JPS6055339A - Color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent reduction in sharpness and color strain such as color turbidity by specifying the ratio of silver halide contained in the emulsion layers of a color photographic sensitive silver halide material contg. a hydroquinone deriv. as a color strain inhibitor to a color image forming coupler and by incorporating a specified compound into the intermediate layer. CONSTITUTION:At least two photosensitive emulsion layers having the practically same color sensitivity and an intermediate layer are formed on a support to obtain a color photographic sensitive silver halide material. At this time, the ratio of silver halide contained in the emulsion layers to a color image forming coupler is regulated to >=10, and a compound represented by the formula is incorporated into the intermediate layer. Thus, graininess can be improved while preventing reduction in sharpness and color stain such as color turbidity. In the formula, each of R<1> and R<2> is 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 1- methylheptyl, 1-ethylhexyl or 1-propylpentyl.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic light-sensitive material which prevents color staining, and more particularly to a silver halide color photographic light-sensitive material containing a hydroquinone derivative as a color stain preventive agent.

In a multilayer color photographic material containing a color forming coupler in a silver halide photographic emulsion and developed using a color developing agent such as norahenylene diamine, the oxidized product of the color developing agent generated during development. So-called "color turbidity" (color mixing) that migrates to the adjacent image forming layer and forms undesirable pigments.
It is well known that this phenomenon occurs. Also color development 1
It is known that an inconvenient "color fog" phenomenon occurs due to air oxidation of the developing agent and fog of the emulsion during printing. In the following, this "color turbidity" and "color fog" will be collectively referred to as "color contamination."

In order to prevent color staining, various methods using hydroquinone have been proposed. For example, for using monolinear alkyl/)hydroquinones, see US Patent λ, 721, t! No., Tokukaisho! P-10432? For information on the use of monobranched alkylhydroquinones, see US Pat. No. 3,700. ≠! No. 3, West German Patent Publication λ.

It is described in Japanese Patent Publication No. 101-101, No. 71, Japanese Patent Publication No. 30-1983, and Japanese Patent Publication No. 101-32.

On the other hand, regarding dilinear alkylnohehydroquinone, the US patent has 2.72g, O! No. ri, same co, No. 732゜300,
British patent 7. tzl+< issue, same/, Or4.201 issue and "Chemical Abstract" magazine! Volume A,? 47h, etc., and for di-branched alkyl/monohydroquinone, US WJ Patent No. 37θotas No. 3, No. 273.2300,
British Patent No. 1ott2or, ``Chemical Abstracts'' magazine, JP-A-Shoyu 0-/! t, '/-31,
Tokuko Showa 60-. 2/, 24 <ri issue, same St-Hiro 0, 1/
There is a description in the za number etc.

In addition, regarding the use of alkyl-hydroquinone as a color stain inhibitor, British patent szr.

No. 211, No. 337.760 (corresponding U.S. Patent No. 3T
O, 2tO), 117.10-2\73i, B
No. ot (corresponding U.S. Patent No. 701./7) U.S. Patent No. 23363.27, No. 2. Hiro03゜72/No. 3.
! gno, No. 333, West German Patent Publication λ, J-Oj, θ
/Otsu No. (corresponding to JP-A-Kokai No. 0-I10337), Tokko-Akira!
/-/2.2! ;No. 0, same! 6-≠O1♂/ is also mentioned in the issue.

In recent years, there has been a strong demand for improving the quality of photographic images, particularly in terms of graininess and sharpness. Among these, in order to improve the graininess, in a specific emulsion layer of the photosensitive material, the total molar ratio of silver halogenide to the color image forming coupler is increased, and the color developing agent formed by the developed silver is Reduce the chance of coupling of the oxidant (!f', fj f:) and set the dye so that it exists uniformly rather than in particles, so that you can feel the apparent roughness of the particles. Here, the effect of the graininess of color photosensitive materials on the human eye varies depending on the hue formed, and the target shape of the green-sensitive layer that develops magenta is the thickest (. ) The red-sensitive layer is followed by the blue-sensitive layer, which develops a yellow color.Therefore, it is most important to improve the green-sensitive layer.

However, when the graininess is improved using the above method, the amount of silver used in the photosensitive material increases significantly, and when normal processing is performed, the resulting silver remains in the photosensitive material ( Due to poor desilvering, the photosensitive layer is divided into two or more layers that sense colors in the same area, and the ratio of silver to color image forming coupler is increased in the layer that deals with the density area where graininess needs to be improved. By doing so, graininess, desilvering properties, and other photographic properties are satisfied.

However, if there is a layer with a high silver coupler ratio, a large amount of oxidized color developing agent is generated relative to the coupler, resulting in color contamination such as "color turbidity (color mixing)". The conventional method described above has sufficient stitching to prevent contamination.
- Sensitive materials containing color stain preventive agents such as idofquinones often have a thick layer containing the color stain preventive agent, resulting in a decrease in sharpness.

