JPH10142732A - Silver halide color reversal photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide color photographic sensitive material low in tendency to cause uneven color development density. SOLUTION: The silver halide color reversal photographic sensitive material is provided on a support with at least one photosensitive layer and at least one nonphotosensitive layer and a hydrophilic colloidal layer located outermost from the support contains at least one kind of polyorganoisiloxane, in an amount of 0.10-0.40g/m<2> , represented by the formula in which R is a 1-3C alkyl group; R1 is a 1-3C alkyl or 1-2C alkoxy group; and (n) is an integer of 0-2000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color reversal light-sensitive material, and more particularly to a silver halide color reversal light-sensitive material having improved color density unevenness.

[0002]

2. Description of the Related Art Generally, a method of fixing a photographic film individually in the vertical direction and sequentially developing the film (hereinafter referred to as hanging development).
In, the photographic properties obtained at the position of the developed film are often slightly different. This phenomenon is caused by a difference in the amount of bubbles of the developing solution adhered to the film surface generated during transport, and is more likely to occur when hanging development having a low linear velocity is used as compared with cine-type development having a high linear velocity. . The above phenomenon is not noticeable when the development density is high,
When the development density is low, it is conspicuous. Therefore, in a color negative which is viewed only by printing, even if there is uneven density, it is not conspicuous on the print. On the other hand, a color reversal film which is often viewed directly tends to be a serious defect. The present inventors have made intensive studies to solve this problem.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color reversal photographic material in which color density unevenness is less likely to occur.

[0004]

[Means for Solving the Problems]

(1) An object of the present invention is to provide a silver halide color reversal photosensitive material having at least one photosensitive layer and at least one non-photosensitive layer provided on a support, respectively. The photosensitive layer contains at least one kind of polyorganosiloxane represented by the following general formula [I] in an amount of 0.10.
It was achieved by a silver halide color reversal light-sensitive material containing g / m ² or more 0.40 g / m ² or less.

[0005]

Embedded image

Wherein R is an alkyl group having 1 to 3 carbon atoms,
R ₁ is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and n is an integer of 0 to 2000. (2) The hydrophilic colloid layer contains barium sulfate and / or strontium sulfate having an average particle size of 5 μm or less and 0.5 μm
m or more of the particles 0.15g / m ² more than 0.30g / m ²
The silver halide color reversal photosensitive material according to (1), which comprises:

[0007]

DETAILED DESCRIPTION OF THE INVENTION A method for synthesizing the above polyorganosiloxane is described in British Patent No. 955,061. The above-mentioned polyorganosiloxane can be applied as it is after emulsifying and dispersing by using a known method, or by mixing with an appropriate binder.

The color reversal photographic light-sensitive material of the present invention is particularly suitable as a film for an advanced photo system (hereinafter referred to as an AP system), and NEXIA A manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NE
Films processed into the AP system format such as XIA F and NEXIA H (in order, ISO 200/100/400) and stored in special cartridges can be mentioned. These APs
The cartridge film for a system is used by being loaded into a camera for an AP system such as an EPION series (EPION 300Z, etc.) manufactured by FUJIFILM Corporation. The film photographed by these is printed through the following steps. (1) Acceptance (Take the exposed cartridge film from the customer) (2) Detach process (transfer the film from the cartridge to the intermediate cartridge for the development process) (3) Film development (4) Rear touch process (developed film) (5) Printing (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably Fujifilm color reversal paper)) (6) Collation and shipping (The cartridge and the index print are collated by ID number and shipped together with the print. In addition, the developed film is the same as the conventional 135 film,
(They may be returned in the form of a mount or a sleeve.) As these systems, Fujifilm Digital Lab System Frontier is preferable. H4R-120D / H6R-360D / CR-412O / CR as color reversal film processor
And a hanging type automatic developing machine such as -6240. It is preferable to use a photosensitive material clip described later and a photosensitive material hanger using the same. FR as a cinematic automatic processor
CP-500 is listed, and as a splicer, selexxa spli
cer 550 and selexxa NRIC 650 as the desplicer. The recommended treatment chemical is CR-56P. Examples of color reversing paper printers include the 8C6910 / FAP3500, and the FAP3500 can also print on duplicate films. As a processor for reverse color paper
CSRII-3160 / CSRII-2460 / RVPII-R204, and the recommended treatment chemical is RP-303. In the frontier system, scanner & image processor SP-1000 and laser printer & paper processor LP-1000P or laser printer LP-1000W are used. The detacher used in the detaching process and the rear toucher used in the rear attaching process are FUJIFILM's DT200 / DT10, respectively.
0 and AT200 / AT100 are preferred.

