JPH06282051A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material having high fidelity in the reproducibility of an original image. CONSTITUTION:In the silver halide color photographic sensitive material, the wavelength showing the max. sensitivity exists between 540-560nm in equi-energy spectral sensitivity distribution of each density in >=1.0 to <=2.0 Magenta analytical density. And the sensitivity in 570nm is 0.1-0.25 times of the max. sensitivity. Furthermore, the difference between the wavelength in the long wavelength side and in the short wavelength side having 1/10 sensitivity of the max. sensitivity is <=70nm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More specifically, high sensitivity,
The present invention relates to a positive-positive type color reversal photographic material having high fidelity in color reproduction with respect to an original image.

[0002]

2. Description of the Related Art As a positive-positive type color reversal silver halide photographic light-sensitive material for the purpose of producing a positive image using a positive image as an original, a reflection type color reversal paper can be mentioned, and a transmissive type is, for example, A representative example is a color reversal film for duplication (hereinafter referred to as a duplication film). These positive-positive color reversal photographic light-sensitive materials are required to faithfully reproduce the colors of the original.

As a design guideline of the spectral sensitivity of the dupe film itself for more faithfully reproducing the color density of an original (hereinafter also referred to as original image) reversal image, for example, T
heTheory of Photographic
Process Chapter 19 (TH James et al. 1
977), the spectral absorption distributions of the yellow, magenta, and cyan image forming dyes contained in the original reversal image and the spectral sensitivity distributions of the respective color-sensitive layers of the duplication film corresponding to these image forming dyes match. Have been shown to be preferred.

On the other hand, it is a market reality that the spectral absorption distribution of the image-forming dye of the original reversal film, which is the original image, differs for each original reversal film.
Therefore, in order to reproduce the color density of each original reversal film (hereinafter referred to as the original color) most faithfully, the spectral sensitivity distribution that matches the spectral absorption of each image forming dye should be selected according to each original reversal film. It is necessary to supply the dupe film that has.

[0005]

However, from the viewpoint of low-priced supply of products to the market, operability from the viewpoint of laboratory users, and improvement of productivity, a versatile dupe film is desired from the market, and this demand is high. Although it is necessary to meet the above requirements, it is difficult to realize with the conventional technology. Although the duplicating film has been described above as an example, similar demands are recognized in other positive-positive type color reversal photographic light-sensitive materials such as color reversal paper.

In view of the above points, the present invention has an object to provide a positive-positive type color reversal photographic light-sensitive material having high fidelity of original color and high versatility.

[0007]

The present invention is directed to a silver halide color having at least one blue-sensitive layer containing a yellow coupler, a green-sensitive layer containing a magenta coupler and a red-sensitive layer containing a cyan coupler on a support. A photographic light-sensitive material having a uniform energy spectral sensitivity distribution at each density of 1.0 to 2.0, which is a magenta analysis density,
The wavelength exhibiting the highest sensitivity exists between 540 nm and 560 nm, the sensitivity at 570 nm is 0.1 to 0.25 times the highest sensitivity, and 1 / of the highest sensitivity.
Provided is a silver halide color photographic light-sensitive material having a sensitivity of 10 and a difference between a wavelength on the long wave side and a wavelength on the short wave side of 70 nm or less.

The above-described silver halide color photographic light-sensitive material of the present invention has a plurality of green-sensitive layers having different sensitivities on a support, and the green-sensitive layers other than the layer having the lowest sensitivity are used. The silver halide emulsion contained in at least one layer is at least one of the spectral sensitizing dyes represented by the general formula (I) and the spectral sensitizing dyes represented by the general formulas (II) to (IV). Is preferably spectrally sensitized with at least one of

[0009]

[Chemical 5] (In the formula, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group,
Represents an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, a cyano group or an alkyl group, and Y ₁ and Y
Either one of ₂ or Y ₃ and Y ₄ may be linked to each other to form a ring to form a naphthoxazole ring. R ₁ represents a hydrogen atom or an alkyl group, R ₂ and R ₃ each represent an alkyl group, X ₁ − represents an anion, and n represents an integer of 1 or 2. However, when n represents 1, R ₂ or R ₃ represents a group capable of forming an inner salt. )