As described above, there is a dilemma that improving graininess results in a decrease in sharpness, and there has been a desire to develop a technology that can achieve both at a high level.

A first object of the present invention is to provide a photographic material with improved graininess. A second object of the present invention is to provide a photographic light-sensitive material with improved graininess without reducing sharpness or causing color stains such as color turbidity. Other objects of the invention will become apparent from the description below.

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having two or more light-sensitive emulsion layers and an intermediate layer having substantially the same color sensitivity on a support. , the number of emulsion layers (all contained within the seven layers...
This can be achieved by having a ratio of silver halide to a color image forming coupler of 70 or more and further containing at least one compound represented by the following general formula (I) in the intermediate layer.

H (in the formula, R and R may be the same or different from each other <, /-v
-y-rhexyl group and l-ethyl represent a group selected from methyl group, /-propylbutyl group, /-methylheptyl group, /-ethylhexyl group and /-propylpentyl group. ) R1% R2 is when the number of carbon atoms is r, i.e. /-methylheptyl group, l-ethylhexyl group, /
The most preferred group is a group selected from -propylpentyl group.

Further, it is preferable that the composition contains a mixture of two or more compounds of general formula (I), especially a mixture of two or more compounds, as a color stain preventive agent.

Some specific examples of the 27 compounds of general formula (I) according to the present invention are listed below.

Compound 1. ．． 2. J'-di(/-methylheptyl)no1
Hydroquinone 2.2. ! -di(/-ethylhexyl)hydroquinone 3, co,j-di(l-propylpentyl)hydroquinone 4.2-(/-methylheptyl)-yo-(/-ethylhexyl)hydroquinone 5.2-(/-methylheptyl )-j-(/-propylpentyl)hydroquinone 6.2-(/-ethylhenyl)-(/-propyl is methyl)hydroquinone 7,. 2. j-di(l-methylhexyl)/%hydroquinone 82, j-di(/-ethylpentyl) nohydroquinone 9,,! , t-di(/-propylbutyl)hydroquinone 10, 2-(-/-methylheptyl)-ter(/-methylhexyl)hydroquinone 11, . 2-(/-ethylhexyl)-j-(/-ethyl is methyl)hydroquinone 12.2-(/-propyl is methyl]-!-(/
-propylbutyl)hydroquinone The synthesis of the compound of general formula (I) according to the present invention is described in French Painting Patent No. 1. Hiro 21. ,1
No. 62, West German Patent No. λ.

This can be easily carried out by the method described in Japanese Patent Application No. 10,321 and other similar methods.

The color stain preventive agent according to the present invention is an oil itself at room temperature and does not cause precipitation of crystals, so it can be dispersed in a hydrophilic colloid composition without using oil as a solvent. It can also be dispersed together with dispersing oils and low-boiling organic solvents commonly known in photographic systems.

The color stain preventive agent according to the present invention can be used in combination with color stain preventive agents other than the present invention. In particular, it is advantageous to use it in combination with hydroquinones. Examples of hydroquinones that can be mixed are: , j-t-octylhydroquinone, λ, tert-t-hexylhydroquinone, 2. Taj-n-octylhydroquinone, 2. 2. Yo-G secondary dodecylhydroquinone, λ-Second octyl nododroquinone λ, 6-G secondary octylhydronone-n-octylter secondary octyl hydroquinone, 2. Examples include j-di-t-bentadecylhydroquinone, comethyl- and secondary octadecylhydroquinone.

The compound represented by the general formula (I) of the present invention is used in an intermediate layer sandwiched between each light-sensitive emulsion layer, and the molar ratio of silver halogenide to color image-forming coupler is 70 or more. It is preferable to use it in an intermediate layer adjacent to an emulsion layer in order to prevent color mixing. In particular, it is used in an intermediate layer sandwiched between a green-sensitive emulsion layer and a red-sensitive emulsion layer because of the graininess of the green-sensitive emulsion layer, which has a large shadow to the human eye, and color mixing with the red-sensitive layer. If preferred.

The compound represented by the general formula (I) of the present invention is preferably O2O3-2g/m2, more preferably O9O! ~/
, 97m2.

These compounds are usually mixed with hydrophilic colloids such as gelatin and used as an intermediate layer.

The compounds of the present invention can also be used as color antifoggants or antioxidants in red, green or blue light-sensitive emulsion layers containing silver halide.

Each light-sensitive emulsion layer of the color photographic light-sensitive material of the present invention is
At least seven of the light-sensitive emulsion layers include at least two layers (ONi and ulWt) having substantially the same color sensitivity.
Here, the U layer, the m layer, and the 0 layer are provided in this order on the support. ), the number of other photosensitive emulsion layers may be seven layers, two layers, three layers, etc.

