JPS61289346A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and desilverability in bleach-fix processing and electrostatic charge ability by forming emulsion layers each containing silver halide grains having an average grain size not above a specified value, an antihalation layer on the emulsion layer side of a support, and a backing layer on the other side of the support opposite to the emulsion layer side. CONSTITUTION:The silver halide grains of each emulsion layer have an average grain size of <=0.4mum, the antihalation layer made of colloidal silver is arranged on the emulsion layer side of the support, and on the opposite side of the support is located the backing layer made of carbon or graphite. As the colloidal silver, it is preferred that is color is black from the respect of antihalation effect, its grain size is especially in the range of 0.20-0.01mum, and its amount to be used is <=0.2g/m<2> from the viewpoints of desilverability and so on, and >=0.05g/m<2> from the viewpoints of sharpness and so on. The antihalation backing layer has, preferably, a density of 0.5-1.5 with respect to white light.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color photographic light-sensitive material, and more specifically, it uses a fine silver halide emulsion to improve sharpness, desilvering property in bleaching process, and chargeability. Improved silver halide color photographic light-sensitive materials (hereinafter referred to as "photosensitive materials")
).

(Prior art) In the technical field of preparing photosensitive materials, there has been a strong desire to improve sharpness as one of the important techniques for improving the quality of reproduced color images, and a great deal of research has been carried out. I've been

On the other hand, the method used in the desilvering process has been changing due to environmental pollution problems in the processing process of color photosensitive materials.

The method used for the desilvering process is to remove the silver image by processing mainly using red blood salts and halides, or to bleach the silver image by oxidizing colloidal silver to silver halide, followed by sodium thiosulfate or chloride. The fixing process consists of converting silver halide into a water-soluble form using a fixing solution mainly containing ammonium osulfate and removing it by dissolving it in water. Although it has a strong desilvering effect, it is not preferred because it has a serious drawback in terms of environmental pollution, which has been attracting attention in recent years. For this reason, in recent years, bleaching solutions mainly containing persulfates such as sodium persulfate and iron-organic acid metal complex salts such as ferric salts of aminopolycarboxylic acids have become the main methods for distillation. However, the problem in this case is that the desilvering ability is relatively weak.
It is necessary to add a desilvering acceleration process and extend the bleaching time.

On the other hand, in print photosensitive materials, macro photosensitive materials, etc., the average grain size of the emulsion used is relatively small from the viewpoint of graininess, and the average grain size is usually 0.4μ or less. There are many things.

We also found that a photosensitive material with a silver halide grain size of 0.4μ or less has a faster desilvering rate than a photosensitive material with a silver halide root grain size of 0.5μ or more. was found to be significantly slower. The cause of this phenomenon is not yet clear, but the developed silver produced in the color development process is fine and the surface area per volume increases, so the adsorption amount of substances (such as sensitizing dyes) that suppress desilvering increases. It is presumed that one of the reasons is that the desilvering speed becomes slower due to the increase in the amount of developed silver.

For this reason, when processing with a bleaching solution with weak oxidizing power such as persulfate, the silver in the film is not completely oxidized under normal processing conditions and remains in the photosensitive material even after processing. have shortcomings.

We conducted various studies regarding this phenomenon and found that the lower the position in the photosensitive material, the slower the bleaching speed, and in particular, the bleaching speed of black colloidal silver contained in the antihalation layer is significantly slower. We have found that this is the case, and have conducted various studies to improve this defective desilvering process.

As a result, it is most effective to reduce the amount of black colloidal silver in the antihalation layer provided at the interface of the emulsion layer on the support, but if the support is exposed to a certain level, the antihalation effect decreases, which is preferable in terms of sharpness. produces no result. In addition, electrostatic charges are accumulated due to contact friction or peeling between photosensitive materials or foreign substances that occur during the manufacturing process and during use, and the photosensitive emulsion layer is exposed to light by discharging it before development processing. Dot-like, dendritic, or feather-like spots (hereinafter referred to as "static marks") appear during development.
It has also been found that failures such as those occurring (denoted as ) occur more frequently when the amount of black colloidal silver is reduced.