[0009] The AP system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, you can directly load a developed AP system cartridge film into the Aladdin 1000, or transfer image information from negative film, positive film, and print to a 35mm film scanner FE.
-550 and flat head scanner PE-550, and the obtained digital image data can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints with existing lab equipment through a film recorder. The Aladdin 1000 can also transfer digital information directly to a floppy disk, Zip disk, or via a CD writer.
You can also output to CD-R. At home, on the other hand, you can enjoy your photos on a TV simply by loading the developed AP system cartridge film into the Fujifilm Photo Player AP-1.
If it is loaded into the PC, image information can be continuously captured at high speed into a personal computer. To input a film, print, or three-dimensional object into a personal computer, a Fuji Vision PhotoVision FV-10 / FV-5 can be used. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. To output high-quality prints from a personal computer, use the Fuji-Film Digital Color Printer NC-2 / N of the light fixing type thermal color print method.
C-2D is preferred. To store the developed AP system cartridge film, use the Fuji Color Pocket Album
AP-5 POP L, AP-1 POP L, AP-1 POP KG or cartridge file 16 is preferred.

[0010] for preparing a color density increment of D ^B by the magnetic recording backing layer, as in Japanese Patent Laid-Open No. 4-73735, not decolorized in the developing process, non-diffusible dyes of the non-imagewise preferably In particular, anthraquinone dyes are more preferable.

When developing the photosensitive material, FIG. 1, FIG.
With the photosensitive material clip shown in FIG. 3 and the photosensitive material hanger using the same, without damaging the photosensitive material,
Can be gripped in good condition.

Referring to FIG. As shown in FIG. 1, a hanger 10 is formed by a horizontal bar 14 having both ends supported by a transport device and a support bar 16 formed in a U-shape and having both ends connected to the horizontal bar 14 by welding or the like. Frame 12 is formed.

A pair of first brackets 18 and three second brackets 20 located between the pair of first brackets 18 are continuously attached to the support rod 16 of the frame 12. First bracket 18
And a lower end of the second bracket 20 is connected to one continuous rod 22.
Are respectively penetrated, and the lower sides of the first bracket 18 and the second bracket 20 are supported.

Further, between the brackets 18 and 20 on the lower side of the frame 12, four support members 24 are arranged with the connecting rod 22 penetrating therethrough. And
The film F is suspended in an inverted U-shape in a form of turning on the support member 24, and the lower portion thereof is gripped by the photosensitive material clip 36 with a weight.

FIGS. 2A and 2B show details of the photosensitive material clip, and FIGS. 3A and 3B show details of the support member 24. FIG.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer, JP-A-61-43748, 59-113
No. 438, 59-113440, 61-20037, couplers as described in the specification of 61-20038, DIR compounds and the like may be contained. May be included. The plurality of silver halide emulsion layers constituting each unit light-sensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in JP-A-06543 and the like, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokunoaki
As described in JP-A-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. JP-A-56-25738, 62-63
As described in the specification of U.S. Pat. No. 936, a blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even in the case of comprising three layers having different sensitivities, as described in JP-A-59-202464, a medium-speed emulsion is provided in the same color-sensitive layer from the side away from the support. Layers / high-speed emulsion layers / low-speed emulsion layers. 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
The arrangement may be changed as described above even in the case of more than layers.

In order to improve color reproducibility, US Pat.
Nos. 663,271, 4,705,744, 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, or RL is disposed adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material. 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. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about
Fine particles having a diameter of 0.2 μm or less or large particles having a projected area diameter of about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used. Silver halide photographic emulsions which can be used in the present invention are described, for example, in Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and the like.
No.18716 (November 1979), p.648, No.307105 (1989
Nov.), pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie)
et Phisique Photographique, PaulMontel, 1967), Duffin's Photographic Emulsion Chemistry, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Production and Coating of Photographic Emulsion" by Zelikman et al., Published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964). Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 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, Photographic Science and E).
14, 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the methods described in JP-A-4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, and may have a layered structure.
Further, silver halides having different compositions may be joined by an epitaxial junction.
It may be bonded to a compound other than silver halide such as lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal latent image type in which a latent image is formed in the inside of a grain or a type having a latent image on both the surface and the inside.
It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion 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. As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives used in such a process are Research Disclosure N
o. 17643, No. 18716 and No. 307105, and the relevant locations are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. U.S. Pat.No. 4,082,553 describes a silver halide grain having a fogged surface, U.S. Pat.No. 4,626,498, a silver halide grain having a fogged interior described in JP-A-59-214852, and colloidal silver. It can be preferably used for a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . The preparation of silver halide grains having a grain interior or surface fog is described in U.S. Pat.
No. 98 and JP-A-59-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain covered,
Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The size of the fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. There is no particular limitation on the particle shape,
Regular grains or polydisperse emulsions may be used,
It is preferably monodisperse (a silver halide grain in which at least 95% of the weight or the number of grains has a grain size within ± 40% of the average grain size). In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably silver iodide is 0.5
-10 mol%. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01
To 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. 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. 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 the following table.