The layer structure of the color photographic light-sensitive material of the present invention includes a blue-sensitive emulsion layer, a green-sensitive emulsion layer, an intermediate layer of a red-sensitive emulsion layer, a protective layer, an anti-ration layer, a filter layer, etc. in any order. It's okay. Generally, in color reversal light-sensitive materials and color negative light-sensitive materials, light-sensitive emulsion layers are provided on a support in the order of red sensitivity, green sensitivity, and blue sensitivity, but in some cases green sensitivity and red sensitivity light sensitivity layers are provided. Sometimes the emulsion layers are replaced. In addition, regarding color photographic paper and color positive for movies, the above-mentioned I! A reverse layer structure is generally used.

Specifically, ■ an antihalation layer, a low-sensitivity red-sensitivity emulsion layer, a high-sensitivity red-sensitivity emulsion layer, an intermediate layer containing the compound of general formula (I), a low-sensitivity green-sensitivity emulsion layer, a high-sensitivity green emulsion layer are formed on the support. A color negative photosensitive material consisting of a light-sensitive emulsion layer, a yellow filter layer, a low-sensitivity blue-sensitivity emulsion layer, a high-sensitivity blue-sensitivity emulsion layer, and a protective layer, ■
Antihalation layer, low red-sensitive emulsion layer on the support,
Low-sensitivity green-sensitive emulsion layer, intermediate layer, high-sensitivity red-sensitivity emulsion layer, intermediate layer containing the compound of general formula (I), high-sensitivity green-sensitivity emulsion layer, yellow filter layer, low-sensitivity blue-sensitivity emulsion layer, high sensitivity A color negative light-sensitive material in which a blue-sensitive emulsion layer and a protective layer are sequentially provided; (1) A low-sensitivity red-sensitivity emulsion layer, a middle window red-sensitivity emulsion layer, a high-sensitivity red-sensitivity emulsion layer, and a compound of general formula (I) on a support; intermediate layer, low green-sensitive emulsion layer, middle window green-sensitive emulsion layer, high green-sensitive emulsion layer,
Intermediate layer, color removal filter layer, low blue-sensitive emulsion layer, intermediate H
Sensitive emulsion layer, highly blue-sensitive emulsion layer, second protection III+t1,
There is a color reversal photosensitive material in which a first protective layer is sequentially provided.

In the present invention, the emulsion layer in which the ratio of silver halide to color image forming coupler is 70 or more generally corresponds to the emulsion layer that shares the low density region, and generally corresponds to the U layer in the case of a color reversal light-sensitive material. In addition, in the case of color negative light-sensitive materials, 0% corresponds to this.

At least one of the emulsion layers of the color photographic light-sensitive material of the present invention has a silver halide to dye-forming coupler ratio of 70.
Although the above is the case, preferably /j to cooo.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material of the present invention. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing silver iodide of /-/j molar ratio.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter is used for spherical or approximately spherical grains, and the spike length is used for cubic grains, and based on the projected area (expressed as an average) is Although not particularly limited, it is preferably 3μ or less.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have a crystalline form (gular) or a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Further, the particles may be particles in which the latent image is mainly formed on the surface (or may be particles in which the latent image is mainly formed inside the particle).

The photographic emulsion used in the present invention is P, Glafkid
Chimie et Physique PIx by es
Otographique (published by Paul Monte 1, / 1967), G, P.

Photographic Emuls by Duffin
ion Chemistry (The Focal Pr.
Published by ess, /! P&&), V, L, Zelikrna
Malcing and Coati by n et al.
ng Photolzraphic Emulsion
(The, ['ocal Press-1:Il,
/ Ta 6 Years).

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, thallium salts, and iridium salts may coexist with their complex salts, and rhodium salts may coexist with their complex salts, iron salts, or iron complex salts.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example [-1, edited by Frleser, Die Grundlagen der Photog
raphischenprozesse mit Si
lberhalogeniden.

(Akademische Verlagsgesel
lschaft.

/91. r) The method described on pages 73-73 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); , amines, hydrazine derivatives, formamidine sulfinic acid, 7-ran compounds); noble metal compounds (e.g., total complex salts,
Pt.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table, such as Ir and Pd, can be used alone or in combination.

These specific examples are as follows:
．． ! 7 Hiro, Rihiro ψ No. ko, G10゜6t Ri No. 2,271, Rihiro No. 7, Rihiro No. 2゜721r, No. 641, same No. 3. U.S. Patent No. J, prj, No. 40, U.S. Pat. No. 2,41. /
For noble metal sensitization methods, see U.S. Patent No. 2.3 Tata, Or3, etc.
Same 2nd. Hirohiro r.

oto, British Patent No. t/1. It is described in various specifications such as No. OtI.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzitriazoles, benzimidazoles (
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-mercaptotetrazole), mercapto Pyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxylic group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (
In particular, the addition of many compounds known as antifoggants or stabilizers such as hydroxy-substituted (/,!, 3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; I can do it.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary It may also contain ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent λ, 1100.332
No. 2,1/-23,1179, No. 2.7/l, O
6J issue, same! , t/7, 21'0, same j, 772
, No. 021, s, rot, oo3, British Patent I.