Furthermore, if a back layer is provided on the back side instead of the antihalation layer and carbon or graphite is added thereto, problems such as poor desilvering and static marks can be significantly improved; The antihalation effect is significantly lower than that of the antihalation layer made of black colloidal silver.

(Problems to be Solved by the Invention) The objects of the present invention are to improve sharpness, and to improve sharpness in bleaching treatment.
An object of the present invention is to provide a fine silver halide color photographic light-sensitive material having improved desilvering properties and charging properties.

(Means for Solving the Problems) As a result of intensive research, the present inventor has found that the above object is to provide a halogen-based emulsion layer having at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support. In a silver chemical color photographic light-sensitive material, the average grain size of each emulsion constituting each emulsion layer is all 0.4 μ or less, and an antihalation layer made of colloidal silver is provided on the emulsion layer side of the support, and No. 10, characterized in that the support has a back layer made of carbon or graphite on the side opposite to the emulsion layer.
We have discovered what can be achieved using silver-genide color photographic materials.

Colloidal silver used in the present invention can be prepared mainly by reducing silver nitrate with a phenol such as hydroquinone or pyrogallol, or alternatively with tannin or the like in the presence of gelatin.

Colloidal silver is also usually used with hydrophilic polymers such as gelatin.

Here, the colloidal silver is preferably black from the viewpoint of the antillulation effect, and the particle size of the colloidal silver is preferably 0.40μ or less, particularly 0.20-0.0μ.
010μ is preferred.

In addition, the amount of colloidal silver applied is 0 from the viewpoint of desilvering properties.
．． It is preferably 25 g/m" or less, more preferably 0.2 g/s+" or less. On the other hand, from the viewpoint of sharpness, etc., it is 0.01
g/m" is preferable, and 0.05 g/m" or more is more preferable.

Bank layers containing carbon or graphite (e.g., carbon blanks, colloidal carbon, carbon graphite) used in the present invention are colloidal, useful in antihalation back layers, such as those described in U.S. Pat. No. 2.27L234. Using carbon dispersions and various alkali-soluble materials such as cellulose acetate phthalate described in U.S. Pat. No. 2,327,828 as a carrier for the antihalation material, organic・Colloidal carbon is finely dispersed in a coating solution diluted with a solvent,
It can be provided by applying it.

Further, carbon or graphite is used as a binder for hydrophilic polymers, particularly polymers that are solubilized under high pH conditions.

As described above, the use of carbon or graphite for the back layer is more advantageous in terms of chargeability, suitability for development processing, etc., than the use of dye or the like.

The antihalation back layer used in the present invention has a density of 0.1 to 2.0 with respect to white light when used under normal conditions.
is preferable, and particularly preferably 0.5 to 1.5.

In the emulsion layer provided on the support, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer may be provided in this order from the support, or the same color-sensitive layer may be provided in the reverse order. , may consist of two or three layers.

The amount of coated silver in the light-sensitive material of the present invention is preferably 1 to 6 g/a+'', including the total amount of silver halide emulsion and colloidal silver.
5 g/m'' is more preferable. If the amount of coated silver is too large, it is not preferable in terms of desilvering when persulfate or iron organic acid metal salt is used as a bleaching agent.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 0.1 mole percent to about 15 mole percent silver iodide.

The silver halide grains in the photographic emulsion layer may be so-called regular grains having regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as spherical shapes. It may be a crystal, a crystal with crystal defects such as twin planes, or a composite form thereof.

The average grain size of the silver halide is 0.4μ or less, preferably 0.4 to 0.05μ. The grain size distribution may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), 17643 (December 1978), 22
~page 23, “1. Emulsion pre
18716 (November 1979), p. 648.

The photographic emulsion used in the present invention is graphite, published by "Physics and Chemistry of Photography", published by Paul Montell (P.

