JPH07128790A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material having high sensitivity and excellent in sharpness. CONSTITUTION:The silver halide color photographic sensitive material has at least each one of blue-, green-, and red-sensitive emulsion layers on a support, at least one photograph constituting layer, located farther apart from the support than the green-sensitive layer, is dyed with a magenta dye fixed to this layer, and a nonphotosensitive layer, located nearer to the support than the green-sensitive layer nearest to the support and in adjacent to the green-sensitive layer, is dyed with a magenta dye fixed to this layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also referred to as "light-sensitive material") having high sensitivity and particularly excellent sharpness.

[0002]

2. Description of the Related Art In recent years, silver halide light-sensitive materials, particularly photographic materials, are expected to have higher sensitivity and further improved image quality. However, conventional light-sensitive materials cannot be said to have sufficient sharpness, and in particular, when printing at a high magnification, poor sharpness may greatly impair the level of print image quality.

As one of means for improving sharpness, there is a method for preventing light scattering. One of the techniques is a method of preventing halation, which is disclosed in, for example, Japanese Patent Laid-Open No. 5-188.
No. 58 discloses a technique for improving the sharpness of a magenta color image by fixing a magenta dye in a non-photosensitive layer adjacent to the side of the green-sensitive emulsion layer close to the support. However, although this method is effective in the sense of minimizing the decrease in sensitivity, the effect of improving sharpness is not sufficient.

Another means for improving sharpness is to prevent irradiation. For example, JP-A-62-103641 and European Patent EP-0556608.
No. 2A1 discloses a method of fixing a magenta dye on the upper layer of the green photosensitive layer. This method can improve the sharpness, but at the same time causes a significant reduction in sensitivity, resulting in a serious loss of performance when designing a light-sensitive material, particularly a photographic light-sensitive material.

US Pat. No. 4,855,220, JP-A-62-166330 and JP-A-62-168148.
JP-A-62-168153, JP-A-62-168
Similarly, No. 154 discloses a technique of fixing a magenta dye to the upper layer or the lower layer of the green photosensitive layer for the purpose of improving the sharpness, but there is no detailed description about the position of fixing the dye, The above-mentioned sufficient effect of improving sharpness and prevention of reduction in sensitivity have not been achieved at the same time.

[0006]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color photographic light-sensitive material having high sensitivity, improved sharpness, and excellent image quality.

[0007]

The above-mentioned object can be achieved by the silver halide color photographic light-sensitive material described below. (1) In a silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, a green-sensitive layer At least one layer of the photographic constituent layers located farther from the support is dyed with the fixed magenta dye, and is located closer to the support than the green-sensitive layer closest to the support. A silver halide color photographic light-sensitive material characterized in that a non-light-sensitive layer adjacent to a light-sensitive layer is dyed with a fixed magenta dye. (2) The silver halide color photographic light-sensitive material as described in the above item (1), wherein the magenta dye is fixed by an emulsion dispersion method. (3) The silver halide color photographic light-sensitive material according to the above item (1), wherein the photographic constituent layer dyed with the fixed magenta dye is a blue-sensitive emulsion layer.

The present invention will be described in detail below. The magenta dye in the present invention may be any one having a maximum spectral absorption wavelength at 500 to 600 nm in a dry film of a light-sensitive material containing a dye, and the dye may be one kind or a combination of two or more kinds. good.

In the present invention, the term "fixed dye" means that the dye added during the preparation of the target layer during the production of the light-sensitive material diffuses to the layers other than the target layer even after the production. None, it means that it exists substantially in the target layer. Any method may be used as the means for fixing the layer to the target layer, and for example, the following method is available.

The method for adding the dye to the target layer is a method of directly dyeing gelatin, an oil-in-water dispersion method of the dye as described below, that is, a high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure. Boiling point of 50 ℃ or more and 160 ℃ if necessary
A method of dissolving using the following organic solvent and adding the emulsion-dispersed product in an aqueous gelatin solution containing a surfactant,
International Patent Publication WO88 / 4974, Japanese Patent Publication No. 1-502
No. 912 and European Patent Publication No. 456,148, there is a method of adding a so-called solid dispersion or a method of preventing diffusion of a dye through a polymer mordant. Representative polymer mordants include, for example, JP-A-5-1.
It is described in Chemical formula 9 of 88548. In the present invention, any of these methods can be used, but addition by the oil-in-water dispersion method is particularly preferable.

