JPH05289225A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having good graininess without decreasing adhesion property nor generation of Newton rings by specifying photosensitive silver halide particles. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on a supporting body and has a protective layer as the outermost layer comprising an nonphotosensitive hydrophilic colloid layer. The photosensitive silver halide particles in the photosensitive silver halide emulsion layer have <=0.4mum average particle size. The outermost protective layer contains particles of a matting agent consisting of the component expressed by the formula with <=3.1 monodispersion degree. In the formula, (x), (y) and (z) as molar ratios satisfy z/(x+y) <0.25. The matting agent consists of polymer particles which are substantially insoluble with alkali and do not dissolve even in a high pH soln. such as a color developer (pH10.0-10.5) during processing.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having substantially improved graininess.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material has at least one light-sensitive silver halide emulsion layer on a support, on which a surface layer or a protective layer made of a hydrophilic colloid substance typified by gelatin is formed. Have layers. Such a photographic light-sensitive material causes an adhesion phenomenon on the surface of the light-sensitive material when stored in a high temperature and high temperature and high humidity environment. This adhesion is a phenomenon that occurs when the light-sensitive materials are brought into contact with each other or with other substances such as the inside of the camera, and they occur at the stage of manufacturing the light-sensitive material, during use, and during storage, which is a problem.

To solve this problem, silica, titanium dioxide, magnesium oxide, magnesium carbonate, or fine particles which are said to be a matting agent such as polymethylmethacrylate, polystyrene and cellulose acetate propionate are used for the outermost surface protective layer. It is widely known to incorporate the so-called matte surface to prevent adhesion. Further, one of the important functions of the matting agent is prevention of Newton's rings. Newton's ring is generated when light-sensitive materials and light-sensitive materials or light-sensitive materials and objects having smooth surfaces such as transparent glass come into contact with each other under pressure, and a typical example thereof is contact printing of movie film. Occurs at times. As a measure for preventing Newton's rings, it is generally known that a large amount of a matting agent is used to enhance the surface matting property.

However, although the increase of the matting property by increasing the amount of the surface matting agent can achieve the prevention of adhesion or Newton's ring, it causes substantial deterioration of graininess. The term "substantially deteriorated graininess" as used herein means that when a photosensitive material containing a matting agent in the outermost layer is subjected to development processing, magnified printing, projection, or projection is performed using a specular light source, or copying using the same light source (for example, It appears remarkably when performing optical printing in the movie industry). Conventionally, it has been difficult to achieve both adhesion and prevention of Newton's rings without this deterioration of graininess.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having good graininess without impairing adhesion and generation of Newton's rings.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have the above-mentioned object of halogen having a protective layer comprising at least one photosensitive silver halide emulsion layer on a support and a non-photosensitive hydrophilic colloid layer on the outermost surface. In the silver halide photographic light-sensitive material, the average particle diameter of the light-sensitive silver halide grains contained in the light-sensitive silver halide emulsion layer is 0.4 μm or less, and the outermost surface protective layer has the following general formula (1). Composition monodispersity 3.1
The silver halide photographic light-sensitive material is characterized by containing the following matting agent particles. General formula (1)

[0007]

[Chemical 2]

Where z / (x + y) <0.25 (x,
y and z are molar ratios)

The present invention will be described in detail below.
The matting agent used in the present invention is substantially insoluble in alkali and has a high pH (pH 10.0 to 1) like a color developing solution.
It is a polymer particle which does not dissolve even in 0.5) during the treatment. The matting agent particles of the present invention have x / (x +) when the composition ratio is expressed in mol as described in the general formula (1).
y) <0.25, preferably x / (x + y) <
It is 0.11. The most preferable composition ratio is 0.0
5 <z / (x + y) <0.11. When the molar ratio of z is 0 to 0.04, the matting agent particles may fall off from the outermost surface when the photosensitive material is processed by a cine type developing machine. The ratio of x and y is arbitrary, but preferably 0 ≦ y / x <1. In the present invention, only the matting agent represented by the general formula (1) is used. The amount of the matting agent used in the present invention is 3 to 15 mg / m ² , preferably 5 to 1
It is 0 mg / m ² . If the addition amount is 3 mg / m ² or less, the effect of surface matting is small, and if it is used in excess of 15 mg / m ² , the graininess is remarkably deteriorated, which is not suitable for the purpose of the present invention.