Glafkides, Chimie et Phys
ique PhotographiquePaul M
ontel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin
+Photographic Emulsion Ch
emisty (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (V, L, Zelikmane
tal、Makingand Coating P
photographicEmulsion+Foca
1 Press+ 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a form of simultaneous mixing method, pAg in the liquid phase in which silver halide is produced is
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling the plug and pH during grain formation. For more information, please see Photographic Science
and engineering (Photographc
5cfence and Engineering)
Volume 6, pp. 159-165 (1962), Journal
Of Photographic Science (Journal
of Photographic 5science),
12, pp. 242-251 (1964), U.S. Patent No. 3
．． 655,394 and British Patent No. 1,413.74
It is stated in No. 8.

In addition, as a monodispersed emulsion, at least about 95% by weight of
Emulsions in which the grain diameter is within ±40% of the average grain diameter are typical. Emulsions having an average grain diameter of at least about 95% by weight or at least about 95% by number of silver halide grains within the range of ±20% of the average grain diameter can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent No. 3,
No. 574,628, No. 3,655,394 and British Patent No. 1.413,748. Also, JP-A-48-8600, JP-A No. 51-39027, JP-A No. 5
No. 1-83097, No. 53-137133, No. 54-
No. 48521, No. 54-99419, No. 58-376
Monodisperse emulsions such as those described in No. 35 and No. 58-49938 can also be preferably used in the present invention.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
nce and Engineering) Volume 14,
248A' p. 257 (1970); U.S. Patent No. 4,4
34.226, 4,414,310, 4,43
No. 3,048, No. 4,439,520 and British Patent No. 2.112.157. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat. No. 4,434.226, etc. is described in detail.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1.027,1.
No. 46, U.S. Patent No. 3,505,068, U.S. Patent No. 4,44
4.877 and Japanese Patent Application No. 58-248469. In addition, silver halides having different compositions may be bonded by evitaggittal bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are described in U.S. Pat.
4.459.358, British Patent No. 2.038.79
No. 2, U.S. Patent No. 4,349.622, U.S. Patent No. 4,395
, No. 478, No. 4,433.501, No. 4,463゜087, No. 3,656,962, No. 3,852.0
No. 67, JP-A-59-162540, etc.

Also, mixtures of particles of various crystal forms may be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are subject to Research Disclosure Prevention 1764.
3 and 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

l Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers,
Pages 23-24 Page 648 Right column Chromatic enhancer
~Page 649 Right column 4 Antifoggant Pages 24-25 6
Page 49 right column and stabilizer 5 Light absorber, stabilizer page 25-26 Page 649 right column Ilter dye - page 650 left column UV absorber 6 Anti-stain page 25 right column 4! I Page 650 left ~
Agent Right column 7 Hard
Film agent page 26 page 651 left column 8 binder
Page 26 Same as above 9 Plasticizer, lubricant Page 27
Page 650, right column 10 Coating aid, pages 26-27 Same as above Surface active agent 11 Static Page 27 Same Various color couplers can be used in civil engineering inventions, and specific examples thereof are given in the Research Disclosure (RD) mentioned above. )
It is described in the patents listed in Magnet 17643, ■-CG. As dye-forming couplers, the three primary colors of the subtractive color method (
That is, couplers that give yellow, magenta, and cyan) by color development are important, and specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers include the aforementioned RD17643,
In addition to the couplers described in the patents described in Sections 1-C and D, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 407,210, No. 2.875.057, No. 3.265,506, etc. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
No. 3,933.501 and No. 4,022,
Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 58-10739, U.S. Patent No. 4.401.752, U.S. Pat.
D18053 (April 1979), British Patent No. 1.4
25.020, West German Application Publication No. 2.219.917, West German Application No. 2,261.361, West German Application No. 2,329.587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 2, No. 2,433,812, and the like. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon- or cyanoacetyl-based couplers, preferably 5-pyrazolone- and pyrazoloazole-based couplers, which have a ballast group. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
No. 311,082, No. 2,343,703, No. 2
．． No. 600.788, No. 2.908.573, No. 3.062,653, No. 3,152.896, No. 3.936,015, etc.

Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897. Also European Patent No. 73
．． The 5-pyrazolone coupler having a ballast group described in No. 636 provides high color density. As a pyrazoloazole coupler, U.S. Patent No. 3,369,879
Pyrazolobenzimidazoles described in US Pat. No. 3,725,067, preferably pyrazolo [
5,1-C)(1,2,4) Triazoles, Research Disclosure 24220 (June 1984)
) and pyrazolotetrazoles described in JP-A-60-33552 and Research Disclosure 2
4230 (June 1984) and JP-A-60-43
Examples include virazolovirazoles described in No. 659.

Imidazole [l, 2-b) pyrazoles described in U.S. Pat. No. 4,500,630 are preferred from the viewpoint of low yellow side absorption of the coloring dye and light fastness, and are preferred as described in European Patent No. 119,860A. Pyrazolo (1,5-b) (
1,2,4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant naphthol and phenolic couplers, preferably the naphthol couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat. 052,
No. 212, No. 4,146.396, No. 4.228
．． Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 1,171, No. 2.772.162, No. 2.8
No. 95,826, etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. No. 3,772,002. Phenolic cyan coupler having U.S. Pat. No. 2,772,162;
Same No. 3.758,308, Same No. 4,126.396, Same No. 4.334.011, Same No. 4.327.173
2,5-diacylamino substituted phenolic couplers described in German Patent Publication No. 3,329,729 and European Patent No. 121,365, and U.S. Pat.
．． 446,622, 4.333,999, 4.451,559, and 4,427,767, which have a phenylureido group at the 2-position and the 5-position. These include phenolic couplers that have a sialamino group.

In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with a color photosensitive material for photographing. Yellow-colored magenta couplers described in U.S. Patent No. 4,163,670 and Japanese Patent Publication No. 57-39413, or U.S. Pat.
No. 9, No. 4,138,258 and British Patent No. 1,
Typical examples include the magenta-colored cyan coupler described in No. 146,368. Other colored couplers are described in RD 17643.4-0 above.

Granularity can be improved by using a coupler with appropriate diffusivity in combination with the coloring dye. Such a coupler is
U.S. Patent No. 4.366.237 and British Patent No. 2,
Specific examples of magenta couplers are found in European Patent No. 96.570 and West German Application No. 3.2.
No. 34,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
No. 0 and No. 4.080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367.2.
It is described in No. 82.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD17643,
The patent couplers listed in Sections .-F. are useful.

Preferred in combination with the present invention is JP-A-57-
Developer deactivated type represented by No. 151944; U.S. Patent No. 4.248.962 and JP-A No. 154234/1983
Timing type represented by No. 1987-39653
Particularly preferred are JP-A-57-151944, JP-A-5B-217932,
Developer deactivation type DIR couplers described in Japanese Patent Application No. 59-75474, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-90438, etc. and Japanese Patent Application No. 1987
This is a reactive DIR coupler described in No.-39653 and the like.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds include British Patent Nos. 2,097.140, 2,131,
It is described in No. 188. Couplers that release nucleating agents that have an adsorption effect on silver halide are particularly preferred;
and No. 59-170840.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of N1117643 and the same, Seed 1B716
It is described from the right column on page 647 to the left column on page 648.

According to the present invention, the color photographic material is the aforementioned RDS!
1h17643, pages 28-29 and the same, 1k1871
6, 651, left column to right column.

In the case of color photographic processing, the photographic material after color development is usually bleached. Bleaching treatment may be performed simultaneously with fixing treatment or separately. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
, compounds of polyvalent metals such as copper (II), peracids, quinones, nitroso compounds, etc. For example, ferricyanide, dichromate, iron ([1) or cobalt (
III), such as ethylenediaminetetraacetic acid,
Complex salts of aminopolycarboxylic acids such as nitrilotriacetic acid and 1,3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric (Iff) ethylenediaminetetraacetate, and ammonium iron(III) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron(II[) complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, it is common to wash two or more oak tanks in a countercurrent manner to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this process, 2 to 9
Various compounds are added to the zero-tube stabilization bath, which requires a countercurrent bath, for the purpose of stabilizing the image. For example, various buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting membrane pH (e.g., pH 3-8). Typical examples include carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (
(benzisothiazolinone, illithiazolone, 4-thiazoline benzimidazole, halogenated phenol, etc.)
Various additives such as surfactants, fluorescent whitening agents, and hardening agents may be used, and two or more compounds for the same or different purposes may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane PL-1 regulator after treatment.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film, color reversal film, color paper, color positive film, and color reversal paper. The present invention also relates to Research Disclosure 17123 (197
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in J.