In the present invention, the amount of the dye added is such that the average optical density in the 500-600 nm region in the dry layer of the target layer is 0.005-0.50, preferably 0.02.
Is about 0.30. This concentration is determined as follows. The actual measurement method is as follows: a dye is coated on a transparent support together with zeratan and dried, and a sample is dried at 500 to 60 with a spectrophotometer.
The concentration of 0 nm is measured, and it is 500 to 600 from the integrated value.
Determine the average optical density in nm.

The magenta dye of the present invention is required to be fixed in the upper layer of the green photosensitive layer and the lower layer (non-photosensitive layer) adjacent to the green photosensitive layer, and the concentration ratio of the dyes used in the upper layer and the lower layer is particularly important. Although not specified, the ratio of upper layer: lower layer is usually used in the range of 1:10 to 5: 1, preferably 1: 5 to 4: 1.
It is particularly preferable that it is 1: 4 to 3: 1. If the ratio of the upper layer is higher than this, the sensitivity is remarkably lowered, and if the ratio of the lower layer is higher than this, the effect of improving the sharpness is small. There is no particular limitation on the type of dye used in the upper layer and the lower layer, even if the same type of dye is used,
Different ones may be used. Further, they may be used alone or as a mixture of several kinds of dyes.

By dyeing the upper layer, the sharpness in the low frequency region can be improved, and by dyeing the lower layer, the sharpness in the high frequency region can be improved. By dyeing the upper layer and the lower layer in the above ratio, the sharpness of the entire region can be improved and the image quality can be remarkably improved.

The fixed magenta dye of the present invention needs to be contained farther from the support than the green photosensitive layer, but it is preferably added to the photosensitive emulsion layer, and the blue photosensitive emulsion layer. Is particularly preferably added to Conventionally, such a fixed magenta dye has been used in the non-light-sensitive emulsion layer as disclosed in JP-A-62-166330.
In particular, it is often added to the protective layer, and it has been considered preferable. However, as a result of various studies, the present inventors have found that addition to the photosensitive emulsion layer is particularly preferable for improving sharpness. Found out. Although the reason is not clear, it is presumed that the light scattering is suppressed by being in the same layer as the photosensitive silver halide emulsion layer which is the light scatterer.

In order to improve the sharpness, it is important to select the thickness of silver halide grains in consideration of the wavelength of light incident on or exposed to a light-sensitive material. 400
Particles having a thickness of 0.08 to 0.10 μm are preferably arranged in a layer that scatters blue light of from 0.5 to 500 nm or a layer that is sensitive to blue light. Next preferred is a thickness of 0.19 to 0.21 μm. 0.11 for a layer that scatters green light of 500 to 600 nm or a layer that is sensitive to green light
It is preferable to arrange particles having a thickness of 0.1 to 0.13 μm. Next preferred is a thickness of 0.23 to 0.25 μm. Particles having a thickness of 0.14 to 0.17 μm are preferably arranged in a layer that scatters red light of 600 to 700 nm or a layer that is sensitive to red light. Next preferred is a thickness of 0.28 to 0.30 μm. Particles having a thickness of 0.17 to 0.19 μm are preferably arranged in a layer that scatters infrared light or a layer that is sensitive to infrared light. 1
When one photosensitive layer consists of multiple photosensitive layers with different sensitivities,
It is best to place particles of preferred thickness in all layers. Next preferred is to place it in the photosensitive layer farther from the support. It is particularly preferable to use a combination of particles having a preferable thickness in each photosensitive layer, for example, to arrange particles having a preferable thickness in both the blue light sensitive layer and the green light sensitive layer. Any combination of blue light, green light, and red light sensitive layers can be selected.

Specific examples of the magenta dye used in the present invention are shown below, but the present invention is not limited thereto.