Types of Additives 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 23-24, page 648, right column, 866- Page 868 Super sensitizer ~ Page 649 right column 4. Brightener 24 page 647 page right column 868 5. Fogging prevention 24 ~ 25 page 649 right column 868 ~ 870 page Agents, stabilizers 6. Light absorber 25-26 page 649 right column page 873 filter-page 650 left column Dyes, UV absorbers 7.Stain 25 page right column 650 page left column 872 inhibitor-right column 8. Dye image 25 page 650 page left Column 872 Stabilizer 9. Hardener page 26 Page 651 Left column 874-875 10. Binder page 26 Page 651 Left column 873-874 11. Plasticizer, Page 27 650 Right column Page 876 Lubricant 12. Coating aids, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactants 13. Statistics, page 27, page 650, right column, pages 876 to 877 Inhibitors 14. Matting agents, pages 878 to 879

In order to prevent photographic performance from deteriorating due to formaldehyde gas, it is preferable to add a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 and fixing the same to the photosensitive material. . U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A-1-28
It is preferable to include a mercapto compound described in No. 3551. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, International Publication WO88 / 04794, dyes dispersed by the method described in JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP-A 1-2593
The dye described in No. 58 is preferably contained. Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in Research Disclosure Nos. 17643, VII-CG, and VII-CG and Nos. 307105 and VII.
-Described in the patents described in CG. As the yellow coupler, for example, U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Patent No. 3,97
Preferred are those described in 3,968, 4,314,023, 4,511,649 and European Patent 249,473A.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897, and EP 73,63.
6, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure No.2
4230 (June 1984), JP-A-60-43659, JP-A-61-72238
No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patents 4,500,630, 4,540,654, 4,5
No. 56,630 and WO 88/04795 are particularly preferable. Cyan couplers include phenolic and naphthol couplers and are described in U.S. Pat.
No. 12, No. 4,146,396, No. 4,228,233, No. 4,2
No. 96,200, No. 2,369,929, No. 2,801,171, No.
No. 2,772,162, No. 2,895,826, No. 3,772,002,
No. 3,758,308, No. 4,334,011, No. 4,327,173
No., West German Patent Publication No. 3,329,729, European Patent No. 121,365
A, 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,616, and 4,451,559
No. 4,427,767, No. 4,690,889, No. 4,25
Nos. 4,212, 4,296,199 and JP-A-61-42658 are preferred. Further, JP-A-64-553 and JP-A-64-553
-554, 64-555 and 64-556, and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
No. 51,820, No. 4,080,211, No. 4,367,282, No.
4,409,320, 4,576,910, UK Patent 2,102,137
And European Patent No. 341,188A. U.S. Pat.No. 4,366,237, British Patent No. 2,125,570, European Patent No.
No. 96,570 and West German Patent Publication No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is Research Disclosure No. 1
No. 7643, VII-G, No. 307105, VII-G, U.S. Pat.No. 4,163,670, JP-B-57-39413, U.S. Pat.
Nos. 4,929, 4,138,258 and British Patent 1,146,368 are preferred. U.S. Pat.No. 4,774,181
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in JP-A-4,777,120 as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are:
RD 17643, VII-F and 307105, VII-
Patents described in section F, JP-A-57-151944, JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
And those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. RD No. 11449, 24241, JP-A-61
The bleaching accelerator releasing couplers described in -201247 and the like are effective in shortening the time of a processing step having bleaching ability,
In particular, the effect is great when added to a light-sensitive material using the above-mentioned tabular silver halide grains. As the coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, those described in British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, by the oxidation-reduction reaction with the oxidized form of the developing agent described in JP-A-1-45687, fogging agent, development accelerator ,
Compounds that release a silver halide solvent or the like are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competing couplers described in US Pat. No. 4,130,427 and the like, and US Pat. Nos. 4,283,472 and 4,3
Nos. 38,393, 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds Or a DIR redox-releasing redox compound, a coupler releasing a dye capable of recoloring after detachment described in European Patent Nos. 173,302A and 313,308A, a ligand releasing coupler described in U.S. Pat. -75747 Leuco dye releasing couplers, U.S. Pat.
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic 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, dichloropropyl
2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic esters (bis (2-ethylhexyl) sebacate, dioctylase) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃
An organic solvent having a temperature of about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include 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 U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747, JP-A-62-272248,
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or fungicides such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, No. 18716, page 647 right column to page 648 left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is controlled at 25 ° C and relative humidity of 55% (2 days)
And the film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.), 19 vol., No. 2, by using a 124 type described on pages to 129 Swellometer (swelling meter) can be measured, T _1/2 in color developer 30 90% of the maximum swollen film thickness reached when the treatment is performed at 3 ° C. for 3 minutes and 15 seconds is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.
The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 1
50-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness. The photosensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a μm hydrophilic colloid layer (referred to as a back layer). The 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 the back layer is preferably from 150 to 500%.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methylaniline. -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 sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution has a pH such as an alkali metal carbonate, borate or phosphate.
It generally contains a buffer, a chloride inhibitor, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, as required, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic 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, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and the like Can be mentioned as typical examples.