The film thickness of the outermost protective layer using the matting agent of the present invention is optional, but is most preferably 0.4 to 1.5 μm. The film thickness here is the thickness of the portion where the matting agent particles do not exist. The average particle diameter (equivalent sphere diameter) of the matting agent of the present invention is preferably 1 to 10 μm, more preferably 1.
It is 5 μm to 5.0 μm. The monodispersity of the matting agent particles of the present invention is the equivalent spherical diameter (Σ
NV ² / ΣNV) is a value represented by the standard deviation / average particle size ratio calculated based on (NV ² / ΣNV), and in the present invention, it is 3.1 or less, preferably 2.8 or less, and more preferably 2.
It is 5 or less.

The method of synthesizing the polymer forming the matting agent particles of the present invention is described in US Pat.
It can be produced by the method described in Nos. 037, 2391181 and 2992101. Also MMA / EMA / MA
The A-type polymer can be easily prepared by the method disclosed in the Examples of JP-A-60-126644. The molecular weight of the polymer used in the present invention is not particularly limited, but it is 5,000.
~ 1,000,000 is common, and 10,000 ~
500,000 is preferred.

The matting agent of the present invention is finely dispersed and contained in the outermost protective layer of the light-sensitive material. These matting agents are prepared by dissolving a solution of the copolymer in a low boiling point organic solvent such as ethyl acetate, butanol-containing ethyl acetate (butanol less than 50% by weight), butanol-containing methanol (butanol less than 50% by weight) in an aqueous gelatin solution. Formed by dispersing under rapid stirring. The average particle size of the matting agent of the present invention can be adjusted fairly easily by changing various conditions such as stirring speed, amount of surfactant, liquid temperature, and concentration of gelatin aqueous solution. However, even if the average particle size can be adjusted, monodispersion is quite difficult. However, by using the classification method, monodisperse particles can be obtained relatively easily. The matting agent particles used in the practice of the present invention were obtained by classification. The specific method of classification is to disperse the ethyl acetate / butanol solution of the polymer in the aqueous gelatin solution with rapid stirring according to the method described above, and dilute the resulting dispersion with water to a gelatin concentration of 3%. Centrifuge (domestic centrifuge K
Centrifuge at 300 rpm for 15 minutes with K-made A-200 type). Next, the liquid (upper liquid) from which the precipitate was removed was 1000 r.
It is possible to use a precipitate obtained by spinning at 15 pm for 15 minutes and discarding the supernatant. Further, by repeating this step 2-3 times, the monodispersity can be increased within a certain range.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-color sensitive layer, a green color sensitive layer and a red color sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution 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. be able to. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-63936
It is also possible to arrange the layers in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is 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 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 distant from the support in the same color-sensitive layer. The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- It is preferable to dispose the donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in the specification of 89850 adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing less than about 30 mol% of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 1 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The grain size of silver halide grains that can be preferably used in the present invention is such that the average sphere-equivalent diameter of all photosensitive layers is 0.
It is 4 μm or less. In the case where a plurality of the same color-sensitive layers are formed, the photosensitive layer as used herein means one of the plurality of layers.
Layer 1 All layers are covered. The silver halide photographic emulsion which can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and No. .18716 (November 1979), p. 648, ibid. No. 307105 (1989)
, Pp. 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemi).
e et Phisique Photographique, PaulMontel, 1967),
Duffin, Photographic Emulsion Chemistry (Focus Press)
al Press, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et a
l., Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like.

Monodisperse emulsions described in US 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, PhotographicScience by Gatov.
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the methods described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The 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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion.
It can be mixed and used in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. No. 4,626,498, JP-A-59-214852, the inside of which is covered with a silver halide grain, and a colloidal silver is a photosensitive halogenated photosensitive grain. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in U.S. Pat.
It is described in No. 9-214852. 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 having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used.