[0010]

[Chemical 6] (In the formula, Y ₅ and Y ₆ and Y ₇ and Y ₈ each represent a group of atoms which are linked to each other to form a ring and form a naphthoxazole ring. Further, R ₄ represents a hydrogen atom or an alkyl group. , R ₅ and R ₆ each represent an alkyl group, X ₂ — represents an anion, and m represents an integer of 1 or 2. provided that when m represents 1,
R ₅ or R ₆ represents a group capable of forming an inner salt. )

[0011]

[Chemical 7] (In the formula, Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, Represents a cyano group or an alkyl group, Y ₉ and Y ₁₀
Alternatively, at least one of Y ₁₁ and Y ₁₂ may be linked to each other to form a ring and form a naphthimidazole ring. R ₇ represents a hydrogen atom or an alkyl group, R ₈
R ₉ , R ₁₀ and R ₁₁ each represent an alkyl group,
X ₃ − represents an anion, and r represents an integer of 1 or 2. However, when r represents 1, R ₈ , R ₉ , R
₁₀ or R ₁₁ represents a group capable of forming an inner salt. )

[0012]

[Chemical 8] (In the formula, Y ₁₃ , Y ₁₄ , Y ₁₅ and Y ₁₆ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, Represents a cyano group or an alkyl group, Y ₁₃ and Y ₁₄
May be linked to each other to form a ring to form a naphthoxazole ring, and Y ₁₅ and Y ₁₆ may be linked to each other to form a ring to form a naphthimidazole ring. Also, R
₁₂ represents a hydrogen atom or an alkyl group, R ₁₃ , R ₁₄ and R ₁₅ each represent an alkyl group, X ₄ − represents an anion, and q represents an integer of 1 or 2. However, when q represents 1, R ₁₃ or R ₁₄ represents a group capable of forming an inner salt. Hereinafter, the present invention will be described in more detail.

In the color photographic light-sensitive material of the present invention, the equienergetic spectral sensitivity distribution at each density of magenta analysis density of 1.0 or more and 2.0 or less has a peak of maximum sensitivity in the range of 540 nm to 560 nm. More preferably, the wavelength exhibiting the highest sensitivity is in the range of 545 nm to 555 nm.

The sensitivity at 570 nm is 0.1 to 0.25 times the maximum sensitivity, preferably 0.1.
It is twice to 0.2 times. Further, the wavelength difference between the short wave side and the long wave side, which has a sensitivity 1/10 of the sensitivity at the highest sensitivity wavelength, is 70 nm or less, and more preferably 60 nm or less.

Here, the analytic density usually means, for each of the cyan, magenta and yellow image forming dyes,
A single photographic density that excludes side absorptions by the other two dyes, for example, The Theory of Pho
Chapter 19 of the Tographic Process (T.
H. James et al., 1977).

As one of the methods for achieving the equienergetic spectral sensitivity distribution of the green-sensitive layer in the color photographic light-sensitive material of the present invention, for example, at least one sensitizing dye represented by the general formula (I), and generally Examples thereof include a method of spectrally sensitizing using at least one sensitizing dye represented by the formulas (II) to (IV). In this case, the total number of moles of the sensitizing dyes (II) to (IV) is preferably 1/2 or less with respect to the total number of moles of the sensitizing dye (I).

It is also possible to use a small amount of a sensitizing dye having a light absorption band of a shorter wavelength or a longer wavelength with respect to the sensitizing dye represented by the general formulas (I) to (IV).