Next, processing solutions and processing steps of the color reversal photosensitive material of the present invention other than the color developing solution will be described. The steps from black development to color development in the processing steps of the color reversal photosensitive material of the present invention are as follows. 1) Black-and-white development-water-reversal-color development 2) Black-white development-water-light reversal-color development 3) Black-white development-water-wash-color development All of the water-washing steps 1) to 3) are U.S. Pat.
Instead of the rinsing step described in JP-A No. 04,616, simplification of treatment and reduction of waste liquid can be achieved. Next, steps after the color development will be described. 4) Color development-Adjustment-Bleaching-Fixing-Rinse-Stable 5) Color development-Water wash-Bleaching-Fixing-Rinse-Stable 6) Color development-Adjustment-Bleaching-Rinse-Fix-Rinse-Stable 7) Color development-Rinse -Bleaching-Washing-Fixing-Washing-Stable 8) Color development-Bleaching-Fixing-Washing-Stable 9) Color development-Bleaching-Bleaching-Washing-Stable 10) Color development-Bleaching-Bleaching-Fixing-Washing-Stable 11) Color development-Bleaching-Rinse-Fix-Rinse-Stable 12) Color development-Adjustment-Bleaching-Rinse-Stable 13) Color development-Rinse-Bleaching-Rinse-Stable 14) Color development-Bleaching-Rinse- Stable 15) Color development-fixing-bleach-fixing-rinsing-stabilizing In the processing steps 4) to 15), the washing step immediately before the stabilizing step may be eliminated, and conversely, the stabilizing step of the final step is not performed. You may. Any one of the above steps 1) to 3) and one of the 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 for the black-and-white developer used in the present invention. As a developing agent, dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-
3-pyrazolidone), aminophenols (for example, N
-Methyl-p-aminophenol), 1-phenyl-3
Pyrazolines, ascorbic acid and U.S. Pat.
Heterocyclic compounds in which a 1,2,3,4-tetrahydroquinoline ring and an indole ring described in JP-A-67,872 are condensed can be used alone or in combination. The black-and-white developer used in the present invention may further contain a preservative (eg, sulfite, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine), an alkali agent (eg, Hydroxides, carbonates), dissolving tablets (eg, polyethylene glycols, esters thereof), pH adjusters (eg, organic acids such as acetic acid),
Sensitizers (eg, quaternary ammonium salts), development accelerators,
A surfactant, an antifoaming agent, a hardening agent, a viscosity imparting agent and the like can be contained. The black-and-white developer used in the present invention must contain a compound that acts as a silver halide solvent, and the sulfite usually added as a preservative serves the role. Examples of the sulfite and other silver halide solvents that can be used include KSCN, NaSC
N, 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 of the developer thus adjusted
The values are selected to be sufficient to provide the desired density and contrast, but range from about 8.5 to about 11.5. In order to perform sensitization processing using such a black-and-white developer, it is usually sufficient to extend the time up to about three times the standard processing. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be reduced.