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 developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles in the projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared 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 chemically sensitized nor spectral sensitization. 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 the layer containing the fine grain 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, page 23 to 24, page 648, right column 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 page 5.fogging prevention page 24 ~ 25 page 649 page right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 page left columns 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static, page 27, page 650, right column, pages 876 to 877, inhibitors

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. .. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No. 24220 (June 1984
Mon), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-71.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4,333,999, 4,775,616, 4,45
No. 1,559, No. 4,427,767, No. 4,690,889, No.
Those described in 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A 64-554, 64-555 and 64-556, and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And the patents described in No. 307105 and VII-F, JP-A-57-151944, 57-154234, and 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in No. 4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-2201247 are effective for shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,1
No. 40, No. 2,131,188, JP-A Nos. 59-157638 and 59-1.
Those described in No. 70840 are preferable. In addition, JP-A-60-10
7029, 60-252340, JP-A-1-44940, 1-456
Compounds which release 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. 87 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers releasing dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive 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. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate). (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-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azetase Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof 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 US Pat. No. 4,199,363, 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, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, and color positive films. Suitable supports that can be used in the present invention are described, for example, in 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 hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C and 55% relative humidity (2 days)
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 Certificates, 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 The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at ℃ for 3 minutes and 15 seconds.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive 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 hydrophilic colloid layer of m (referred to as a back layer). This back layer includes the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, matting agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No.17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but 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, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or sulfuric acid Salt is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developers include alkali metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids, 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 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 them Can be mentioned as a representative example.

When the reversal process is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented 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 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and high pH and using the color developing agent at a high concentration.

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A No. 53-32736, No. 53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715,
Iodide salt described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions 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.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like 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, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
It is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method of improving the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to make the emulsion surface turbulent to further improve the stirring effect, 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, 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 effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, 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 process 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 system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
May, May issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society edited by "The Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. 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 washing time can also be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably
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 directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. 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 antifungal agents can also be added to this stabilizing bath.

The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color 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-based compounds described in U.S. Pat. Metal salt complexes described, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various types of 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl-3-phenyl-3-phenyl-3- (phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-fluoro-3-bromo-3-chloro-3-bromo-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-phenyl-3-phenyl-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-bromo-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-chloro-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo 3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3- did lead;
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 42 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality and the stability of the processing solution. be able to.

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Back Layer Coating A back layer was coated on the surface of the anti-photosensitive layer of the support with the following composition liquid. The application amount was adjusted so that the density was 1.0 with respect to white light. A cellulose triacetate film was used as a support. (Composition of coating liquid) Methyl methacrylate methacrylic acid copolymer (copolymerization molar ratio 1: 1) 1.5 parts Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%, acetyl group 8%, phthalyl group 36 %) 1.5 parts Acetone 50 parts Methanol 25 parts Methyl cellosolve 25 parts Colloidal carbon 1.2 parts

Sample 101, a multilayer color light-sensitive material having the following composition, was prepared on a support coated with a back layer. 1st layer: Antihalation layer Black colloidal silver ...................................... Gelatin layer containing 0.30 g / m ² 2nd layer: Intermediate layer Compound H-1 ...................................... 0.18 g / m ² UV absorber C-1 …………………… 0.08 〃 C-2 ……………… 0.11 3rd layer; 1st red-sensitive emulsion layer Silver iodobromide emulsion Coating amount of silver: 0.38 g / m ² (4 mol% of silver iodide, average grain size: 0.08 μ) Sensitizing dye I: 1 mol of silver 7.0 × 10 ^-5 mol Sensitizing dye II ………………………………………………………………………… ..2 × 10 ^-5 mol Sensitizing dye III …………………… For 1 mol silver On the other hand, 2.8 × 10 ⁻⁴ mol Sensitizing dye IV ……………………………………………………………… 2.times.10 ⁻⁵ mol Coupler C-3 ………………. 40 g / m ² coupler C-4 ............... ...... 0.02g / m ² Coupler C-5 ........................ 0.02g / m ² High-boiling solvent Solv-1 ........................ 0.11g / m ² 〃 Solv-2 Gelatin layer containing 0.11 g / m ² 4th layer; second red-sensitive emulsion layer Silver coating amount of silver iodobromide emulsion 0.13 g / m ² (4 mol% silver iodide, average grain size 0.16μ) Sensitizing dye I ………………………… 5.2 × 10 ^-5 mol sensitizing dye II ………… for 1 mol silver. ............ silver 1.5 × 10 ^-5 mol sensitizing dye moles III ........................ 1 mol of silver relative to 2.1 × 10 ^-4 mol sensitizing dye IV ...... ……………… 1.5 × 10 ^-5 mol coupler to silver 1 mol coupler C-3 ……………… 0.20 g / m ² coupler C-4 ………………………… 0.01 g / m ² coupler C-5 ............ Gelatin containing ......... 0.01g / m ² High-boiling solvent Solv-1 ........................ 0.06g / m ² 〃 ^Solv-2 ........................ 0.05g / m 2 Layer 5th layer; 3rd red-sensitive emulsion layer Silver coating amount of silver iodobromide emulsion 0.18 g / m ² (4 mol% silver iodide, average grain size 0.25 μ) increase Sensitizing dye I ………………………… 5.5 x 10 ^-5 mol per mol silver sensitizing dye II …………………… 1.6 x 10 ^-5 mol per mol silver mol sensitizing dye III ........................ 1.6 × 10 per 1 mol of silver 2.2 × 10 ^-5 mol sensitizing dye IV ........................ 1 mol of silver relative to ^-5 mol coupler C-3 …………………… 0.10 g / m ² High boiling point solvent Solv-1 ……………… 0.02 g / m ² 〃 Solv-2 ……………… ……… Gelatin containing 0.03 g / m ² Layer 6th layer; Intermediate layer Compound H-1: gelatin layer containing 0.02 g / m ²