(Examples) The present invention will be illustrated below with examples, but the present invention is not limited to these examples.

Example 1 A multilayer color photosensitive material 1 consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support as a sample.
01 was created.

1st layer; antihalation layer gelatin layer containing black colloidal silver 0.30 g/m2 2nd layer; middle window layer Compound H-1 0.18 g/m”
3rd layer of gelatin layer containing: 1st red-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion: 0.38 g/la
"(Iodide 114 mol%, average grain size 0.08μ) Sensitizing dye I......for 1 mol of silver?, 0X10
-'molar sensitizing dye ■・・・・・・2.0×1 per mole of silver
0-'Mole sensitizing dye ■・・・2.8X1 per mole of silver
0-'Mole sensitizing dye■・・・・・・2.0X1 per mole of silver
0-S molar coupler C-3...0.40 g/m" coupler C-4...0.02 g/la" coupler C-5...0 Gelatin layer containing .02 g/m'' 4th layer: 2nd red-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion...0.13 g/+a
(Silver iodide 4 mol%, average grain size 0.16μ) Sensitizing dye ■・・・・・・5.2XlO− per 1 mol of silver
'Molar sensitizing dye■・・・・・・1.5X1 per mole of silver
0-'Mole sensitizing dye■・・・・・・2.1X1 per mole of silver
0-'Mole sensitizing dye■・・・・・・1.5X1 per mole of silver
0-' molar coupler C-3・ ・ ・ ・ ・ ・ 0.20
g/-2 coupler C-4・・・・・・・・0.
01 g/la” coupler C-5・・・・・・・o
, 5th gelatin layer containing 0.01 g/118; 3rd red-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion: 0.18 g/al
"(silver iodide 4 mol%, average grain size 0.25μ) Sensitizing dye I...1!5.5X10 per 1 mol
-'Molar sensitizing dye H...1.6X1 per mole of silver
0-'mol sensitizing dye m...2.2X1 per mole of silver
0-'Mole sensitizing dye ■・・・・・・1.6Xl per 1 mole of silver
Gelatin layer 6th layer containing O-' molar coupler """3""" ・0.10 g/m"; Intermediate layer compound H-1...0.02 g/ra
7th layer of gelatin layer; 1st green-sensitive emulsion layer Coating silver of silver iodobromide emulsion...0.35 g/l12 (
Sensitizing dye (tJ! 4 mol%, average particle size 0.08μ) 4.0X10- for 1 mol of silver
'Molar sensitizing dye■...4.0XI per mole of silver
O-' molar coupler C-6...0.20g/112 coupler c-7...o, 04g/1II2 coupler c-8...o, 04g/ 8th layer of gelatin layer containing s+2 coupler c-9...o, 01g/1IIz; second green-sensitive emulsion layer coated silver amount of silver iodobromide emulsion...0.20g/+++"
(Silver iodide 4 mol%, average grain size 0.16μ) Sensitizing dye ■・・・・・・3.5XlO-' per 1 mol of silver
Molar sensitizing dye ■・・・・・・3.5Xl per mole of silver
Gelatin containing O-' molar coupler C-9...0.10g/112 coupler C-7...o, 00157m1 coupler C-8...o, oo1g/112 Layer 9: Third green-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion...0.14 g/m"
(4 mol% iodide 'R, average grain size 0.25μ) Sensitizing dye V...3.0XIO- per 1 mol of silver
'Molar sensitizing dye■...3.0X1 per mole of silver
0-' molar coupler C-9...0.03 g/m"
Coupler C-8 10th gelatin layer containing 0.001 g/m; yellow filter with yellow colloid 0.16 g/m Compound H-1 11th layer of gelatin layer containing 0.20 g/la"; coated silver amount of silver iodobromide emulsion in first blue-sensitive emulsion layer: 0.25 g/m" (coating of silver iodobromide emulsion) Silveride 1 mol%, average grain size 0.15μ) coupler
12th gelatin layer containing C-10...0.68 g/m''; second blue-sensitive emulsion layer coated silver amount of silver iodobromide emulsion...0.20 g/mz (iodide 1!1 mol%, average grain size 0.20μ) coupler C-10...0.16 g/11'' gelatin layer 13th layer; 3rd blue-sensitive emulsion layer of silver iodobromide emulsion Coated silver amount...0.40 g/m"
(Silver iodide 1 mol%, average grain size 0.30μ) Coupler C-10...0.14 g, 14th gelatin layer containing 'ta'; 1st protective layer UV absorber C- 1...0.20 g/+w
"Ultraviolet absorber C-2...o, 90g/l11
15th layer of gelatin layer containing 2; 2nd protective layer polymethyl methacrylate particles (diameter 1.5μ)...
In addition to the above composition, gelatin hardening agent C-11 and a surfactant were added to each gelatin layer containing 0.05 g/m''.The sample prepared as described above was designated as sample 101. .