The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed.
Generally, the amount is 3 liters or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷ [volume of processing solution (cm ³ )] The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method of reducing the aperture ratio in this manner, in addition to providing a shield 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, 63-216050 can be mentioned. Reducing the aperture ratio is not only a step of color development and a step of black-and-white development, but also various subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The reversal bath used after black-and-white development can contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (U.S. Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (JP-B-56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
No. 50), stannic ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (British Patent No. 1,011,0)
No. 00) and the like. The pH of the fogging bath (reversal bath) ranges from an acidic side to an alkaline side, and is in a range of pH 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
Light reversal treatment by re-exposure may be performed instead of the reversal bath, and the reversal step can 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 subjected to bleaching or bleach-fixing after color development. These processes may be performed immediately after the color development without going through other processing steps,
In order to prevent unnecessary post-development and air fogging, to reduce the amount of color developing solution brought into the desilvering process, and to use in photographic materials such as sensitizing dyes and dyes contained in photographic materials and photographic materials. In order to wash out and render the impregnated color developing agent harmless, the color developing process may be followed by a bleaching process or a bleach-fixing process after processing steps such as stopping, adjusting, and washing with water.

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. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid Etc. can be used. Of these, ethylenediaminetetraacetate (III) complex salt and 1,3-diaminopropanetetraacetate (I
II) Iron (III) aminopolycarboxylate complex salts such as complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing. Bleach,
A bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification: US Pat.
No. 3,858, West German Patent Nos. 1,290,812, 2,059,988,
JP-A Nos. 53-32736, 53-57831, 53-37418, 53
-72623, 53-95630, 53-95631, 53-104232
No. 53-124424, No. 53-141623, No. 53-28426,
Research Disclosure No.17129 (July 1978
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129; Japanese Patent Publication Nos. 45-8506 and 52-20832, 53
-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16,235; West German Patents 966,410, 2,748,430
No. 45-883
Polyamine compound described in No. 6; Other JP-A-49-40,943
Nos. 49-59,644, 53-94,927, 54-35,727
Compounds described in Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Pat. Further, the compounds described in U.S. 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 photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in European Patent No. 294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to
45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for 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 consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have the photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture a.
nd Television Engineers Vol. 64, pp. 248-253 (1955)
May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used. PH of washing water in processing the photosensitive material of the present invention
Is 4 to 9, preferably 5 to 8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, the application, etc.
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.
Various chelating agents and fungicides can also be added to this stabilizing bath. The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. In the processing using an automatic developing machine 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 light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Indoaniline compounds described in No. 42,597, No. 3,342,5
No. 99, Research Disclosure No. 14,850 and 1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development.
Typical compounds are JP-A-56-64339, JP-A-57-144547,
And No. 58-115438. The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

[0037]

【Example】

(Embodiment 1) Hereinafter, the present invention will be described in detail with reference to embodiments, but is not limited thereto. Preparation of Sample 101 On a support described later, a multilayer color light-sensitive material composed of each layer having the following composition was prepared to obtain Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.10 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g g High boiling organic solvent Oil-4 / Oil-5 (1/1) 0.06 g Dye E-1 0.03 g

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average grain size: 0.06 μm, coefficient of variation: 18%, AgI content: 1 mol%) g gelatin 0.40g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.30 g Emulsion B silver amount 0.20 g gelatin 1.00 g Coupler C-1 0.15 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-9 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Fifth layer: middle-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling organic solvent Oil-2 0.10g Additive P-1 0.10g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.70 g Additive P-1 0.10 g

Seventh layer: Intermediate layer Gelatin 0.60 g Additive M-1 0.30 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High boiling organic solvent Oil -1 0.020g

Eighth layer: Intermediate layer A 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 0.020 g Yellow colloidal silver Silver amount 0.020 g Gelatin 1.00 g Additive P-1 0.20 g Color mixing inhibitor Cpd-A 0.10 g Compound Cpd-C 0.10 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E silver amount 0.10 g Emulsion F silver amount 0.20 g Emulsion G silver amount 0.20 g gelatin 0.50 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-8 0.10 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-1 0.10 g High boiling organic Solvent Oil-2 0.10g

Tenth layer: Medium-sensitive green-sensitive emulsion layer Emulsion G silver amount 0.30 g Emulsion H silver amount 0.10 g gelatin 0.60 g coupler C-4 0.070 g coupler C-7 0.050 g coupler C-8 0.050 g compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g Compound Cpd-L 0.050 g High boiling organic solvent Oil-2 0.010 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 1.00 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.050 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-2 0.020 g

12th layer: Intermediate layer Gelatin 0.60 g Compound Cpd-L 0.050 g High boiling organic solvent Oil-1 0.050 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.020 g Gelatin 1.10 g Color mixing inhibitor Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling organic solvent Oil-1 0.010 g Fine crystals of dye E-2 Solid dispersion 0.030 g Microcrystalline solid dispersion of dye E-3 0.020 g