Art, No. 721, etc. can be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, and synthetic hydrophilic polymer substances can be used. can.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are available from Research Disclosure.
arch Disclosure) / Volume 7A / 761
13 (published July 2, 1971), page 23, Section 5.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, which develops color by oxidative coupling with an aromatic 7th class amine developer (e.g., phenylene diamine derivative, amine phenol derivative, etc.) during color development treatment. may contain compounds that can be used, for example, as magenta couplers! -Vilazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. penzoylacetani + heptads, pivaloylacetanilides), etc. Cyan couplers include naphthol couplers and phenol couplers.

These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either di-equivalent or di-equivalent to silver ion.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (a so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain a coupling compound.

A specific example of a magenta colored coupler is disclosed in US Patent λ.

too, No. 711, 2, 9. ! i'3. AOI No. 3, Ot2. I33, same 3. /, 27.2tP No. 3, 3//, ≠76, No. 3. ', t/ri, 3ri No. 7,
Same 3. ! /ri, ≠λri, same 3. jj1.3/ri issue, same j, 3♂λ, 322, same 3. t/j.

rot number, 3.8'34t, 901, same j, J?
/, 4L≠j, West German patent/, tlO,≠6φ, West German patent application (OLS) 2. Hiroor, ttz, 2.4t
/7. Dehong! No. 2. ≠it, riSurigo, sameu, ≠2
ψ, ≠ 67, special public show ψ 0-603 / issue, same number 92λ, same number 12, 41-7'
IO, No. 27, J-0-/, t 331. No., same j2
-1/-2/, 2/ issue, Intermediate Turf ti-oλg issue, same! 0-tO, No. 233, same! 1-22! ≠ / issue, same j3
-It is described in Yoyo issue 12.2, etc.

Further, polymer couplers described in JP-A No. 217-217 and the like can also be preferably used.

A specific example of a yellow coupler is U.S. Patent λ, ♂7! ,03
No. 7. Same 3. ．． 2tj, jrOt issue. Same 3゜≠θg, /
Tag issue. Same 3. jJ/, /j! No. 3, j12.32
No. 2. 3.7.23.07.2, same j, IF/
, Hiro 4 Aj issue. West German Patent/, j'17゜I6za, West German Application Publication λ, 2/Ri, Ri No. 77, λ, 2t/, 31
．． / No., Same λ, ≠7'1.006, British Patent/, Hiroko J, No. 82.0, Special Publication Show! il11-1O7, JP-A-4A7-2t/33, JP-A-1IT-73/4t7, JP-A-4A7-2T/33, JP-A-4A7-2T/33, JP-A-1IT-73/4T7, JP-A-4A7-2T/33. /-1021,3 otsu issue, 10-6311/ issue, same j
TO-/, No. 23.3412, same! 0-130'AlA
No. 2, No. 6/-2/127, No. so-♂7AjO,
It is described in the same j2-♂kohirokohiro issue, the same 32-//j2/ri issue, etc.

A specific example of Schiff y Force Ir is in the U.S. Patent No. 3, 27
No. 12, same, Ko 3 Hiro, 27.2, same 2.4t71
/-, No. 293, 2. j2/, rior issue, same 2゜1?
j, I2 No. j, No. 0311.192, No. 3.3
//, Gua No. 6, same 3. Hiro! Za, 3/! issue.

Same 3. ≠74. j4j issue, same j, 313, 7/
No. 3. ! ri/, 3g No. 3, 3, 747, HiroI
No. 1, Dohiro, ool/-, Ri No. 2, West German patent application (O
I, 3), 2. F/! , fJ (No. 7, same 2.4 CjlA
.

32? issue, Tokukai Sho≠za-59 and 3g issue, same evening 1-21.
No. 031A, pr-toJ'j, j/-/4
It is described in t6za2 No., j, 2-, 4ri tλhiro No., and jλ-taOri No. 32.

As a colored coupler, for example, U.S. Patent 3° Riff 6
．． No. 560, special public official Akihirohiro-201, No. 3l-2J,
No. 33, IA2-//30ILI-, Intermediate 4'-
32g6/issue, JP-A-Shoj/-2t03≠ specification, same!
Co≠2/2/Specification, West German patent application (OLS), 2
．． Hiroshi/Za-ri! You can use the ones listed in No.

As a DIR coupler, for example, U.S. Pat.
,! J Hirogo, same 3. t/7, 2ri No. 7, 3.70/
, No. 713, No. 3.7ri 0.3zag, No. 3. A32.
3≠! No., West German patent application (OLS) Ko, Hiroshi/≠, oot
Issue, same number, ≠j Hiro, 30/ issue, same number, Hiro! ≠, No. 322, British Patent No. 33. Guyo≠ issue, JP-A-Shoj, 2-4262
1It issue, same≠tarlλ233! No., Tokuko Shoj/-/l
/≠Those listed in No. 1 can be used.

In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, as described in US Pat. Koj77, F! No.j, 1'1flj, 3
7F, 12F, West German patent application (OLS) 2, Hiroshi/
7. ri/≠ issue, Tokukai ShojZ-/327/ issue, Tokukai Sho! 3
-T//l, those described in No. 1 can be used.

