (high-sensitivity green-sensitive emulsion layer): Same as the 10th layer (high-sensitivity green-sensitive emulsion layer) Layer 12 (Ye Low filter layer): Same as layer 11 (yellow filter layer) Same as layer 13 (high-sensitivity blue-sensitive emulsion layer): Same as layer 10 (high-sensitivity blue-sensitive emulsion layer) Layer 14 (first layer) Protective layer): Same as the eleventh layer (first protective layer) Fifteenth layer (the second protective layer): Same as the same as the twelfth layer (the second protective layer)

A sample 101 of the present invention example having the above-described layer structure was prepared and processed into a form of 135-24Ex (normal 35 mm, containing 24 cartridges) according to the ISO1007 standard in the same manner as the comparative sample A. Used.

[0248] 2. Photographic property test The sample 101 having the layer structure of the present invention and the sample A for comparison were subjected to IS
Sensitometric exposure was carried out through a standard C light source and a continuous light wedge of neutral color (density gradient 0.4 D / cm, density range 0.02 to 4.8) according to the method described in O5800 (sensitivity measurement method for color negative film). went. In the following development processing,
The photographic characteristics (sensitivity, gradation and fog) were determined using this exposed sample.

[Development processing] Development processing was carried out using the following color negative developing machine and processing specifications. The color developing solution contains 1.95 × 10 ⁻² mol / liter of a color developing agent and a gradation adjusting agent as shown in Table 4. The processing machine used was an automatic processor FP-36 manufactured by Fuji Photo Film Co., Ltd.
An experimental machine with a modified processing time of 3SC was used.

The processing steps and the composition of the processing solution are shown below. The use of this development is a high-temperature rapid processing compared to the general-purpose processing commonly used in each country for general-purpose color negative films in the market. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 2 minutes 10 seconds 41.0 ° C 15 ml 10.3 L Bleaching 25 seconds 40 ° C 5 ml 3.6 L Setting (1) 25 seconds 40 ° C-3. 6L fixed (2) 25 seconds 40 ° C 7.5ml 3.6L stable (1) 14 seconds 40 ° C-1.9L stable (2) 13 seconds 40 ° C-1.9L stable (3) 13 seconds 40 ℃ 30ml 1.9L Drying 30 seconds 60 ° C * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1 bottle)

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. Also, 15 ml of the tank solution of the stabilizing solution (2) flows into the fixing solution (2), which corresponds to the replenishing amount. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 ml per 1.1 mm width of 35 mm photosensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution Replenisher Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.5 g Disodium-N, N-bis (sulfonateethyl ) Hydroxylamine 10.0 g 15.0 g Sodium sulfite 4.0 g 9.0 g Potassium bromide 1.4 g-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 5. 7 g 12.7 g Potassium carbonate 39 g 59 g Compounds listed in Table 4 (See Table 4) (See Table 4) 1.0 L 1.0 L pH by adding water (adjusted with sulfuric acid and KOH) 10.12 11.25

(Bleaching solution) Tank solution Replenisher 1,3-diaminopropanetetraacetic acid ammonium ferric ammonium monohydrate 160 g 240 g Ammonium bromide 50 g 70 g Succinic acid 15 g 25 g Imidazole 60 g 90 g Add water 1.0 L 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 4.6 4.0

(Fixing solution) Tank solution Replenisher Ammonium thiosulfate (750 g / L) 295 ml 785 ml Aqueous ammonium bisulfite solution (72%) 20 g 80 g Imidazole 5 g 45 g 2-mercaptotriazole 1 g 3 g Ethylenediaminetetraacetic acid 8 g 12 g Water was added to 1 L 1 L pH (adjusted with aqueous ammonia and nitric acid) 7.0 7.0

(Stabilizing solution) Common to tank solution and replenisher p-toluenesulfinic acid rim 0.03 g p-nonylphenoxypolyglycidol (glycidol average degree of polymerization 10) 0.4 g disodium ethylenediaminetetraacetate 0.05 g 1 1,2,4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2-benzisothiazolin-3-one 0.10 g 0L pH 8.5

In order to show that the development processing of the method of the present invention is a rapid processing, a standard which is substantially common to each country and used by general color developing laboratories for general purpose color negative films is referred to. The processing specifications are described below. In this development processing specification, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate is used as a color developing agent at 1.6 × 10 ⁻² mol / l. I have. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity ** Color development 3 minutes 05 seconds 38.0 ° C 15ml 10.3L Bleaching 50 seconds 38 ° C 5ml 3.6L Settling (1) 50 seconds 38 ° C- 3.6L Settling (2) 50 seconds 38 ° C 7.5ml 3.6L Stability (1) 30 seconds 38 ° C-1.9L Stability (2) 20 seconds 38 ° C-1.9L Stability (3) 20 Seconds 38 ° C 30ml 1.9L Drying 1 minute 30 seconds 60 ° C Note * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1 bottle) ** Tank capacity is the same as that used in Example 1. Only the capacity of the developing machine is shown, but it has no direct relation to the international standard processing specifications.