Fourteenth layer: Intermediate layer Gelatin 0.60 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J silver amount 0.20 g emulsion K silver amount 0.30 g gelatin 0.80 g coupler C-5 0.20 g coupler C-6 0.10 g coupler C-10 0.40 g

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.30 g Emulsion M silver amount 0.30 g gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g

17th layer: Highly sensitive blue-sensitive emulsion layer Emulsion N silver amount 0.20 g Emulsion O silver amount 0.20 g gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.10g

18th layer: 1st protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Formalin scavenger Cpd-H 0.40 g Dye D-1 0.15 g Dye D-2 0.050 g Dye D-3 0.10 g

Nineteenth layer: Second protective layer Yellow colloidal silver Silver content 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.10 g Gelatin 0.40 g

20th layer: 3rd protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and methacrylic acid 6: 4 (average particle size 1.5 μ) 0.10 g Silicone oil SO-1 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

Further, additives F-1 to F-8 were added to all the emulsion layers in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and butyl p-benzoate were added as preservatives and fungicides. Preparation of Dispersion of Organic Solid Disperse Dye Dye E-2 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a wet cake of a dye containing 30% of methanol, followed by stirring to obtain a slurry having a dye concentration of 6%. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
The slurry was pulverized for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. The beads were removed by filtration, diluted with water by adding water to a dye concentration of 3%, and heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained fine dye particles was 0.54 μm, and the width of the particle size distribution (particle size standard deviation × 100 / average particle size) was 18%.

In the same manner, a solid dispersion of Dye E-3 was obtained. The average particle size was 0.56 μm.

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[Table 1]

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[Table 2]

[0076]

[Table 3]

1) Support The support used in this example was prepared by the following method. 100 parts by weight of polyethylene 2,6 naphthalate and an ultraviolet absorber (Tinuvin P. 326, Ciba
2 parts by weight (manufactured by Geigy Co., Ltd.), dried at 300 ° C., extruded from a T-die, and stretched 3.3 times at 140 ° C. Subsequently, the film is stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a thickness of 90 μm.
m of polyethylene naphthalate (PEN) film was obtained. The PEN film includes a blue dye, a magenta dye and a yellow dye (I-described in JP-A-94-6023).
-1, I-4, I-6, I-24, I-26, I-2
7, II-5) was added in an appropriate amount. Furthermore, diameter 20cm
And a heat history of 110 ° C. for 48 hours was given to obtain a support that is less likely to have a curl. The length in the width direction of the support is 14 cm.

2) Coating of undercoat layer After corona discharge treatment, UV irradiation treatment, and glow discharge treatment on both surfaces of the support, gelatin 0.1 g / m ² , α-sulfurose 2 was applied to both surfaces on the high temperature side during stretching. -Ethylhexyl sodium succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m
² , (CH ₂ 2CHSO ₂ CH ₂ CH ₂ NHCO) ₂ C
H ^₂ 0.012g / m _2, the undercoat liquid of the polyamide chromatography epichlorohydrin polycondensate 0.02 g / m ² was applied (10 cc / m ^2, a bar coater used) was provided an undercoat layer. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of antistatic backing layer Fine powder of tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm (specific resistance: 5Ω) was provided on the surface opposite to the side on which the undercoat layer of the support was provided. .Cm) dispersion (secondary aggregate particle diameter: about 0.08 μm) 0.2 g / m ² , gelatin 0.05 g / m ² , (CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂₎
NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005
g / m ² and resorcinol were applied to provide an antistatic backing layer.

4) Coating of magnetic recording backing layer On the antistatic backing layer, 3-poly (degree of polymerization: 1)
5) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / g, long axis: 0.14 μm, single axis: 0.03 μm, saturation Magnetization: 89 emu / g, Fe ⁺²
/ Fe = 6/94, surface: dispersion of 32 mg / m ² in 1.2 g / m ^{2 of} diacetylcellulose (dispersion using an open kneader and a sand mill) Practice), C ₂ H as a curing agent
_{3 C (CH 2 OCONH-C} 6 H 3 (CH 3) NCO)
₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to provide a 1.2 μm-thick magnetic recording backing layer. In addition, silica particles (0.3 μm) as a matting agent
And 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxylane (15% by weight) as an abrasive
The aluminum oxide (0.15 μm) coated with the above was added at a concentration of 20 mg / m ² . 11 for drying
The test was performed at 5 ° C. for 6 minutes (all rollers and transporting devices in the drying zone were 115 ° C.). X-light (blue filter)
Magnetic recording backing layer of the D color density increment is about 0.06 of ^B in the saturation magnetization moment of the magnetic recording backing layer 2.5emu / m ^2, coercive force 980Oe, and squareness ratio was 65% .