A known method such as that described in U.S. Pat. Examples include phthalic acid argyl esters (butyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl phosphate, tributyl acid), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutquine ethyl succinate, dioctyl azelate), phenols (e.g. - diter/yalyamylphenol), trimenoic acid esters (e.g. tributyl trimenoate), or organic solvents with a boiling point of about 3°C to /jO0C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, After being dissolved in secondary butyl alcohol, methyl isobutyl lactone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Mafc Special Publication Show J-/-32,133, Japanese Patent Publication Show Jl-j
The dispersion method using a polymer described in Rihiro No. 3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The color photographic material of the present invention includes Re5earchD
isclosure vol, /7 A (/ri7
f) Hardeners and dyes described in RD-/764+-3;
Coating aids, plasticizers, slipping agents, matting agents, brightening agents, etc. can be used.

Specific examples of color photographic materials to which the present invention can be applied include color reversal films, color negative films, color photographic papers, color positives for movies, and the like. However, especially in color photosensitive materials for photography,
Particularly effective.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (Research Disclosure), etc.
re) / 7A No. j,! '-30 pages (RD-/full ψ
Any of the known methods and known treatment liquids as described in 3) can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is normal
It is selected between r0C and jOoC, but /♂'CJ: lower temperature or fc! The temperature may exceed O0C.

Conventional methods for forming dye images can be applied. For example, negative-positive method (e.g. Journal of the Society
ty of Motion Picture andT
elevision Engineers', lr
/vol. 1953, pp. 747-7θ/); develop with a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fogging treatment and subsequent color development; a silver coloring method in which a photographic emulsion containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye. A method such as plain bleaching can be used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamide/s (e.g. ≠-amino-N, N-diethylaniline, 3-methyl-Hiro-amino-N, N-diethylaniline, Hiro-amino- N-ethyl-N-β-hydroxyethylaniline, 3-methyl-F -7mi/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photograph by F. A. Mason
icProcessing Chemistry (Fo
CalPress, 1966), pp. 226-22, U.S. Patent Co., 1966, U.S. Patent Co., L. 3.0/Evening Issue, Co.! octopus.

3, those described in JP-A No. 33, JP-A Sho≠g-t≠, and RI 33 may be used.

The color developer may also contain a pH buffer, a development inhibitor or an antifoggant.

Also, as required: Water softener, preservative, organic solvent, development accelerator, dye-forming coupler, competitive coupler, fogging agent, auxiliary developer, viscosity imparting agent, polycarboxylic acid chelating agent, antioxidant. It may also include.

The photographic emulsion layer after color development is usually bleached. Bleaching may be carried out simultaneously with the fixing process or separately. As the bleaching agent, iron(1), iron(1), Compounds of polyvalent metals such as cobalt, chromium (Vl), and steel (II), peracids, quinones, and nitroso compounds are used.

For bleaching or bleach-fixing solutions, see U.S. Patent 3.0 Hiroko, 52
No. 0, same 3. Ko 4A/, Ri 6 No., Tokko Sho tAs-ts
ot issue, Tokko Sho <45-gr31. In addition to the bleaching accelerator described in JP-A No. 33-41732 and the thiol compound described in JP-A No. 33-41732, mild additives may also be added.

Example 1 Sample A was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with the following layers.

1st layer; low-sensitivity red-sensitivity emulsion layer 77/co(heptafluorobutyramide> r (x/ (2//, 17"-di-t-aminophenoxy)butyramide)-phenol 1009, which is a coupler, Zyl phosphate 1 OIQ and ethyl acetate 1
The emulsion hoop obtained by dissolving in OOAC and stirring at high speed with a 10% gelatin aqueous solution IkI was mixed with a red-sensitive low-iodensitivity silver iodobromide emulsion containing a sensitizing dye containing 9C'' silver halide grains. It is silver iodobromide with a size distribution in which 11% of the grains exist in the range of average grain size ≠ θ%, and silver 7
0g, gelatin 60g, iodine content 6 mol%)
Mix K and dry film) Apply to a thickness of 1-2μ fc
(Amount of silver O, evening, j9/m).

λth layer; middle window red-sensitive emulsion layer 100 g of cyan coupler Co(heptafluorobutyramide)-J'-(λ/(2//, Hiro"-di-t-aminophenoxy)butyramide)-phenol, Tricresyl phosphate 10 oc, dissolved in 4 ml and ethyl acetate 1 oo ac, vcw, 10 ml gelatin aqueous solution/
The emulsion iooog obtained by high-speed stirring with l(,9) is
Red-sensitive silver iodobromide emulsion containing sensitizing dye tkg
(The size distribution mentioned for the first layer emulsion is 7Jqb
(containing 70 fl of silver, tOI of gelatin, and iodine content of 6 moles) was mixed and coated to give a dry film thickness of lμ (silver amount: O0, !i'/m ).