Typical sensitizing dyes represented by formulas (I) to (IV) used in the color photographic light-sensitive material of the present invention are shown below, but the present invention is not limited thereto. Absent. (Exemplary compounds of general formula (I))

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12] (Exemplary compound of general formula (II))

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15] (Exemplified compound of general formula (III))

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23] (Exemplary compound of general formula (IV))

[0034]

[Chemical formula 24] The green sensitivity of the silver halide color photographic light-sensitive material of the present invention is composed of a single or a plurality of silver halide emulsion layers having different sensitivities. The silver halide color photographic light-sensitive material of the present invention comprises at least one sensitizing dye of the general formula (I) and at least one of the general formula (II)
It is preferable to use a silver halide emulsion spectrally sensitized with at least one of the sensitizing dyes of (IV), more preferably to all green-sensitive layers other than the minimum green-sensitive layer.

The silver halide color photographic light-sensitive material of the present invention has at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided on a support. The number and order of layers of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And 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, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-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.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., 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 (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, 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 middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / 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, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448,
BL, GL, described in the specification of 63-89850.
It is preferable to arrange 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 in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, 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 (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and "Graphide's Physics and Chemistry" by Graphide, published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

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, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide such as silver rhodan and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. 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.

As the silver halide emulsion, those which have been subjected to physical ripening, chemical ripening and spectral sensitization are usually used. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the corresponding portions are summarized in Table A below.

The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in 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 capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. 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 grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

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 if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. 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 preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of the light-sensitive material of the present invention is 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table A below.

Table A Additive Types RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column Page 650 Left column Page 872 Right column 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 left column 874 to 875 10. Binder pages 26 pages 651 left column 873 to 874 pages 11. Plasticizers and lubricants page 27 650 right columns 876 pages 12. Coating aids, 26 to 27 Page 650 page right column 875 to 876 surface active agent 13. static, page 27 page 650 right column 876 to 877 page inhibitor 14. matting agent page 878 to 879 To prevent deterioration of photographic performance due to formaldehyde gas It is preferred to add to the photographic material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 to immobilize it.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the light-sensitive material of the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-C-
G, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Further, JP-A 64-553 and 64-5.
No. 54, No. 64-555 and No. 64-556, and pyrazoloazole couplers described in US Pat.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color-forming dyes are Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258, and British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, VII-F section and No. 307105, V
Patents described in the section II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

R. D. No. 11449 and 2424
1, the bleaching accelerator releasing coupler described in JP-A-61-2201247 is effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to the material. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, there is disclosed in British Patent 2,097,1.
40, No. 2,131,188, JP-A-59-15.
Those described in 7638 and 59-170840 are preferable. Moreover, JP-A-60-107029 and JP-A-60-
252340, JP-A-1-44940, and 1-45.
Compounds releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive coupler described in U.S. Pat. No. 4,283,47.
No. 2, No. 4,338,393, No. 4,310,6
No. 18, etc., multi-equivalent couplers, JP-A-60-185.
950, DIR described in JP-A-62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
Nos. 73,302A and 313,308A, which release dyes that restore color after withdrawal, and US Pat.
Examples thereof include ligand releasing couplers described in US Pat. No. 555,477, couplers releasing a leuco dye described in JP-A-63-75747, couplers releasing a fluorescent dye described in US Pat. No. 4,774,181, and the like. To be

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)).
Phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate) , Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc., benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-
p-hydroxybenzoate, etc., amides (N, N
-Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl))
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 5
An organic solvent having a temperature of 0 ° C. or more and about 160 ° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-125747.
No. 272248 and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptic agents or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

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

In the photographic 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, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling rate 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%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The photographic 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, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

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. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples thereof include sulfonates. Among these, especially 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in 2
It is also possible to use together more than one species.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

Next, processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described.

Among the processing steps of the color reversal photosensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-and-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described.

4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Coloring development-washing-bleaching-washing-fixing-washing-stable 7) Color development Development-washing-bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Color development-bleaching-bleaching fixing-fixing- Washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Coloring development-washing-bleaching fixing-washing-stable 14) Color development-bleach-fixing -Washing-Stable 15) In the processing steps of color development-fixing-bleach-fixing-water washing-stable 4) to 15), the washing step immediately before the stabilizing step may be omitted, or conversely, the stabilizing step of the final step may be omitted. It does not have to be done. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and U.S. Pat. No. 4,067,8.
A heterocyclic compound such as 1,2,3,4-tetrahydroquinoline ring and an indrene ring described in No. 72 can be used alone or in combination.