[0017]

[Chemical 1]

[0018]

[Chemical 2]

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

The above exemplified compounds are disclosed in JP-A-61-488.
54, 61-7838, 60-243654.
No. 60-32851, No. 62-276539,
52-92716, International Patent WO88 / 04794.
No. 3, JP-A-3-7931, No. 4-45436, No. 5
No. 43809, or can be synthesized according to the method described.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are formed by sequentially exposing two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL
It can also be arranged in the order of / RL. In addition, JP-A-56-2573
8 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. In addition, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as RL, adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p.648, ibid.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl.
afkides, Chimie et Phisique Photographique, Paul M
ontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion C
hemistry, Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZel).
ikman, et al., Making and Coating Photographic Emu
lsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 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 Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157.

Further, more preferable results may be obtained by using monodisperse tabular grains having a narrow grain size distribution. U.S. Pat. No. 4,797,354 and JP-A-2
No. 838 describes a method for producing monodisperse hexagonal tabular grains having a high tabularization rate. In addition, European Patent No. 51
No. 4,742 describes a method for producing tabular grains having a variation coefficient of grain size distribution of less than 10% using a polyalkylene oxide block copolymer.
It is preferable to use these tabular grains in the present invention.
Further, particles having a high coefficient of variation in particle thickness of 30% or less and high thickness uniformity are also preferable.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are RD No. 17643 and RD No. 17643.
8716 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in 214852 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm.
, Particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but monodispersity (at least the weight or the number of grains of silver halide grains)
95% has a particle size within ± 40% of the average particle size)
Is preferred.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer 648 page right column 3. Spectral sensitizer, pages 23 to 24 page 648 right column 866 to 868 supersensitizer to page 649 right column 4. Whitening agent page 24 647 right column 868 page 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Right column 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); -134523, a coupler represented by the general formula (I) of claim 1; US 5,066,576, column 1, lines 45 to 55; a coupler represented by the general formula (I); Couplers of the formula I); couplers according to claim 1 of EP 498,38A1 on page 40 (in particular D-35 on page 18); formulas of page 4 of EP 447,969A1
A coupler represented by (Y) (especially Y-1 (page 17), Y-54 (41
)); US 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) couplers (especially II-17, 19 (column 17), II
-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (bottom right of page 12), L-77 (bottom right of page 13); [A-4] -6 in EP 456,257
3 (134 pages), [A-4] -73, -75 (139 pages); EP 486,965 M-4, -6
(Page 26), M-7 (Page 27); M-4 of Paragraph 0024 of Japanese Patent Application No. 4-234120
5; M-1 in paragraph 0036 of Japanese Patent Application No. 4-36917; M-22 in paragraph 0237 of Japanese Patent Application Laid-Open No. 4-362631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42-43); Japanese Patent Application No. 4-23633
A coupler represented by the general formula (Ia) or (Ib) of claim 1. Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).

Examples of couplers in which the color forming dye has a suitable diffusibility include US 4,366,237, GB 2,125,570, EP 96,570,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler 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
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (particularly T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), a compound represented by the formula (1) of Japanese Patent Application No. 4-134523 (particularly (23) in paragraph 0027), and formulas (I) and (II in EP 440,195A2 on pages 5 to 6). ), (III) (particularly I- (1) on page 29); Bleach accelerator releasing compounds: EP 310,125A2-5
Compounds represented by formulas (I) and (I ') on page (especially (60) on page 61,
(61)) and a compound represented by the formula (I) in claim 1 of Japanese Patent Application No. 4-325564 (particularly (7) in paragraph 0022); a ligand-releasing compound: LIG-X described in claim 1 of US 4,555,478. Compounds represented (especially compounds on lines 21 to 41 of column 12); Leuco dye releasing compounds: compounds 1 to 6 of columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: COUP-DYE of claim 1 of US 4,774,181 Compounds represented (especially columns 7-10)
Compounds 1 to 11); development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22) of column 25) and EP 450,6
ExZK-2, 37A2, page 75, lines 36-38; compounds that release a dye group only upon leaving: a compound of formula (I) in claim 1 of US 4,857,447 (especially Y- in columns 25-36). 1 ~
Y-19).