3rd layer: Highly sensitive red-sensitive emulsion layer Cyan coupler Co(heptafluorobutyramide) -,! -(J'-(2", Hiro"-di-t-aminophenoxy)butyramide)-phenol ioog, 100% tricresyl phosphate and 100% ethyl acetate.
The emulsion iooog obtained by dissolving in 00Qc4 and stirring at high speed with IO% gelatin aqueous solution/kg was added to 1ky of red-sensitive highly sensitive silver iodobromide emulsion containing a sensitizing dye (the above size distribution is related to 7). It contained silver 709.gelatin 6θI, iodine content was 6 molar) and was coated to give a dry film thickness of 1 μ (silver amount O, g, j7/m 2 ).

44th layer: Intermediate layer λ, J'-di-t-octyl/)hydroquinone jOg, dibutyl phthalate 100% and ethyl acetate/00
Qc41c dissolved in 14% gelatin and aqueous solution Ik
9 was mixed with IO% gelatin/kfllc into the emulsion obtained by stirring at high speed. ! D-t-octylhydroquinone was applied in an amount of 2001 q/m2.

5th layer: low-sensitivity green-sensitivity emulsion layer with magenta coupler instead of cyan coupler /-(
+2,4! ,,&-)liclochphenyl)-3-(J-
Emulsion 21017 obtained in the same manner as the emulsion of the first layer except that (2,4A-di-t-amylphenocyacetamide)benzamide)-j-pyrazolone was used was designated as sensitizing dye B. B/C green-sensitive, low-sensitivity silver bromide emulsion containing a molar ratio of 0.3/kg (the above size distribution is rt
(containing 70 g of silver, zOg of gelatin, and iodine content of 56.2 mol%) and applied to a dry film thickness of 2゜θμ (amount of silver 07jJ/m2, silver color r). relative to forming couplers 23).

6th layer: Nakaza green-sensitive emulsion layer with magenta coupler instead of cyan coupler /-(
U,≠,6-dolychlorophenyl)-3-(3-(,2
, Hiro-di-t-amylphenoxyacetamido)benzamide)-terpyrazolo/emulsion 10009 obtained in the same manner as the emulsion of the first layer was used as sensitizing dye B. B/C Green-sensitive highly iodosilver bromide emulsion/kji (mole ratio...0.3) (the size distribution is 71%, contains 70 g of silver, 60 g of gelatin, and has an iodine content of 2 mol%) (Amount of coated silver: 0- J j , li' / rn 2
, the ratio of silver to color image-forming coupler, about 6).

7th layer: Highly sensitive green emulsion 1. Magenta coupler is used instead of cyan coupler /-(
2,44,l,-trichlorophenyl)-3-(j-(
Using Emulsion 10009 obtained in the same manner as the emulsion of the first layer, Tomo et al.
A green-sensitive highly iodobromide emulsion/klc containing a B/C molar ratio of -0,1) has the above size distribution of 7Jrfi, contains 70g of silver, 60g of gelatin, and has an iodine content of 5.2 (mol ratio) and coated to a dry film thickness of lμ (coated silver i0, j j i 7 m2, ratio of silver to color image forming coupler: 6).

R-th layer: Intermediate layer The emulsion lkI used in the 4th L-layer was mixed with 1 kg of 1oatr gelatin and applied to give a dry film thickness/μ.

2nd layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness/μ.

io layer; low-sensitivity blue-sensitivity emulsion layer with yellow coupler instead of cyan coupler, α-
(pivaloyl)-α-(/-hensyl-yo-ethoxy-
3-fold/toynyl)-2-chloro-! - 7000 g of a solid emulsion obtained in the same manner as the 1st% emulsion except that totisyloxycarbonylacetanilide was used was used as a blue-sensitive, low-iodophilic silver bromide emulsion with the above size distribution of 77% and silver 709, contains gelatin tOI and has a high iodine content.

5 mol%) K mixed, dry film thickness. It was coated to a thickness of Oμ (coated silver amount: 0.697 m ).

1st/Layer: Medium-sensitivity blue-sensitivity emulsion layer with yellow coupler instead of cyan coupler, α-
(piparoyl)-α-(/-hensyl-!-ethoxy 3-fold/toynyl)-2-chloro-yo-dodecyloxycarbonylacetanilide, but obtained in the same manner as the first layer emulsion. yooog is a blue-sensitive highly brominated emulsion 1kEC with the above size distribution of 72%, containing 70g of silver, 60g of gelatin, and the iodine content!
.

j morch) and coated to give a dry film thickness of 0.317/m2 (coated silver amount: 0.317/m2).

Layer 7.2: Highly sensitive blue-sensitive emulsion layer with yellow coupler instead of cyan coupler, α-
(pivaloyl)-α-(/-benzyl-!-ethoxy3-hydantoinyl)-2-p.

A blue-sensitive highly sensitive silver iodobromide emulsion lk , silver 709, gelatin≦o
g, and the iodine content is S.

j morch) and coated to give a dry film thickness of 0μ (coated silver amount o, 5g7m2).