Seventh layer: first green-sensitive emulsion layer Silver coating amount of silver iodobromide emulsion 0.35 g / m ² (4 mol% silver iodide, average grain size 0.08 μm) ) sensitizing dye V ........................ 1 mol of silver relative to 4.0 × 10 ^-4 mol sensitizing dye VI ........................ 1 mol of silver relative to 4.0 × 10 ^-5 mole coupler C-6 0.20g / m ² coupler C-7 0.04g / m ² coupler C-8 …………………… … 0.04g / m ² Coupler C-9 …………………… 0.01g / m ² High boiling point solvent Solv-1 …………………… 0.15g / m ² 〃 Solv-2… …………………… Gelatin layer containing 0.15 g / m ² Eighth layer; Second green emulsion layer Silver coating amount of silver iodobromide emulsion ……………… 0.20 g / m ² (4 mol% silver iodide, average grain size 0.16Myu) Sensitizing dye V ........................ silver 1 mol per 3 to the 3.5 × 10 ^-4 mol sensitizing dye VI ........................ silver mole. 5 × 10 ^-5 mol Coupler C-9 …………………… 0.10 g / m ² Coupler C-7 ……………… 0.001 g / m ² Coupler C-8 ………… ............ 0.001g / m ² high-boiling solvent gelatin layer ninth layer comprising ^{Solv-1 ........................ 0.10g / m 2} ; the third green-sensitive emulsion layer silver iodobromide emulsion Coating silver amount …………………… 0.14g / m ² (4 mol% silver iodide, average grain size 0.25μ) Sensitizing dye V …………………… for 1 mol silver 3.0 × 10 ⁻⁴ mole Sensitizing dye VI …………………………………………………………………………………………………………………………………… At 0.03 g / 3.0 × 10 ^-5 mole coupler C-9 m ² coupler C-8 .................. ... 0.001 g / m ² High-boiling solvent Solv-1 ........................ gelatin layer tenth layer containing 0.03 g / m ^2; the yellow filter layer Yellow colloidal silver ........................ 0 .16 g / m ² compound H-1 ………………………… Gelatin layer containing 0.20 g / m ²

Eleventh layer: First blue-sensitive emulsion layer Silver coating amount of silver iodobromide emulsion 0.25 g / m ² (1 mol% silver iodide, average grain size 0.15 μm) ) coupler C-10 ........................ 0.68g / m ² high-boiling solvent Solv-1 ........................ 0.24g / m gelatin layer 12th layer comprising ^2; second blue Emulsion-sensitive layer Silver coating amount of silver iodobromide emulsion 0.20 g / m ² (silver iodide 1 mol%, average grain size 0.20 μ) Coupler C-10 ………… 0.16g / m ² High boiling point solvent Solv-1 ………………………… 0.06g / m ² containing gelatin layer 13th; 3rd blue sensitive emulsion layer Silver iodobromide emulsion coating silver ........................ 0.40g / m ² (silver iodide 1 mol%, mean grain size 0.30Myu) coupler C-10 ........................ 0.14g / m ² Gelatin layer 14th layer containing boiling solvent ^{Solv-1 ........................ 0.05g / m 2} ; the first protective layer UV absorber C-1 ........................ 0.20g / m ² Ultraviolet absorber C-2 ………………………… 0.10g / m ² High boiling point solvent Solv-1 …………………… Gelatin layer containing 0.16g / m ² 15th layer; 2 protective layer MMA / EMA / MAA = 90/ 0/10 ( molar ratio) ........................ 7 mg / m ² monodispersity 2.6 slipping agent B-1 ........................ 0 Gelatin layer containing 10 g / m ^{2 In} addition to the above composition, a gelatin hardening agent C-1
1, surfactants W-1 to W-4, antifoggant F-1, and 2,
Thickener B-2 and the like were also used as appropriate.