In the black-and-white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents may be added, if necessary. (Eg, hydroxide, carbonate), dissolution tablet (eg, polyethylene glycols,
These esters), pH adjusters (for example, organic acids such as acetic acid), sensitizers (for example, quaternary ammonium salts), development accelerators, surfactants, defoamers, hardeners, viscosity imparting agents, etc. Can be included.

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used are specifically KSCN, NaSCN, K
₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O
₅ , K ₂ S ₂ O ₃ , Na ₂ S ₂ O _{3 and the} like can be mentioned.

The pH value of the developer thus adjusted is selected to an extent sufficient to give a desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is reduced to 500 or less by reducing the bromide ion concentration in the replenishing solution. 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 contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below.

That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably It is preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization 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 reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog and to reduce the carry-in of the color developing solution to the desilvering process. Also, in order to wash out and detoxify the sensitizing dyes, dyes and other sensitive material parts contained in the photographic light-sensitive material and the color developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after color development processing. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

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 according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Among these, aminopolycarboxylic acid iron (II) complexes including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts.
I) Complex salts are preferable from the viewpoint of rapid processing 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 iron (III) aminopolycarboxylic acid 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 Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927, and 54-35, 727, 5
Compounds described in JP-A Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. 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. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid and hydroxyacetic acid are preferred.

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. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like 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 European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing 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 step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, 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, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. 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 developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive 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 method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage counterflow method is described in the Journal of the Societ.
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly 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, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-288,838 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Microbial and Antifungal Encyclopedia" (1986) Can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

Further, after the washing treatment, there is a case where the stabilizing treatment is further carried out. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. 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 or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color photographic light-sensitive 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 various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597,
Schiff base type compounds described in U.S. Pat. No. 3,342,599, Research Disclosures 14,850 and 15,159, aldol compounds described in U.S. Pat. No. 13,924, and U.S. Pat. No. 3,719,492. Examples thereof include metal salt complexes and urethane compounds described in JP-A-53-135628.