As the additives other than the coupler, the following are preferable. 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 (pages 140-144); Latex for impregnation of oil-soluble organic compounds: Latex described in US Pat. (Especially I-, (1), (2), (6), (12)
(Columns 4-5), US 4,923,787, column 2, lines 5-10 (particularly compound 1 (column 3); stain inhibitor: EP
298321A, page 4, lines 30-33, formulas (I)-(III), especially I-47,72,
III-1,27 (pages 24-48); 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
(Pages 69-118), US 5,122,444, columns 25-38, II-1 to II.
I-23, especially III-10, EP 471347A, pages 8-12, I-1 to III-
4, especially II-2, US 5,139,931 columns 32-40 A-1 ~ 48,
In particular A-39,42; Materials that reduce the amount of color-enhancing agents or color-mixing inhibitors used: I-1 to II-15, EP 411324A, pages 5 to 24,
Especially I-46; Formalin Scavenger: EP 477932A 24
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, column 13-
23, compounds (H-1 to 54) represented by formulas (VII) to (XII), compounds (H-1 to 54) represented by formula (6) at the lower right of page 8 of JP-A-2-214852.
-1 to 76), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: JP-A-62-168139
P-24,37,39 (pages 6 to 7); Compounds as claimed in claim 1 of US 5,019,492, especially column 7, 28,29; preservatives, fungicides:
US 4,923,790 columns 3 to 15 I-1 to III-43, especially II-
1,9,10,18, III-25; Stabilizer, antifoggant: US 4,923,
793 columns 6-16 I-1 ~ (14), especially I-1,60, (2), (13),
US 4,952,483 columns 25-32 compounds 1-65, especially 3
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially V-1, EP 445627A FI on pages 33 to 55
-1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 2
Page 8 III-1 to 36, especially III-1,3, WO 88/04794 8-26
Dye-1 to 124 microcrystalline dispersion, EP 319999A, Compounds 1 to 22 on pages 6 to 11, especially Compound 1, EP 519306A, compounds D-1 to 87 (of formulas (1) to (3)). 3 to 28), US 4,2
68,622 Compounds 1 to 22 represented by the formula (I) (column 3 to
10), a compound (1) represented by the formula (I) of US 4,923,788 ~
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
(Page 9), compounds (3) to (6 represented by formula (I) of EP 520938A.
6) (pages 10 to 44) and the compound HBT-1 represented by the formula (III).
~ 10 (page 14), compounds represented by formula (1) of EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention include
For example, the RD. No. 17643, page 28, same No. 18716
Page 647, right column to page 648, left column, and 879 of the same No. 307105
Page. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less,
It is more preferably not more than μm, particularly preferably not more than 16 μm.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C for 3 minutes 15
When 90% of the maximum swollen film thickness reached at the time of second treatment is taken as the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.
Green) et al. Photographic Science and
Engineering (Photogr.Sci.Eng.), 19 squares, 2,124
It can be measured by using a swellometer of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating.
The swelling rate is preferably 150 to 400%. What is swelling rate?
It can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention has the above-mentioned RD. No. 17
Development can be carried out by a usual method described on pages 28 to 29 of 643, 651 left column to right column of No. 18716, and pages 880 to 881 of No. 307105. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include an inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Add ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 and JP-A-63-216050 are disclosed. The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development step and the black-and-white development step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing, stabilizing and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature, high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US 3,893,858, DE 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, compounds 53-141623, 53-28426 and RD No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506. , JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in US 3,706,561; DE 1,127,715,
Iodide salts described in JP-A-58-16,235; DE 966,410,
2,748,430, polyoxyethylene compounds; JP-B-45-8836, polyamine compounds; and others, JP-A-49-4
0,943, 49-59,644, 53-94,927, 54-35,727,
55-26,506 and 58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US 3,893,858, DE 1,290,812, JP-A-53-95,63.
The compounds described in 0 are preferred. Further, the compounds described in US 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. Also,
Thiosulfates and thiocyanates, thioether compounds,
A combined use of thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, addition of aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution is preferable for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or a stirring effect by using a rotating means of JP-A-62-183461 is used. Method of raising, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, the circulation flow rate of the entire processing solution There is a method of increasing it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material transporting means described in 60-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, has a high effect of preventing the performance deterioration of the treatment liquid, and It is particularly effective in shortening the processing time and reducing the replenishment amount of the processing liquid.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and various other conditions Can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
It can be determined by the method described in rs Volume 64, P. 248 to 253 (May 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problem arises. As a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antifungal agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8.
The washing water temperature and washing time can be set depending on the characteristics and use of the light-sensitive material, but in general, a range of 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C is selected. . Furthermore,
The light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. For such stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be applied. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing. You can Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The photographic material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use a precursor of a color developing agent. For example US 3,34
2,597 described indoaniline compound, 3,342,599,
Research Disclosure No.14,850 and No.15,1
Schiff base type compounds described in 59, aldol compounds described in 13,924, metal salt complexes described in US 3,719,492, JP-A-53
The urethane compounds described in -135628 can be mentioned. The photographic material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339,
57-144547 and 58-115438. The processing solution used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can.