The stabilizing solution is of the countercurrent type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developer brought into the bleaching process,
The amount of the bleaching solution brought into the fixing step and the amount of the fixing solution brought into the washing step were 2.5 ml, 2.0 ml and 2.0 ml, respectively, per 0.039 m2 of the light-sensitive material. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

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

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

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium bisulfite (72% solution) 20 80 Aqueous ammonium thiosulfate (750 g / L) 280 mL 745 mL Imidazole 5 45 2- (N, N-dimethyl) ) Ethylaminomercaptotetrazole 1.0 3.0 Ethylenediaminetetraacetic acid 8 12 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.0 7.0

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.4 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 1.0 liter with water pH 8.5

[Evaluation and Evaluation Results] The evaluation of the test was based on the evaluation of color turbidity as a measure of sensitivity, granularity and color reproducibility.
Evaluation items were performed. The sensitivity was evaluated by relative sensitivity. That is, the reciprocal of the exposure amount corresponding to the minimum density (Dmin) +0.3 is determined as a sensitivity value in accordance with the sensitivity measurement method for color negative films of the international standard (ISO5800), and the sensitivity value of the sample A in the standard processing is used as a reference. The difference (ΔS) was calculated. The larger the positive value, the higher the sensitivity. Graininess is determined by the neutral color step exposure part (white light exposure part) of each sample
The RMS granularity value at a density of minimum density (Dmin) +2.1 with an aperture having a diameter of 48 μm and an aperture of 48 μm was determined. The color reproducibility is determined by applying a stepwise exposure of blue light to each sample and performing development processing, and the density of the green filter light at an exposure amount at which the density of the blue filter (yellow density) is the minimum density (Dmin) +2.1. The value obtained by subtracting the green filter light density (magenta density) at the minimum density part of the characteristic curve of the yellow image from (magenta density) was determined as the degree of color turbidity for each sample. The smaller the value is, the less the color turbidity is, indicating that the color reproducibility is excellent. Table 4 shows the evaluation results.
Shown in

[0263]

[Table 4]

[0264]

[Table 5]

As shown in Table 4, when the sample 101 having the layer constitution of the unit emulsion layer of the present invention was treated with each color developing solution,
Although the sensitivity is higher than that of Comparative Sample A, focusing on the type of the color developer, when the additive (gradation adjuster) of the present invention is not contained in both the standard processing and the rapid processing (Test No. 2, 4) is extremely poor in graininess and color reproducibility (especially in a high density portion, that is, a high exposure portion). On the other hand, it can be seen that the granularity and the color reproducibility are improved at least as much as Comparative Sample A in some cases by the rapid processing and the addition of the additive (gradation adjusting agent) of the present invention. That is, the granularity and color reproducibility were maintained or improved by changing the arrangement of the unit emulsion layers to the arrangement of the present invention and adding the additive of the present invention to the developer. On the other hand, in the sample A of the comparative example, the sensitivity is low, and the addition of the gradation adjusting agent shows very little improvement in granularity and color reproducibility. Furthermore, it was also recognized that when these tone adjusting agents having excellent effects were used in combination, the effect was further increased in Sample 101 having the layer configuration of the present invention (Test Nos. 34 and 36).

Example 2 Using the photosensitive material sample 101 used in Example 1, the comparative sample A, and a color developer, a test was performed to obtain an image of a developed film in the form of digital image information. Automatic processing machine FP-363 manufactured by Fuji Photo Film Co., Ltd. as a development processing and image information reading device
An image reading device and an intermediate heating / drying unit were provided in the SC, and a development processing device with an image reading device for an experiment, which was modified in the manner described with reference to FIGS. And read the image information. That is, the bleaching tank of the automatic developing machine FP-363SC manufactured by Fuji Photo Film Co., Ltd. is changed to a stopping liquid tank, and a conveying path is provided for allowing the film passing through the squeegee blade to be taken out of the stopping liquid tank. The reservoir and the first image information (reflected light image information) reading unit, the heating / drying unit, and then the reservoir and the second image information (transmitted light image information) reading unit are arranged in this order. A change was made so that a path for discharging the film read from the second image information reading section and a path for returning the film to the desilvering processing tank of the developing device could be selected.