The silver halide color photographic light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
144547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0117]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. <Preparation of Sample 101> Sample 101 was prepared by preparing a multilayer color photographic light-sensitive material having the following composition from the first layer to the twentieth layer on an undercoated 127 μm thick cellulose triacetate film support. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.3 g Gelatin 2.2 g UV absorber U-1 0.1 g UV absorber U-3 0.05 g UV absorber U-4 0.1 g High boiling point Organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 3 mg Compound Cpd-K 3 mg High-boiling point organic solvent Oil-3 0.1 g Dye D-49 mg Third layer: intermediate layer Finely grained silver iodobromide emulsion with a fogged surface and inside (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.5 g Emulsion B Silver amount 0.3 g Gelatin 0.8 g Coupler C- 1 0.1 g Coupler C-2 0.2 g Coupler C-3 0.1 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High-boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Fifth layer: medium-sensitive red-sensitive emulsion Layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.05 g Coupler C-2 0.15 g Coupler C-3 0.2 g High boiling point organic solvent Oil- 2 0.1 g Additive P-1 0.1 g Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.05 g Coupler C-2 0. 15 g Coupler C-3 0.1 g Coupler C-9 0.15 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd- I 0.03 g Dye D-5 0.02 g Compound Cpd-J 5 mg High-boiling point organic solvent Oil-1 0.02 g Eighth layer: intermediate layer Silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g 9th layer: low-sensitivity green-sensitive emulsion layer Emulsion E- 1 Silver amount 0.3 g Emulsion F-1 Silver amount 0.3 g Emulsion G-1 Silver amount 0.3 g Gelatin 0.5 g Coupler C-4 0.05 g Coupler C-11 0.1 g Coupler C- 7 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-J 10 mg Compound Cpd-L 0 0.02g High boiling point organic solvent Oil 1 0.1 g High boiling point organic solvent Oil-2 0.1 g 10th layer: Medium-speed green sensitive emulsion layer Emulsion G-1 Silver amount 0.3 g Emulsion H-1 Silver amount 0.2 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-11 0.15 g Coupler C-7 0.05 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0 .02 g Compound Cpd-F 0.05 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-2 0.01 g Eleventh layer: high-sensitivity green-sensitive emulsion layer Emulsion I-1 Silver amount 0.3 g Emulsion J-1 Silver amount 0.2 g Gelatin 1.0 g Coupler C-4 0.15 g Coupler C-11 0.15 g Coupler C-7 0.05 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd- E 0.02 Compound Cpd-F 0.04 g Compound Cpd-K 5 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color-mixing inhibitor Cpd-A 0.01 g Compound Cpd- L 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of Dye E-2 0.05 g 14th layer: intermediate layer gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion layer Emulsion K Silver amount 0.4 g Emulsion L Silver amount 0.4 g Gelatin 0.8 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g 16th layer: Medium sensitivity blue sensitive emulsion layer Emulsion M Silver amount 0.2 g Emulsion N Silver amount 0.3 g Gelatin 0.9 g Coupler C-5 0.4 g Coupler C-6 0.05 g Coupler C-10 0.15 g No. 17 layers: High-sensitivity blue-sensitive emulsion layer Emulsion O Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling organic solvent Oil-2 0.1 g Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin Scavenger Cpd-H 0.4 g Dye D-1 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: second protective layer Colloidal silver Ag amount 0.1 mg Fine grain silver iodobromide Emulsion (average particle size 0.06 μm, AgI content 1 mol% ) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μm) 0.1 g Methyl methacrylate-acrylic acid copolymer (methyl Methacrylate: acrylic acid = 4: 6; average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g In addition, all emulsion layers In addition to the above composition, the additive F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added.

The silver iodobromide emulsions used in Samples 101 to 110 are as follows.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

[Chemical 25]

[0126]

[Chemical formula 26]

[0127]

[Chemical 27]

[0128]

[Chemical 28]

[0129]

[Chemical 29]

[0130]

[Chemical 30]

[0131]

[Chemical 31]

[0132]

[Chemical 32]

[0133]

[Chemical 33]

[0134]

[Chemical 34]

[0135]

[Chemical 35]

[0136]

[Chemical 36]

[0137]

[Chemical 37]

[0138]

[Chemical 38] <Preparation of Samples 102 to 111> For Sample 101, Table 6 and Table 6 show the spectral sensitization of the silver halide emulsions used in the ninth to eleventh layers and / or the change of the coating amount of the yellow colloidal silver in the thirteenth layer. Sample 102 performed as shown in FIG.
~ 111 were produced.

[0139]

[Table 6]

[0140]

[Table 7] Table 8 shows each parameter obtained from the equienergy spectral sensitivity distributions of the samples 101 to 111 prepared as described above.

[0141]

[Table 8] <Preparation of original reversal strips and evaluation of samples>
Various original image reversal strips were prepared as follows.

Fuji Photo Film Co., Ltd. RDP (milk number # 14
7), RVP (milk number # 525) manufactured by the same company, EPR (milk number # 939) manufactured by Eastman Kodak Company and PKR manufactured by the same company
A white light source with a color temperature of 4800 ° K was used for two strips each cut from (milk number # 157), one was subjected to wedge exposure with white light without a filter, and the other was Fuji Photo Film Co., Ltd. Filter BP-55
Through which wedge exposure with green light was performed. These strips were subjected to the standard process described in the specifications accompanying each reversal film to obtain a gray or green gradation original reversal strip for each reversal film. Perform sensitometry on these strips,
Gray at magenta analysis density 1.0 and 2.0
The sensitivity difference ΔSr between the magenta images of strips and green strips was determined. The results are shown in Table 9.

[0143]

[Table 9] Note: Sensitivity is the exposure dose (CMS) that gives each magenta density.
The unit is shown as the difference in Log value.