The compounds used to prepare the samples are shown below.

C-/ C-co t-C4H.

C-da CH.

-A Ct Ct c-i.

Ct -ii H Sensitizing dye I Sensitizing dye■ Sensitizing dye■ (CH2), So, Na Sensitizing dye■ birth C2H.

Sensitizing Dye V Sensitizing Dye■ Next, Sample 14-102 was the same as Sample-101, except that the coating amount of black colloidal silver in the first antihalation layer was O, at a rate of 18 g/-2. It was made as follows.

Next, sample-103 was coated after removing the black colloidal silver in the first antihalation layer, and the following bank layer (16th layer) was coated on the back side of the support, but sample-101 was also coated. It was produced in the same manner.

15th layer: Back layer Methyl methacrylate-methacrylic acid copolymer (copolymerization molar ratio 1:1) 1.5 parts Cellulose acetate hexahydrophthalate (4% hydroxypropyl groups, 15% methyl groups, 8% acetyl groups, Phthalyl group (36%) 1.5 parts Acetone 50 parts Methanol 25 parts Methyl cellosolve 25 parts Colloidal carbon
A coating solution was prepared at a ratio of 1°2 parts or more, and applied so that the degree of fritness against white light was 1.0.

Next, Sample 104 was prepared in the same manner as Sample 103, except that the coating amount of black colloidal silver in the first antihalation layer was 0.18 g/la''.

Next, Sample-105 was prepared in the same manner as Sample-103 except that the coating amount of black colloidal silver in the first antihalation layer was 0.10 g/m''.

Sample-106 was then prepared from each layer having the composition shown below on a cellulose triacetate film support.