Therefore, the flow of the color film in this device is as follows. That is, after the color film is developed in the developing tank, the development is stopped by the stop solution, sent out by the transport mechanism, reaches the first image information reading unit via the reservoir, and reads the first image information. Was made. After this reading, the color film reaches the heating and drying unit by the transport mechanism and is dried. The dried color film reached the second image information reading unit via the reservoir along the transport path, and the second image information was read by transmitted light.
For reading of each image information, the status A (red, blue, green) corresponding to the color image of each photosensitive layer was used.

The color film that has been read in these two ways is discarded. However, in addition to obtaining an image in the form of digital image information or a color print that outputs the information, it is also necessary to leave a developed film. Therefore, in this experimental apparatus, the original stabilizing baths (1) and (2) are further changed to bleach-fixing baths and filled with bleach-fixing solution.
The stabilizing bath (3) is filled with a stabilizing solution. Therefore, after the image is read, the film is desilvered in a bleach-fixing tank, the image is stabilized in a stabilizing bath, and a developed film having the same image quality as that processed in a color lab in the market via a drying unit can be obtained. .

The processing steps of Example 1 of the present invention described above were performed according to the following specifications. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 2 minutes 10 seconds 41.0 ° C 15 ml 10.3 L Stop bath 10 seconds 38.0 ° C 10 ml 3.6 L First image information reading Heat drying 17 seconds 80 2.0 ° C (maximum temperature) Reading of second image information * Replenishment amount per photosensitive material 35 mm width 1.1 m (equivalent to 24 Ex. 1 line)

The formulation of the color developing solution was the same as that used in Test Nos. 3 and 4 of Example 1, and those used in 35 and 36, and a 3% by mass aqueous solution of acetic acid was used as the stop solution.

Image reading and image processing were performed as follows. That is, the first and second image information read by the first and second image information reading units 112 and 114 described in FIGS. 2 and 4 are converted into a positive image by the digital image processing unit 70 described in FIG. Generated and output to printer. The reading of the first image information was substantially carried out on the high-sensitivity bluish unit emulsion layer. All the emulsion layers were read by the second image information reading section. The image information of the yellow image is subjected to high-precision correction of the first image information by the read value of the second image information reading device.

A high-speed scanner / image processing workstation SP is an example of a commercially available input device capable of converting an input image produced by the above configuration into an electric image signal and producing a positive image by inputting the signal. -1500 (manufactured by Fuji Photo Film Co., Ltd.), a laser printer / paper processor LP-1500SC as an example of a commercially available output device
(Frontier 350 manufactured by Fuji Photo Film Co., Ltd.) was used. In addition, SP-1500 was used after changing the program software so that the image processing could be performed.

For printing of the developed films of Test Nos. 1 to 4 (see Table 5), commercially available Fuji Color Paper SUPER FA Type D was used as the color paper.
The development processing is a general color paper processing formula CP-48.
S and its treating agent (both manufactured by Fuji Photo Film Co., Ltd.)
This was performed using

The photographic characteristics test and evaluation method are as follows. Each test film was exposed to a standard C light source described in ISO5800 (sensitivity measurement method for color negative film), and was exposed to two levels of standard exposure of 5 aperture overexposure and 3 aperture underexposure. Was photographed, processed under the above development processing conditions and image processing conditions, exposed to color paper and developed to obtain a print image for evaluation. The image quality evaluation focusing on the shadow gradation (sensitivity), the granularity, and the color saturation of this evaluation image was evaluated by the following five-point method by 50 randomly extracted persons, and evaluated by the average score.

1 point 2 points inferior 2 points 3 points slightly inferior 3 points Normal (same level as print quality used in daily life) 4 points 5 points ·····good

The test results are shown in Table 5.

[0277]

[Table 6]

As can be seen from Table 5, photosensitive material sample 101
In the present invention example (Test No. 4) in which was treated with a color developer to which a gradation adjusting agent was added, excellent image quality evaluation was obtained.
In Comparative Sample A, the graininess and color turbidity of the shadow portion and the darkness of the image (insufficient sensitivity) were observed even after the image processing was performed (Test Nos. 1 and 3). In addition, photosensitive material sample 1
Even when using No. 01, when no gradation adjusting agent was contained (Test No. 2), the degree of improvement in image quality was small. this is,
It was noticeable in the over-exposed area. Therefore, in the case of the present invention example in which the photosensitive material sample 101 was treated with the color developing solution to which the gradation adjusting agent was added, a wide exposure latitude was maintained (with the sensitivity, granularity, and color reproducibility maintained).
Rapid development is possible, and by performing photoelectric image reading as shown in this embodiment, subsequent steps such as desilvering can be omitted, and further simpler and faster development processing is possible. It was shown that. In addition, there is an economical advantage that a processing agent for desilvering or stabilizing bath is not required.