Next, these gray and green original reversal strips were closely attached in parallel to the test pieces cut from the above-mentioned samples 101 to 111, which are duplication films, at a color temperature of 3200 ° K. By appropriately adjusting the irradiation light amount and the density of the color correction filter to be used by the light source, the density of yellow, magenta and cyan at the point of the magenta analysis density 1.0 of the gray original image reversal strip is The test pieces were baked to have the same density in each of them, and then subjected to the following treatments. Treatment process Time Temperature Tank capacity Replenishment amount 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / m ² Color development 6 minutes 38 ° C. 12 liters 2200 ml / m ² adjustment 2 minutes 38 ° C. 4 liters 1100 ml / m ² Bleaching 6 min 38 ° C. 12 liters 220 ml / m ² Fixing 4 min 38 ° C. 8 liters 1100 ml / m ² second water washing 4 minutes 38 ° C. the composition 8 liters of 7500 ml / m ² Stabilizing 1 min 25 ° C. 2 liters 1100 ml / m ² each processing solution was as follows. (First developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.5 g 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sulfurous acid Sodium 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 pH is hydrochloric acid or potassium hydroxide. I adjusted it with. (Reversal liquid) (Tank liquid) (Replenishing liquid) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. (Color developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate-12 water Salt 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazic acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12. The pH was adjusted with hydrochloric acid or potassium hydroxide. (Adjusting liquid) (Tank liquid) (Replenishing liquid) Ethylenediamine tetraacetic acid / sodium salt / dihydrate 8.0 g 8.0 g Sodium sulfite 12 g 12 g 1-thioglycerol 0.4 g 0.4 g Formaldehyde sodium bisulfite addition Substance 30 g 35 g Water was added 1000 ml 1000 ml pH 6.30 6.10 pH was adjusted with hydrochloric acid or potassium hydroxide. (Bleaching solution) (Tank solution) (Replenishing solution) Ethylenediamine tetraacetic acid / disodium salt / dihydrate 2.0 g 4.0 g Ethylenediamine tetraacetic acid / Fe (III) / ammonium / dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added and 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with hydrochloric acid or potassium hydroxide. (Fixing solution) (Tank solution) (Replenishing solution) Ammonium thiosulfate 80 g The same sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. (Stabilizing liquid) (Tank liquid) (Replenishing liquid) Benzisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 g 0.3 g Water In addition, after 1000 ml 1000 ml pH 7.0 7.0 treatment, for each of Samples 101 to 111, sensitometry of the burned portion of gray strips and green strips was performed as in the case of the original reversal film, and magenta was measured. The sensitivity difference (ΔSd) between the magenta images of the gray and green duplication portions at the analytical densities of 1.0 and 2.0 was examined. The value of this sensitivity difference ΔSd and the sensitivity difference Δ in the original image reversal film
The deviation of the Sr value | ΔSr−ΔSd | is compared to find the fidelity to the original image in the color reproduction of green.
From the sum of the squares of r-ΔSd |, the magnitude of the variation depending on the type of original image reversal film was examined. The results are shown in Table 10.
Shown in.

[0145]

[Table 10] Note 1) Original color fidelity is indicated by | ΔSd-ΔSr |. Note 2) Variation in fidelity due to difference in originals is | ΔSd-ΔSr | squared by each original reversal image.
It is shown as the sum of 10 ⁴ .

As can be seen from Table 10, the samples 101, 102, and 10 in which the spectral sensitivity distribution is too wide (broad)
Nos. 4 and 105 have low fidelity to the whole, and the spectral sensitivity distribution is narrow (sharp) like the sample 106, but the peaks of the spectral absorption distributions of the dyes of the original reversal film are far from each other. Low. Also, sample 1
In the case of No. 01, which has a spectral sensitivity distribution that is too sharp and has no spectral sensitivity at long wavelengths, the reproducibility fidelity remarkably differs depending on the type of original image reversal film. On the other hand, Sample 1 using the silver halide emulsion of the present invention
07 to 111 have good fidelity regardless of the type of original reversal film.