1st layer; antihalation layer black colloidal silver 0.30 g 7m2
2nd gelatin layer containing interlayer compound H-1...O, 18g 7m2; 1st red-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion ...0.57 g/vl
"(silver iodide 4 mol%, average grain size 0.5μ) sensitizing dye f...1.1X10-' per 1 mol of silver
Molar sensitizing dye ■・・・・・・3.2×1 per mole of silver
0-'molar sensitizing dye■・・・・・・! 4.5X per mole of I
10-3 mol sensitizing dye ■・・・・・・3.2XI per 1 mol of silver
O-6 molar coupler C-3...0.40g/m" coupler C-4...0.02g/m" coupler C-5...0. Gelatin layer 4th layer containing 0.02 g/ls"; Second red-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion: 0.20 g/m"
(Silver iodide 4 mol%, average grain size 0.8μ) Sensitizing dye ■・・・・・・1.0×10−′ mol per 1 mol of silver Sensitizing dye ■・・・・・・ Silver 3.0X1 per mole
0-”mol sensitizing dye ■・・・・・・4.2×1 per mole of silver
0-'mol sensitizing dye ■・・・・・・3 per mole of silver, Ox
10-'-t-coupler C-3...0.20 g/ml
"Coupler C-4...0.01g/Ilz
Coupler C-5...0.01 g/m"
5th gelatin layer; 3rd red-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion: 0.27 g/m"
(Silver iodide 4 mol%, average grain size 1.2 μ) Sensitizing dye ■・・・・・・1, l×10−’ mol per 1 mol of silver Sensitizing dye ■・・・・・・ Silver 3.3X1 per mole
0-” mol sensitizing dye ■・・・・・・4.5×1 per 1 mol of silver
0-”Mole sensitizing dye ■・・・3.3X1 per mole of silver
0-6 mole coupler C-3...0.10g/m! Gelatin layer 6th layer containing: Intermediate layer Compound H-1...0.02 g/s+" gelatin layer 7th layer; 1st green-sensitive emulsion layer Coating of silver iodobromide emulsion Silver amount...0.53 g/m"
(Iodization!!! 4 mol%, average grain size 0.5 μ) Sensitizing dye ■・・・6.4×10− for 1 mol of silver
'Molar sensitizing dye ■...6.4XI per mole of silver
O-"molar coupler C-6...0.20 g/m" coupler C-7...0.04 g/la" coupler C-8... . . . 0 .04g/m”
Coupler C-4...0.01 g/la
Gelatin layer 8th layer containing "2nd green-sensitive emulsion layer Coating weight of silver iodobromide emulsion...0.30 g/m" (silver iodide 4 mol%, average grain size 0.8 μ) Sensitization Dye ■・
...7.0 x 10-' mol sensitizing dye for 1 mol of silver ■ 7.0 x 1 for 1 mol of silver
Oh-h molar coupler C-9...0.10g/Ilz coupler C-7...0.001 g/m" coupler C-8...0.001 g 9th gelatin layer containing /m''; 3rd green-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion: 0.21 g/m'' (silver iodide 4 mol%, average grain size 1.2 μm) ) Sensitizing dye V・
...6.3X10-' moles per mole of silver sensitizing dye■...6.3X1 per mole of silver
0-' molar coupler C-9...0.03g/ll1z
Coupler C-8 10th layer of gelatin layer containing 0.001 g/mz; yellow filter layer yellow colloidal silver 0.16 g/m”
Compound H-1...0.20g/IIIz
Gelatin layer 1st layer containing: 1st blue-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion: 0.38 g/m" (silver iodide 1 mol%, average grain size 0.8 μ) Coupler C
-lo... 12th gelatin layer containing 0.68 g/mz; second blue-sensitive emulsion layer coated silver amount of silver iodobromide emulsion...0.30 g/m2 (silver iodide 1 Mol%, average particle size 1.0μ) coupler C
-10...0.16 g/la2 Gelatin layer 13th layer 5 Second blue-sensitive emulsion layer Coated silver amount of silver iodobromide emulsion...0.60 g/m" (iodide Silver 1 mol%, average particle size 1.4 μ) Coupler C
14th gelatin layer containing -10...0.14 g/m"; first protective layer ultraviolet absorber C-1...0.20 g/m" ultraviolet absorber C- 2... 15th layer of gelatin layer containing 0.90 g/la''; 2nd protective layer polymethyl methacrylate particles (diameter 1.5 μ)...
- Gelatin layer containing 0.05 g/ra2 In addition to the above composition, gelatin hardening agent C-11 and a surfactant were added to each layer.

Sample-107 was then coated with the above-mentioned back layer (
It was produced in the same manner as Sample-106 except that the 16th layer) was applied.

The above samples were exposed to light according to the method described in ISO 5800, and then processed according to the following processing steps.

Treatment process Temperature (℃) Time Before
Bath 27±1 10 seconds■Backing removal
27-38 5 seconds and spray washing■ Color development 41.1±0.1 3 minutes■
Stop 27-38 30 seconds ■ Accelerate bleaching
27±1 30 seconds■ Bleaching 38±1
3 minutes■ Wash with water 27-38 1 minute■
Fixation 38±1 2 minutes■ Wash with water
27-38 2 minutes [shares] Stable 27-38
The formulation of the treatment liquid used in the 10-second treatment step is as follows.