[0279]

The red-sensitive, green-sensitive and blue-sensitive silver halide light-sensitive layers are composed of unit emulsion layers having the same spectral sensitivity range but different sensitivities. Both the high-sensitivity green-sensitive unit emulsion layer develops a light-sensitive material having a layer arrangement farther from the support than any of the lowest-sensitivity red-sensitive unit emulsion layer and the lowest-sensitivity green-sensitive unit emulsion layer. By using the color developing method of the present invention using a color developing solution containing at least 1.8 × 10 ^-2 mol / liter of a developing agent and a gradation adjusting agent, the sensitivity, granularity, and the like can be improved even when rapid development is performed. Since there is no decrease in color reproducibility, rapid development processing can be realized without impairing the original sensitivity, graininess and color reproducibility of the photosensitive material.
Further, by reading the image information of the image obtained by developing using the photosensitive material and the color developer photoelectrically and performing digital image processing, a color image can be obtained more quickly,
In addition, connection to various electronic image media is facilitated.

[Brief description of the drawings]

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

FIG. 2 is a block diagram schematically showing a configuration of a first image information reading unit 112.

FIG. 3 shows light sources 11 and 2 of a first image information reading unit 112.
FIG. 4 is a timing chart showing a lighting pattern of No. 1;

FIG. 4 is a block diagram schematically showing a configuration of a second image information reading unit 114.

FIG. 5 is a block diagram showing a configuration of an image generation unit 60.

FIG. 6 is a block diagram showing a configuration of a digital image processing unit 70.

[Explanation of symbols]

 F film 11, 31, 81 Light source 12, 32, 82 Mirror 14, 34, 84 Light amount adjustment unit 16, 36, 86 Lens 15, 35, 85 CCD area sensor 17, 37, 87 Amplifier 18, 38, 88 A / D Converters 19, 39, 89 CCD correction means 20, 40, 90 Log converters 21, 41, 91 Interface 60 Image generator 61, 62, 63 Memory 64 Linear converter 65 Adder 70 Digital image processor 71 Digital camera 72 Scanner 73 Floppy drive 74 MO (CD) 75 Modem 76 Image memory 77 Color gradation processing unit 78 Hypertone processing unit 79 Hyper sharpness processing unit 110 Film processing and image reading unit 111 Developing unit 112 First image information reading unit 113 Heat drying Riki 114 second drawing Information reading unit 120 image processing unit

Claims (4)

[Claims] 1. A red-sensitive silver halide light-sensitive layer, a green light-sensitive silver halide light-sensitive layer, and a blue light-sensitive silver halide light-sensitive layer comprising at least two unit emulsion layers each having the same spectral sensitivity region and different sensitivities on a support. In the method for processing a photographic light-sensitive material having a photographic light-sensitive material, the photographic light-sensitive material has a red-sensitive unit emulsion layer having the lowest sensitivity and a green-sensitive unit emulsion layer having the highest sensitivity. A layer arrangement provided on the side farther from the support than any of the green sensitive unit emulsion layers of the high sensitivity, and the development processing comprises a color developing agent having a gradation of at least 1.8 × 10 ^-2 mol / l. A method for developing a silver halide color photographic light-sensitive material, wherein the method is carried out using a color developer containing a modifier. 2. The halogenation according to claim 1, wherein the gradation adjusting agent is bromine ion, and its concentration in the color developer is at least 1.6 × 10 ⁻² mol / l. A method for developing silver color photographic light-sensitive materials. 3. The method according to claim 1, wherein the gradation adjusting agent is at least one compound selected from the group consisting of alkyl sulfonic acid, polyethylene glycol, polyethylene glycol alkyl ether, urea and derivatives thereof, and polyvinylpyrrolidone. For developing silver halide color photographic light-sensitive materials. 4. The method according to claim 1, wherein image information is photoelectrically read from an image obtained by the development processing, the read image information is converted into electrical digital image information, and image processing is performed on the electrical digital image information. The method for developing a silver halide color photographic light-sensitive material according to claim 1.