5-1) Preparation of slip agent dispersion n-C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ -C
_{OO-n-C 40 H 81} 15.0g and C ₅₀ H ₁₀₁ O
(CH ₂ CH ₂ O) ₁₆ H in 15.0 g, xylene / propylene glycol monomethyl ether (1/1 weight ratio,
1.0 kg of a solvent (1) was added, and a crude dispersion was prepared with a homomixer. The crude dispersion was added to the solvent (1) 0.1.
3 kg, isopropyl alcohol (IPA) 6.5 k
g, 0.25 kg of methyl alcohol, 80 g of a 5% by weight IPA solvent of hydroxypropylcellulose as a binder, 60 g of a 5% by weight methyl alcohol solvent as a surfactant, and a silicone compound (polyester-modified dimethylpolysiloxane, BYK-310). And 4 g of a 4% by weight IPA solution (manufactured by Big Chemie Japan KK) were added, and the mixture was subjected to ultrasonic dispersion at a low temperature (about -10 ° C) to prepare a fine particle dispersion having an average particle size of 0.50 µm. .

5-2) Coating of Surface Backing Layer The above dispersion was applied by a bar coater method at a coating speed of 50 m so that the coating amount of each component was as follows.
/ Min over the magnetic recording backing layer.

<< Surface Backing Layer Component >> ───────────────────────────── Binder (hydroxypropylcellulose) 2.0mg / m^Two Slip agent (n-C₆H₁₃CH (OH) C_TenH₂₀-COO-n-C₄₀H₈₁) 7.5 mg / m^Two Slip agent (C₅₀H₁₀₁O (CH_TwoCH_TwoO)₁₆H) 7.5 mg / m ^Two Slip agent (silicone compound, BYK-310) 1.5 mg / m ^Two Surfactant (C₈H₁₇SO_TwoN (C_ThreeH₇)-(CH_TwoCH_TwoO)_n− (CH _Two )_Four-SO_ThreeNa (n = 4)) 1.5 mg / m ^Two ─────────────────────────────────── ─

Incidentally, as for the slipping agent, DSC (Differen
The heat of fusion was determined by tial Scattering Calorimeter), it was measured and the thermal _{changes, (n-C 6 H 13} CH
_{(OH) C 10 H 20 -COO} -n-C 40 H 81) is, 90 ° C.
A clear endothermic peak was observed. On the other hand, (C ₅₀ H
_{For 101} O (CH ₂ CH ₂ O) ₁₆ H), an endothermic peak was also observed at 108 ° C.

Drying is equivalent to a web length of 50 m during the preheating period (initial set zone), and 250 m in the constant rate drying period.
The drying zone is set by a string-winding type air-floating system, and the drying rate is reduced by a web length of 1
It is equivalent to 00 m, of which 50 m corresponds to a pass roller which is moved straight between movable rollers which are alternately opposed to each other up and down, and the remaining 50 m corresponds to a U-shape and finally a drying zone for winding. At this time, a fixed amount of low-humidity air jet was blown so that the drying temperature during the constant rate drying period and the reduced rate drying period was in the range of 60 to 110 ° C, and drying was performed. The coating length is 1000 m.

Next, sample 102 was prepared in the same manner as sample 101 except that the silicone oil (SO-1) in the twentieth layer of sample 101 was changed to the polyorganosiloxane (SO-2, SO-3) of the present invention. , 103 were produced. Further, Samples 104 to 112 were produced by changing the amount of SO-1 added to Sample 101, the amount of SO-2 added to Sample 102, and the amount of SO-3 added to Sample 103. These contents are shown in Table 4.
Are shown together.

[0087]

Embedded image

[0088]

[Table 4]

The obtained samples 101 to 112 were exposed so that a gray density of about 0.7 was obtained at the wedge of the raw glass. The sample after the exposure was subjected to a color reversal process by the following processing steps. However, processing was carried out after bubbles were sufficiently formed with a developing solution which ran sufficiently to easily detect density unevenness.

After the development, the obtained samples were evaluated for uneven density and adhesion by five evaluators. Density unevenness was determined by visual observation. The judgment was performed by five persons, and the judgment criteria were as follows. 1: Not at all disturbed 2: Not at all disturbed 3: Slightly disturbed 4: Slightly disturbed 5: Notably problematic The evaluation was made as an average of five persons. Regarding the adhesion, the developed film (40 sheets) was stored in an AP system cartridge, left in an atmosphere of 30 ° C. and 80% RH for 3 weeks, pulled out, and the number of frames of the adhesion mark affecting the screen was determined. The results are summarized in Table 4.