[0042]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material composed of each layer having the composition shown below, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, Ex
M: Magenta coupler, ExY: Yellow coupler, C
pd; additive

First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.33 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 1.0 × 10 ^-2 ExF -2 4.0 x 10 ^-2 ExF-3 5.0 x 10 ^-3 ExM-3 0.11 Cpd-5 1.0 x 10 ^-3 Solv-1 0.16 Solv-2 0.10

Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount of silver 0.35 Silver iodobromide emulsion B Coating amount of 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 x 10 ^-4 ExS-7 4.1 x 10 ^-6 ExC-1 9.0 x 10 ^-2 ExC-2 5.0 x 10 ^-3 ExC-3 4.0 x 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 2.5 x 10 ^-2 Cpd-4 2.2 x 10 ^-2

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Coating Silver Amount 0.55 Gelatin 1.46 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.4 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 1.0 × 10 ^-2 ExC-3 1.0 × 10 ^-2 ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0 × 10 ^-2 ExC- 7 2.5 x 10 ^-2 ExC-9 3.0 x 10 ^-2 Cpd-4 1.5 x 10 ^-3

4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 1.05 Gelatin 1.38 ExS-1 2.0 × 10 ^-4 ExS-2 1.1 × 10 ^-4 ExS-5 1.9 × 10 ^-4 ExS-7 1.4 x 10 ^-5 ExC-1 2.0 x 10 ^-2 ExC-3 2.0 x 10 ^-2 ExC-4 9.0 x 10 ^-2 ExC-5 5.0 x 10 ^-2 ExC-8 1.0 x10 ^-2 ExC- 9 1.0 x 10 ^-2 Cpd-4 1.0 x 10 ^-3 Solv-1 0.70 Solv-2 0.15

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2

Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Coated silver amount 0.10 Silver iodobromide emulsion F Coated silver amount 0.28 Gelatin 0.31 ExS-3 1.0 × 10 ^-4 ExS-4 3.1 × 10 ^-4 ExS-5 6.4 x 10 ^-5 ExM-1 0.12 ExM-7 2.1 x 10 ^-2 Solv-1 0.09 Solv-3 7.0 x 10 ^-3

Seventh layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion G Coating amount 0.37 Gelatin 0.54 ExS-3 2.7 × 10 ^-4 ExS-4 8.2 × 10 ^-4 ExS-5 1.7 × 10 ^-4 ExM-1 0.27 ExM-7 7.2 x 10 ^-2 ExY-1 5.4 x 10 ^-2 Solv-1 0.23 Solv-3 1.8 x 10 ^-2

Eighth layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion H Coating amount 0.53 Gelatin 0.61 ExS-4 4.3 × 10 ^-4 ExS-5 8.6 × 10 ^-5 ExS-8 2.8 × 10 ^-5 ExM-2 5.5 x 10 ^-3 ExM-3 1.0 x 10 ^-2 ExM-5 1.0 x 10 ^-2 ExM-6 3.0 x 10 ^-2 ExY-1 1.0 x 10 ^-2 ExC-1 4.0 x10 ^-3 ExC- 4 2.5 × 10 ^-3 Cpd-6 1.0 × 10 ^-2 Solv-1 0.12

Ninth layer (intermediate layer) Gelatin 0.56 UV-4 4.0 × 10 ^-2 UV-5 3.0 × 10 ^-2 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2