Preparation of Samples 102 to 104 The dispersion degree of the 15th layer matting agent of Sample 101 was 2.
Amount added (weight), except changed to 2, 1.9 and 1.8
Was created in the same way. The dispersion degree was changed by centrifugation.

Preparation of Samples 105 to 112 Sample 105 was prepared by changing the monomer composition ratio (MMA / EMA / MAA molar ratio) of the matting agent to the ratio shown in Table 1 and changing the monodispersity of the matting agent as shown in Table 1. ~ 112 were created.

Preparation of Samples 113 to 116 The silver halide emulsion grain diameter of the highest sensitive layer of the photosensitive emulsion layer was increased as shown in Table 1 and Sample 110 was a polydisperse matting agent, and Sample 111 was a monodisperse emulsion of the present invention. It was created using a matting agent.

Preparation of Samples 117 to 120 The fifteenth layer matting agent of Sample 103 was added in an amount of 4.0 shown in Table 1,
Samples 117 to 120 were prepared in the same manner except that the amounts were changed to 2.0, 14.0 and 21.0 mg / m ² .

Samples 101 to 12 thus obtained
For 0, a pattern for RMS measurement, which is usually performed to measure graininess, was burned in, and the development processing described later was performed. The obtained RMS pattern was subjected to microconcentration measurement with a V (visual) filter to calculate the RMS value, and Table 1
Summarized in. The smaller the value, the better the graininess. Further, in order to confirm the improvement in graininess, a sample for visual observation was prepared by the following procedure.

For samples 101 to 120, a width of 35 m / m,
Prepare 2 pieces each of 5m long, perforated samples for kine maneges, and print a developed negative film (Fuji Color Negative Film F-125 type 8530) on which a model subject was photographed in advance, on the first sample of the above sample. , Development processing was performed. Using the obtained developed samples 101 to 120, optical printing (printing with specular light) is performed on one remaining unexposed sample corresponding to each sample number, and development processing is performed. Treated samples 101 to 120 newly obtained here
Was subjected to contact printing on a color positive film for movies (Fuji Color Positive Film Type 8816), and then subjected to a positive development process for movies (ECP-IIA process designated by Eastman Kodak Company). Samples 101-120
The color positive finally obtained through the above was projected by a 35 m / m projector, and the superiority and inferiority of the graininess was determined by visual observation, and the results are shown in Table 1. The younger the rank, the better the graininess, and the ones observed to have the same degree were ranked the same.

In order to compare the adhesive properties of the samples 101 to 120 after the development processing, each of the development-treated samples was cut into 5 cm × 5 cm pieces, each of which was cut and aligned in an atmosphere of 30 ° C. and 70% relative humidity. The temperature was controlled for 24 hours without touching the sample, then all the samples were piled up in the same direction, and a load of 3.0 kg was applied and left for 5 days. After that, the samples were peeled one by one, and the ratio of the bonded portion to the total area was calculated and shown in Table 1. The smaller the number, the smaller the adhesive portion and the better. The chemical formulas of the materials used for preparing the samples 101 to 120 are shown below.

[0043]

[Chemical 3]

[0044]

[Chemical 4]

[0045]

[Chemical 5]

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

Samples 101-116 were processed as described below. Treatment process Temperature (℃) Time (1) Pre-bath 27 ± 1 10 seconds (2) Backing removal 27-385 seconds and spray water washing (3) Color development 41.1 ± 0.1 3 minutes (4) Stop 27 ~ 38 30 seconds (5) Bleach acceleration 27 ± 1 30 seconds (6) Bleach 38 ± 13 minutes (7) Washing with water 27-381 1 minute (8) Stationary 38 ± 12 minutes (9) Washing with water 27 ~ 38 2 minutes (10) Stability 27-38 10 seconds (11) Drying 32-436 minutes The processing solutions used in each processing step are as follows. Prescription of each treatment liquid (1) Pre-bath Prescription value Water at 27-38 ° C 800 ml Borax (decahydrate) 20.0 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1.0 g Water added 1.00 liter pH (27 ° C) 9.25