13th layer: Protective layer The emulsion/IJ used in the 3rd layer was mixed with IQ% gelatin ikg
was mixed and coated to a dry film thickness of λμ.

74th L layer; 1st protective layer Fine grain emulsion (grain size θ, /jμ) that is not chemically sensitized
, a 1 molar silver iodobromide emulsion) was coated to give a silver coating amount of 0.3 g/m 2 and a dry film thickness of lμ.

The obtained multilayer coated film is designated as Sample A.

Sensitizing Dye Human Sensitizing Dye B Sensitizing Dye C Sensitizing Dye C Sensitizing Dye B Sensitizing Dye C Sample 13 was prepared by changing the amount of the emulsion and the amount used of the idroyanone derivative as shown in Table 1 only for the ≠ layer (intermediate layer) of the sample. -N was created.

Note that dibutyl phthalate is not used in the CN emulsion.

Samples A-N were then exposed through a red filter and a wedge of successively different gray densities for the following processing.

Processing process Time Temperature 1st development 4'31'C (±0.3) Washing with water, 2/ Reversal 2' Color development 4/ Adjustment λ' Bleaching 6' Fixing Glue Washing with water Stable l' Normally wet and dry First developing water 700 Sodium Gotetrapolyphosphate 2g Sodium sulfite 2017 Hydroquinone monosulfonate 30g Sodium carbonate (l hydrate) 30 ji/-Phenyl
Goomethyl Hiro-methoxy-3-pyrazolidone YuJ Potassium bromide 2.rg Potassium thiocyanate /, 2.51 Potassium iodide (O, 7% (volume), add 2rnl water 1000
M Inverted water 7θOml Nitrilo・N-N-,N-trimethylenephosphonic acid・6 Na salt 3g Stannous chloride (dihydrate)/9 P-aminophenol 0. /ji Sodium hydroxide ♂y Glacial acetic acid /jrnl Add water / 000 Go color developing water 7ooml Sodium tetrapolyphosphate 2g Sodium sulfite 7y Sodium tertiary phosphate (dihydrate) 3417 Potassium bromide ip Potassium iodide (o , i% solution) Sodium hydroxide 3. ! iI Citrazic acid i, zg ≠-Amino-3-methyl-N-ethyl-β-hydroxyethylaniline sulfate monohydrate iig Ethylenediamine 3g Add water 10100O Adjusted water 700 Sodium sulfite 12y Sodium ethylenediaminetetraacetate (2 tri Thioglycerin O1≠Glacial acetic acid 3ml Add water 1ooorttt Bleach water rooal Sodium ethylenediaminetetraacetate (λ hydrate) 2. o9 Ethylenediamine/iron(If)tetraacetate ammonium (dihydrate) iso, og Potassium bromide 100.011 Add water /, 01 Fixing water 100ml Ammonium thiosulfate to, og Sodium sulfite r, og Sodium bisulfite z, ol Add water i, op Stable water 100ml Formalin (37% by weight) t, omt Fuji Drywell j, 0rttl Add water /, O1 Measure the R concentration of the sample A-N after treatment, and check the R concentration of the R photosensitive layer. The color density, that is, the cyan density was measured.

Here, when the compound added to the intermediate layer has a high ability to prevent color mixture, the minimum cyan density decreases and the red color becomes more vivid.

Further, after exposing the adjusted sample A-N through a sharpness measurement wedge, the above-mentioned processing is performed, and then measurement is performed using a sharpness measurement device. Values at 20 cycles/mm are shown based on sample A (/, 00). The higher the value, the better the response to the original and the higher the sharpness.

As shown in Table 2, compared to the samples using conventional hydroquinone derivatives (A, B, I to N), the compounds of the present invention, CO,! -G sec -The sample (C-H) using octyl.hydroquinone has the effect of improving both the color mixture prevention ability and sharpness in a well-balanced manner (at a high level).

Patent applicant Fuji Photo Film Co., Ltd. Procedural Amendment Showa! Presented to the Commissioner of the Patent Office on 7th/Month/2019 1, Case Indication 1997 Patent Application No. 163-71 2,
Title of the invention Halogen 1 Arsenic color photographic light-sensitive material 3 Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4. Subject of amendment Column 5 of ``% Claims'' and ``Detailed Description of the Invention'' of the specification. Contents of amendment (1) The scope of claims of the specification Correct as shown in the attached sheet.

(2) Circular No. ≠ page 72 line "Developed silver" "Silver development" and correct it.

(3) Circular No. 1, page 1, Evening row “Feel” "Decrease" and correct it.

(4) “Effects” in lines 76 and 17 of page ≠ of the circular "Influence" and correct it.

(5) On page 5 of the same book, line S, [so, from line j to ``graininess,'' are corrected as follows.

[. Therefore, it is necessary to divide the photosensitive layer into two or more layers that sense colors in the same area, expand the latitude by using emulsions with different sensitivities, and improve the graininess of these two or more layers. By increasing the molar ratio of silver to the color image-forming coupler in the photosensitive layer that covers the density range, and by relatively ejecting other layers, the latitude is expanded and the graininess is improved.'' (6) Ibid., page 6, line 73. Correct the “ratio” to the “molar ratio”.