10th layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion I Coating amount 0.40 Silver iodobromide emulsion J Coating amount 0.20 Silver iodobromide emulsion K Coating silver amount 0.39 Gelatin 0.87 ExS -3 6.7 x 10 ^-4 ExM-2 0.16 ExM-4 3.0 x 10 ^-2 ExM-5 5.0 x 10 ^-2 ExY-2 2.5 x 10 ^-3 ExY-5 2.0 x 10 ^-2 Solv-1 0.30 Solv-5 3.0 x 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 3.5 × 10 ^-2 gelatin 0.84 Cpd-1 5.0 × 10 ^-2 Cpd-2 5.0 × 10 ^-2 Cpd-5 2.0 × 10 ^-3 ExF-4 8.0 × 10 ^-2 Solv-1 0.13 H-1 0.25

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Coating amount 0.50 Silver iodobromide emulsion M Coating silver amount 0.40 Gelatin 1.75 ExS-6 9.0 × 10 ^-4 ExY-1 8.5 × 10 ^-2 ExY-2 5.5 x 10 ^-3 ExY-3 6.0 x 10 ^-2 ExY-5 1.00 ExC-1 5.0 x 10 ^-2 ExC-2 8.0 x 10 ^-2 Solv-1 0.54

13th layer (intermediate layer) Gelatin 0.30 ExY-4 0.14 Solv-1 0.14

14th layer (high-sensitivity blue emulsion layer) Silver iodobromide emulsion N Coating amount of 0.40 Gelatin 0.95 ExS-6 2.6 × 10 ^-4 ExY-2 1.0 × 10 ^-2 ExY-3 2.0 × 10 ^-2 ExY-5 0.18 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth layer (first protective layer) Fine grain silver iodobromide emulsion O Coating amount of 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Cpd-3 0.10 Solv-4 2.0 × 10 ^-2 polyethyl acrylate latex 9.0 × 10 ^-2

16th layer (second protective layer) Fine grain silver iodobromide emulsion O Coating amount 0.36 Gelatin 0.85 B-1 (diameter 2.0 μm) 8.0 × 10 ⁻² B-2 (diameter 2.0 μm) 8.0 × 10 ^{− 2} B-3 2.0 x 10 ^-2 W-5 2.0 x 10 ^-2 H-1 0.18

In addition to the above, the samples thus prepared include
1,2-Benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. In addition, each layer has appropriate storage properties, processability, pressure resistance, mildew / bacterial resistance,
In order to improve the antistatic property and coating property, W-1 to W-
6, B-1 to B-6, F-1 to F-16, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

[0061]

[Table 1]

In Table-A, (1) Emulsions A to N were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to N were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It has been subjected. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope. (5) Emulsions A to N are BH Carroll, Photographic Scien
Ce and Engineering, 24, 265 (1980) and the like contain iridium inside the particles.

[0063]

[Chemical 6]

[0064]

[Chemical 7]

[0065]

[Chemical 8]

[0066]

[Chemical 9]

[0067]

[Chemical 10]

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

[0073]

[Chemical 16]

[0074]

[Chemical 17]

[0075]

[Chemical 18]

[0076]

[Chemical 19]

[0077]

[Chemical 20]

[0078]

[Chemical 21]

[0079]

[Chemical formula 22]

[0080]

[Chemical formula 23]

Sample 101 was prepared by adding the magenta dye D-5 of the present invention to the fifteenth layer (non-photosensitive layer on the side farther from the support than the green-sensitive emulsion layer). The addition method of the magenta dye D-5 is as follows. 17.5 g of magenta dye (D-5) and 15 cc of high boiling organic solvent (H
BS-1) and 100 cc of ethyl acetate were added, and the mixture was heated to 40 ° C and completely dissolved. This ethyl acetate solution was used as a 13% gelatin aqueous solution containing 7.0 g of a surfactant (W-4) 4
It was mixed with 00 g and emulsified and dispersed by a homoblender. The emulsified dispersion thus obtained was used as D-5
Was added to the intended layer so that the coating amount of was the value shown in Table-B. In the same manner, the layers to be added with the magenta dye and the addition amount were changed, and as shown in Table-B, Samples 102 to 10 were used.
Created 7. In addition, 1 of Magenta Dye D-7 of the present invention
% Methanol solution was added and sample 1 was added as shown in Table-B.
08 was created.