(3) Color Development Prescription Value Water at 21 to 38 ° C. 850 ml Kodak Anticalcium No. 4 2.0 ml Sodium Sulfite (anhydrous) 2.0 g Eastman Antifog No. 9 0.22 g Sodium Bromide (anhydrous) 1.20 g Sodium carbonate (anhydrous) 25.6 g Sodium bicarbonate 2.7 g Color developing agent; 4- (N-ethyl-N- (β-methanesulfonamidoethyl) -n-toluidine 4.0 g Water was added 1 1.00 liter pH (27 ° C) 10.20 (4) Suspended water with a prescription value of 21 to 38 ° C 900 ml 7.0N sulfuric acid 50 ml Water was added to 1.00 liter pH (27 ° C) 0.9

(5) Bleach accelerating solution Prescription value Water 900 ml Sodium metabisulfite (anhydrous) 10.0 g Glacial acetic acid 25.0 ml Sodium acetate 10.0 g EDTA-4Na 0.7 g PBA 5.5 g Water was added 1.0 Liter pH (27 ° C.) 3.8 ± 0.2 PBA stands for 2-dimethylaminoethylisothiourea dihydrochloride. (6) Bleaching solution Prescription value Water at 24-38 ° C 800 ml Gelatin 0.5 g Sodium persulfate 33.0 g Sodium chloride 15.0 g Sodium monophosphate (anhydrous) 9.0 g Phosphoric acid (85%) 2.5 ml Water 1.0 liter pH (27 ° C) 2.3 ± 0.2

(8) Fixing Prescription value Water at 20 to 38 ° C. 700 ml Kodak anticalcium No. 4 2.0 ml 58% ammonium thiosulfate solution 185 ml Sodium sulfite (anhydrous) 10.0 g Sodium bisulfite (anhydrous) 8.4 g Water In addition 1.0 liter pH (27 ° C) 6.5 (10) Stable Prescription value 21-27 ° C water 1.00 liter Kodak Stabilizer Additive 0.14 ml Formalin (37.5% solution) 1.50 ml

[0062]

[Table 1]

It can be seen from Table 1 that Samples 101 to 104 are different in the degree of monodispersion of the matting agent. When the degree of monodispersion is 3.0, the graininess is clearly improved and the adhesiveness is also improved. It is considered that this is because the number of coarse particles, which adversely affects the graininess, was reduced, while the fine matting agent, which had little effect on the adhesiveness, was reduced, and the graininess and the adhesiveness were effectively worked.
Matting agent composition ratio (MAA) / (M of Samples 111 to 112)
MA + EMA) was 0.33, which was outside the upper limit of 0.25 of the present invention, and the matting agent particles were dissolved and disappeared in the development processing step, resulting in good graininess but unacceptable adhesion. There is. Samples 104, 106, 10
From 8, 110, it can be seen that if the value of (MAA) / (MMA + EMA) is 0.25 or less, the effect of the present invention is exhibited even if the MMA / EMA ratio is changed. Samples 113 to 114, 11 in which photosensitive silver halide emulsion grains are coarsened
It is understood that the effects of the present invention are hardly recognized even when the monodispersity of the matting agent is increased from 5 to 116. In Samples 104 and 117 to 120, the amount of the matting agent added was varied, and it can be seen that the adhesiveness is sharply deteriorated at 3 mg / m ² or less, and the granularity is sharply deteriorated at 15 mg / m ² or more.

[0064]

The present invention is a light-sensitive material using an extremely fine-grained light-sensitive silver halide emulsion. By using a monodisperse alkali-insoluble matting agent in the outermost protective layer, good adhesion resistance and excellent graininess are obtained. A photosensitive material is obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a protective layer comprising at least one light-sensitive silver halide emulsion layer on a support and a non-light-sensitive hydrophilic colloid layer on the outermost surface thereof. A matting agent having an average grain size of 0.4 μm or less and a monodisperse degree of 3.1 or less having the composition of the following general formula (1) in the outermost surface protective layer of the photosensitive silver halide grains contained in the emulsion layer. A silver halide photographic light-sensitive material containing grains. General formula (1) Where z / (x + y) <0.25 (x, y, z are molar ratios)