Prescription of each treatment solution ■Prescription bath 800mj of water with a prescription value of 27-38℃! Filling sand (decahydrate) 20.0 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1.0 g Add water
1.001pl+(27℃)
9.25■ Color development
Prescription Water with a value of 21-38℃
850mj! Kodak Anti Calcium Pkh
4 2. Om 1 Sodium sulfite (anhydrous)
2.0g Eastman Anti Fog 1
1m9 0.22g Sodium Bromide (Anhydrous)
1.20g sodium carbonate (anhydrous)
25.6 g sodium bicarbonate
2.7g color developing agent; 4-(N-ethyl-N-(β-methanesul) 4.0g honamidoethyl)-n-toluidine Add water 1. OOjl!
pH (27℃) 10.20■Stop 900ml of water with a prescription value of 21-38℃! 7,
ON sulfuric acid 50mj! Add water to 1.0 ol■ Bleach accelerator prescription Plant tree
900ml Sodium metabisulfite (anhydrous) 10.0g Glacial acetic acid
25.0 ml Sodium Acetate IQ, OgEDTA-4Na
0.7gP BA
Add 5.5 g water
1. O1ρ■ (27℃) 3.8
±0.2 PBA represents 2-dimethylaminoethylisothiourea dihydrochloride.

■Bleach solution: 800mj of water with a prescription value of 24-38℃! Gelatin 0.5 g Sodium persulfate 33.0 g Sodium chloride 15.0 g Monobasic sodium phosphate (anhydrous) 9.0 g Phosphoric acid (85%)
2.5 ml ■Fixed
Prescription value 20-38℃ water 700ml Kodak Anti-Calcium NkL4 2. Om 15
8% ammonium thiosulfate solution 185ml Sodium sulfite (anhydrous) 10.0g Sodium bisulfite (anhydrous) 8.4g Add water
1.1! pH (27°C)6.
5 [Phase] Stable Prescription value Water at 21-27℃ 1.001 Kodak Stabilizer - 0.14ml 1 Additive formalin (37.5% solution) 1.50ml
The sharpness of the m2 image is determined by the response function [modulation transfer function (Modulati
on Transfer Function)
(hereinafter referred to as rMTFJ), M at the spatial frequency consisting of
Comparison was made based on the magnitude of TF value. The MTF was measured according to the method described in "Nondestructive Testing", Vol. 16, pp. 472-482, written by Masao Takano and Ikuo Fujimura, 1967.

The desilvering speed is 1 minute each for the bleaching process described.
The treatment was carried out for 2 minutes and 3 minutes, and after the completion of the treatment, the amount of silver remaining in the maximum color density area of the photosensitive material was measured using a fluorescent X-ray measuring device.

Antistatic property was determined by heating an unexposed sample at 25°C and 10% R).
After conditioning the humidity for a period of time, the sample was rubbed with a rubber roller and a Delrin roller in a dark room under the same air conditioning conditions, and then developed with the developer described above to examine the degree of static mark occurrence.

Incidentally, the evaluation of the degree of occurrence of static marks was A: No occurrence of static marks was observed.

B: Slightly recognized.

C: Quite acceptable.

The results obtained by the above method are shown in Table 1.

As is clear from the results in Table 1, the present invention provides a silver halide color photographic light-sensitive material that has better performance in sharpness, desilvering property, and chargeability as compared to the comparative example.

Showa JO, Q, 16E1 Director General of the Patent Office Michibe Uga 1, Indication of Case Patent Application No. 132142 of 1985
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3. Relationship with the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 5. Date of amendment order September 24, 1985 Ill. As shown in the engraving and attachment of the originally attached statement (no changes to the contents)

Claims (1)

[Claims] In a silver halide color photographic material having at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support, the average grain size of each emulsion constituting each emulsion layer is all 0. .4μ or less, and has an antihalation layer made of colloidal silver on the emulsion layer side of the support, and a back layer made of carbon or graphite on the opposite side of the support from the emulsion layer. Silver halide color photographic material.