The following performance evaluation was performed on these samples 101 to 108. White light (color temperature of light source 48
Wedge exposure for sensitometry at 00 ° K)
After the color development process shown below, G of the processed sample
The concentration was measured, and the sensitivity was obtained from the characteristic curve. The sensitivity was calculated by calculating the logarithm of the reciprocal of the exposure dose that gives the density of the minimum density + 0.5, and calculating the difference with reference to the sample 101.
It was shown to.

Next, as an evaluation of the sharpness, each sample was subjected to MTF pattern exposure with white light and subjected to the following development processing, and then the MTF value (25 cycles / mm) of a magenta color image was measured. The comparison of the sharpness was performed by the relative value based on the sample 101, and the results are shown in Table-B.

[0084]

[Table 2]

Each processing was carried out as follows using an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ℃ 23 ml 17 liters Bleach 50 seconds 38.0 ℃ 5 ml 5 liters Bleach fixing 50 seconds 38.0 ℃ -5 liters Fixed 50 seconds 38.0 ℃ 16 ml 5 liters Water wash 30 seconds 38.0 ℃ 34 ml 3.5 liters Stability (1) 20 seconds 38.0 ℃ ― 3 liters Stability (2) 20 seconds 38.0 ℃ 20 ml 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount is 35mm width 1.1m length per length (equivalent to 24 Ex.)

The stabilizing solution is a countercurrent system from (2) to (1),
The overflow of washing water was introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. I was allowed to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step and the amount of fixing solution brought into the washing step were as follows: They were 2.5 ml, 2.0 ml, 2.0 ml, and 2.0 ml per 1 m, respectively. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 25 38 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.0

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (PH 7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water added 1.0 l 1.0 l pH (Adjust with ammonia water and acetic acid) 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

[0093]

From the results shown in Table B, the photographic constituent layers located farther from the support than any of the green-sensitive emulsion layers and the side closer to the support than any of the green-sensitive layers were adjacent to the green-sensitive layer. It is apparent that the samples 106 and 107 of the present invention, in which the magenta dye is fixed to the non-photosensitive layer, are preferably improved in sharpness as compared with Comparative samples 101 to 105 without impairing photographic sensitivity. In addition, the samples 106 and 107 of the present invention in which the magenta dye is emulsified and dispersed are
Sample 108 of the present invention using magenta dye added as a solution
It can be seen that the sharpness is higher than that of No. 1, and is particularly preferable.

Further, the sample 107 of the present invention in which the magenta dye was fixed to the blue-sensitive emulsion layer as a photographic constituent layer located on the side farther from the support than the green-sensitive layer, was particularly excellent in sensitivity and sharpness. You can see that

Example 2 Instead of the magenta dye D-5 used in Example 1, D-
When a sample similar to that of Example 1 was prepared using 7, D-8, D-11, and D-16 and evaluated, the same result as that of Example 1 was obtained.

[0097]

According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity and excellent sharpness was obtained. That is,
At least one layer of blue-sensitivity / green-sensitivity on the support
It has a red-sensitive silver halide emulsion layer, at least one of the photographic constituent layers located on the side farther from the support than the green-sensitive layer is dyed with a fixed magenta dye, and the green-sensitive layer closest to the support. Located closer to the support than the layers,
By sharpening the non-photosensitive layer adjacent to the green-sensitive layer with the fixed magenta dye, the sharpness can be improved without impairing the sensitivity. In particular, when the photographic constituent layer dyed with the fixed magenta dye (the photographic constituent layer located on the side farther from the support than the green-sensitive layer) is a blue-sensitive emulsion layer, the performance of sensitivity and sharpness is remarkable. Are better.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G03C 7/20 7/26 (72) Inventor Shigeru Ono 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. In the company

Claims (3)

[Claims] 1. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and at least one layer each on a support.
And a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, at least one layer of the photographic constituent layers located on the side farther from the support than the green-sensitive layer is dyed with a magenta dye immobilized, And a halogenation characterized in that the non-photosensitive layer located closer to the support than the green-sensitive layer closest to the support and adjacent to the green-sensitive layer is dyed with a fixed magenta dye. Silver color photographic light-sensitive material. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the magenta dye is fixed by an emulsion dispersion method. 3. A silver halide color photographic light-sensitive material according to claim 1, wherein the photographic constituent layer dyed with the fixed magenta dye is a blue-sensitive emulsion layer.