As is clear from Table 4, the sample of the present invention has a better evaluation of the density unevenness than the comparative sample, and does not deteriorate the adhesion after the treatment.

(Example 2) Sample 107 in Example 1
Matting agent of the 20th layer (6: 4 polymer of methyl methacrylate and methacrylic acid (average particle size 1.5 μm) 0.1
0 g) of the matting agent of the present invention (strontium sulfate and barium sulfate at a weight ratio of 3: 1 and an average particle size of 1.5%).
μm) except that the same amount was used.
1 was produced.

Next, samples 202 to 206 were prepared by changing the amount of the matting agent of the present invention added to sample 201 as shown in Table 5.

For these samples, in addition to the same evaluation as in Example 1, haze and adhesion before treatment were evaluated. Haze was measured with a haze meter. 25 ° C before treatment
After adjusting the humidity to 65% RH, fill in white plastic bags, and weigh 60 kg at 30 ° C.
After applying a load of 3 days, the area of uneven glossiness was evaluated.
The same effect as in Example 1 was obtained for the uneven density and the adhesion after the treatment. Table 5 shows the evaluation results of the adhesion and the haze after the treatment.

[0095]

[Table 5]

As is evident from Table 5, the sample of the present invention has a good haze and a good glossy area with a small gloss unevenness as compared with the comparative sample.

Processing Step Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water wash 2 minutes 38 ° C. 4 liters 7500 ml / m ² Reversal 2 minutes 38 ° C. 4 liters 1100 ml / m m ² color development 6 minutes 38 ° C 12 liters 2200 ml / m ² before bleaching 2 minutes 38 ° C 4 liters 1100 ml / m ² bleaching 6 minutes 38 ° C 12 liters 220 ml / m ² fixed 4 minutes 38 ° C 8 liters 1100 ml / m ² Second water washing 4 minutes 38 ° C 8 liter 7500 ml / m ² Final rinse 1 minute 25 ° C 2 liter 1100 ml / m ²

The composition of each processing solution was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphone pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone 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 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversal solution] [Tank solution] [Replenishment solution] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.0 g p-amino acid Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 dehydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazinic 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 Add water 1000 ml 1000 ml l pH 11.80 12.00 pH adjusted with sulfuric acid or potassium hydroxide did.

[Pre-bleaching] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Sodium bisulfite formaldehyde adduct 30 g 35 g Water was added, 1000 ml 1000 ml, pH 6.30 6.10 The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium dihydrate 120 g 240 g Bromide Potassium 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml to pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g Same sodium sulfite 5.0 g ナ ト リ ウ ム Sodium bisulfite 5.0 g 〃 Add water to 1000 ml ｐＨ pH 6.60 Adjust pH with acetic acid or aqueous ammonia did.

[Stabilizing solution] [Tank solution] [Replenishing solution] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g 0.3 g Polymalein Acid (average molecular weight 2,000) 0.1 g 0.15 g Add water to make 1000 ml 1000 ml. PH 7.0 7.0

[Brief description of the drawings]

FIG. 1 is a front view showing a hanger for a photosensitive material in which a photosensitive material supporting member used for processing the photosensitive material of the present invention is incorporated.

FIGS. 2A and 2B are diagrams of a photosensitive material clip, wherein FIG. 2A is a front view and FIG. 2B is a side view.

3A and 3B are diagrams of a photosensitive material support member 24, wherein FIG. 3A is a side view as viewed from the inside of a support plate, and FIG. 3B is a front view.

[Explanation of symbols]

 Reference Signs List 10 hanger for photosensitive material 24 photosensitive material support member 36 clip for photosensitive material

Claims (2)

[Claims] 1. A silver halide color reversal photosensitive material comprising at least one light-sensitive layer and at least one non-light-sensitive layer provided on a support, respectively. 0.10 g of at least one polyorganosiloxane represented by the following general formula [I]
The silver halide color reversal light-sensitive material characterized by containing / m ² or more 0.40 g / m ² or less. Embedded image (In the formula, R is an alkyl group having 1 to 3 carbon atoms, R ₁ is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and n is an integer of 0 to 2000.) 2. The hydrophilic colloid layer contains particles of barium sulfate and / or strontium sulfate having an average particle size of 5 μm to 0.5 μm or more and 0.15 g / m ^{2 to} 0.30 g / m <sup>2.
2. The</sup> silver halide color reversal light-sensitive material according to claim 1, wherein the content is not more than g / m < ² >.