(7) Same book @/page 2/line l’ "ratio" "Molar ratio" and correct it.

(8) Same book, page 73, line j "ratio" "Molar ratio" and correct it.

(9) Circular page 31 "Table 1" "Table 1" and correct it.

(The name of the compound in Table 2 on page ≠≠ of the 10th book, "2.!-G-5ee-octylno-hydroquinone" is changed to "2.T-5ee-octylno-hydroquinone isomer mixture", "2. t-di-dodecylhydroquinone” is converted into “λ, ter-di-dodecylhydroquinone isomer mixture j
And also ", 2. Taj-pentadecyl hydroquinone"
is corrected to ``, z, j-di-pentadecylhytroquinone isomer mixture.''

111 Insert the example shown in Attachment-λ after the 6th line of the #≠T page.

Attachment 1 2. Claims In a silver halide color photographic light-sensitive material comprising at least two or more light-sensitive emulsion layers having substantially the same color sensitivity and an intermediate layer on a support, the emulsion The ratio of the silver halide to the color image-forming coupler contained in at least seven of the layers is 10 or more, and the intermediate layer further contains at least a compound represented by the general formula A halogen-depleted color photographic light-sensitive material.

H (In the formula, R and Ri may be the same or different from each other! Attachment - Example 2 In Sample C of Example 1, the color of silver halide was changed by changing the amount of arsenic in the low green-sensitive emulsion layer. The molar ratio f to the one-quadrant-forming coupler was varied from 5 to 3.
It was created as shown in the table. In addition, the test '#+ of Example 1
In E, samples were prepared as shown in Table 3, in which only the addition cap of the emulsion in the low green-sensitive emulsion layer was changed, and the molar ratio of silver halide to the color image-forming coupler was changed to fjt-23. did.

All of these samples were subjected to the same treatment as shown in Example 1, and the results obtained are shown in Table 3.

From the above results, the degree of color mixing hardly changes when the molar ratio of silver to color image forming coupler is less than io2, but
When it reaches 70 or more, it increases sharply.

In order to suppress the degree of color mixing, when the compound of the present invention is used in the intermediate layer, sufficient sharpness can be obtained even if a large amount of 1.00 m 97 m 2 is used.

Procedural amendment January 1, 2015 2. Title of invention: Silver halide color photographic material 3.
Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4, subject of amendment Column 5 of "Detailed Description of the Invention" of the specification, contents of amendment (1) "The following layer" in line 7 of the first page of the specification is changed to "undercoat layer" ” he corrected.

(2) Page 22, line 7j of the same book After "dissolved in 100(f:,") "Dodecylbenzenesulfonic acid soda 10g" Insert.

(3) Line 30, page 30 of the same book After "dissolved in /00C1," "Sodium dodecylbenzenesulfonic acid 10jq" Insert the meeting.

(4) “1ooc” on page 31 of the same book, line λ and/or line 2
Insert [Sodium dotecylbenzenesulfonic acid lOg] after ``dissolve in t,''.

(5) Same book, page 37/, 2nd line "For gelatin" "gelatin" and correct it.

(6) Line 3, page 3 of the same book [Ratio to] "Molar ratio to" and correct it.

(7) Same book, page 32, line 77 "Highly sensitive silver bromide" "Nakamado Ibromated Kaburi" and correct it.

(8) Same book No. 3! page 17th line From “3rd layer”/I1 line "Mix to 1 kg," until t Correct as shown below.

"Ultraviolet absorber j-chloro-λ-(-monohydroxy-3.j-di-t-butylphenyl-2H-benzotriazole),z-(,2-hydroxy-j--j-butylphenyl)- , 2H-benzitriazole 3og Co(2-hydroxy-3-sec-butyl-1-1-butylphenyl-2H-benzotriazole 35g Dodecyl 5-(
N,N-diethylamine)-λ-pensene sulfonyl-2, Hiro-pentadienoate 1009 Tricresyl phosphate 200cc Ethyl acetate 2
00C1:.

Sodium dodecylbenzenesulfonate -209io% gelatin aqueous solution 2 is stirred at high speed to obtain an emulsion/klil-i/θ%
Mix with gelatin, water, and coating aids.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising, on a support, at least two or more light-sensitive emulsion layers having substantially the same color sensitivity and an intermediate layer, in which at least two of the emulsion layers have substantially the same color sensitivity. The ratio of silver halide to color image-forming coupler contained within one layer is i. A silver halide color photographic light-sensitive material having the above structure and further containing at least seven kinds of compounds represented by the following general formula CI) in the intermediate layer. (In the formula, R1 and R2 may be the same or different from each other (, l
- Represents a group selected from methylbexyl group, l-ethylpentyl group, l-propylbutyl group, l-methylhebutyl group, l-ethylhexyl group and l-propylpentyl group. )