As is clear from the above results, the silver halide color photographic light-sensitive material of the present invention can be used as a dupe film not only in the fidelity that is closer to the original in the green color reproduction of the original reversal image, but also in the original reversal. It was confirmed that it also has general versatility that there is little difference depending on the type of film.

[0148]

As described above, in the silver halide color photographic light-sensitive material of the present invention, the equienergetic spectral sensitivity distribution at each density of magenta analysis density of 1.0 or more and 2.0 or less has a predetermined characteristic. It is set. As a result, the fidelity of the original color is high, and the original color can be reproduced faithfully regardless of the type of the original reversal film.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive layer containing a yellow coupler, a green-sensitive layer containing a magenta coupler, and a red-sensitive layer containing a cyan coupler on a support. In the equienergetic spectral sensitivity distribution at each concentration of 1.0 to 2.0, the maximum sensitivity wavelength is 54
The wavelengths on the long-wave side and the short-wave side, which exist between 0 nm and 560 nm, have a sensitivity at 570 nm of 0.1 to 0.25 times the maximum sensitivity, and have a sensitivity of 1/10 of the maximum sensitivity. A silver halide color photographic light-sensitive material having a wavelength difference of 70 nm or less. 2. A silver halide emulsion comprising a plurality of green-sensitive layers having different sensitivities on a support and contained in at least one layer other than the layer having the lowest sensitivity among the plurality of green-sensitive layers, Be spectrally sensitized with at least one spectral sensitizing dye represented by the general formula (I) and at least one spectral sensitizing dye represented by the general formulas (II) to (IV). A silver halide color photographic light-sensitive material according to claim 1. [Chemical 1] (In the formula, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group,
Represents an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, a cyano group or an alkyl group, and Y ₁ and Y
Either one of ₂ or Y ₃ and Y ₄ may be linked to each other to form a ring to form a naphthoxazole ring. R ₁ represents a hydrogen atom or an alkyl group, R ₂ and R ₃ each represent an alkyl group, X ₁ − represents an anion, and n represents an integer of 1 or 2. However, when n represents 1, R ₂ or R ₃ represents a group capable of forming an inner salt. ) [Chemical 2] (In the formula, Y ₅ and Y ₆ and Y ₇ and Y ₈ each represent a group of atoms which are linked to each other to form a ring and form a naphthoxazole ring. Further, R ₄ represents a hydrogen atom or an alkyl group. , R ₅ and R ₆ each represent an alkyl group, X ₂ — represents an anion, and m represents an integer of 1 or 2. provided that when m represents 1,
R ₅ or R ₆ represents a group capable of forming an inner salt. ) [Chemical 3] (In the formula, Y ₉ , Y ₁₀ , Y ₁₁ and Y ₁₂ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, Represents a cyano group or an alkyl group, Y ₉ and Y ₁₀
Alternatively, at least one of Y ₁₁ and Y ₁₂ may be linked to each other to form a ring and form a naphthimidazole ring. R ₇ represents a hydrogen atom or an alkyl group, R ₈
R ₉ , R ₁₀ and R ₁₁ each represent an alkyl group,
X ₃ − represents an anion, and r represents an integer of 1 or 2. However, when r represents 1, R ₈ , R ₉ , R
₁₀ or R ₁₁ represents a group capable of forming an inner salt. ) [Chemical 4] (In the formula, Y ₁₃ , Y ₁₄ , Y ₁₅ and Y ₁₆ are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, Represents a cyano group or an alkyl group, Y ₁₃ and Y ₁₄
May be linked to each other to form a ring to form a naphthoxazole ring, and Y ₁₅ and Y ₁₆ may be linked to each other to form a ring to form a naphthimidazole ring. Also, R
₁₂ represents a hydrogen atom or an alkyl group, R ₁₃ , R ₁₄ and R ₁₅ each represent an alkyl group, X ₄ − represents an anion, and q represents an integer of 1 or 2. However, when q represents 1, R ₁₃ or R ₁₄ represents a group capable of forming an inner salt. )