JPS62247367A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To rapidly form a high-quality image by incorporating a solution prepared by dissolving a specified compound in at least 2 kinds of high-boiling organic solvents and using a high chloride content silver halide emulsion in a silver halide emulsion layer. CONSTITUTION:The silver halide emulsion layer contains the solution prepared by dissolving the compound represented by formula I in at least 2 kinds of high-boiling organic solvents. The silver halide emulsion layer contains the high chloride content silver halide emulsion composed of at least 80mol% silver chloride. In formula I, Z1 is an atomic group necessary to form an N-containing heterocyclic group; R1 is H, halogen, or the like; R2 is -COOR21, -COOR22- COOR21, or the like; R21 is a 6-30C diffusion resistant group; and R22 is alkylene.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material suitable for printing. The present invention relates to a silver halide color photographic material that can produce color prints with excellent tonal reproduction.

[Background of the invention]

Silver halide color photographic materials are widely used today because of their high sensitivity and excellent gradation. Furthermore, improvements were made to printers and automatic processors, which made it possible to continuously process large amounts of silver halide color photographic materials, resulting in high productivity. The above value is extremely high.

Although they have such excellent properties, the development processing of silver halide color photographic light-sensitive materials is a so-called wet processing, and it takes time and effort to prepare a processing solution. Drainage fluid containing various chemicals comes out which makes it dirty. A darkroom is required. There were various drawbacks, such as a long time from the start of operation until the first print was obtained. In order to compensate for these shortcomings and take advantage of the advantages of silver halide color photographic materials mentioned above, until now, everything from developing color negatives to producing color prints has been carried out by skilled technicians in a small number of large photofinishing laboratories. A concentrated approach has been adopted.

Currently, although the essence of wet processing has not changed, improvements in printers and automatic processors have led to the development of cleaner and easier-to-handle technology. Furthermore, improvements in silver halide color photographic materials and photographic processing solutions have made photographic processing and handling easier, and the processing time has become shorter. Coupled with these trends, the number of so-called minilabs, which accept orders at stores and print immediately on the spot, is increasing, and the number is expected to increase even more in the future.

Under these circumstances, although a number of improvements have been made as mentioned above and the processing time has been shortened, it cannot be said that sufficient improvements have been made, and it is hoped that even faster processing will be possible. There is.

In order to achieve rapid processing of silver halide color photographic light-sensitive materials, it is necessary to shorten each step of the color photographic development process. In particular, the color development process takes a long time, so the improvement effect is significant. One way to shorten the processing time in the color development step is to use a development accelerator when developing an exposed silver halide color photographic light-sensitive material using an aromatic primary amine color developing agent. It is known. Among such development accelerators, compounds with relatively high activity often have the disadvantage of forming fog.

Furthermore, even if a compound has few of these drawbacks, its effects differ depending on each layer of the silver halide emulsion layer.
It has been difficult to obtain a sufficient development promoting effect while maintaining appropriate gradation balance. Furthermore, many compounds among development accelerators are not very stable under alkaline conditions, and the processing solution tends to change significantly over time.

Another method for reducing processing time in the color development step is to utilize high chloride silver halide emulsions. In this method, the silver halide is developed very quickly, but the tones in the legs become hard, while the tones in the shoulders become soft, and the color becomes muddy in the magenta layer, resulting in unsatisfactory image quality. It wasn't worth it.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic material for printing etc. that can quickly obtain high-quality images. An object of the present invention is to provide a silver halide color photographic light-sensitive material for printing, etc., which can obtain high-quality images without deterioration in tonal reproducibility.

[Structure of the invention]

In order to achieve the above object, the present inventors have conducted intensive research and found that the support has at least one silver halide emulsion layer, and the silver halide emulsion layer has the following general formula [I]. A highly chlorinated compound containing a compound represented by dissolved in at least two high-boiling organic solvents, and in which the silver halide emulsion in the silver halide emulsion layer contains at least 80 mol% or more of silver chloride. The inventors have discovered that the above object can be achieved by a silver halide color photographic light-sensitive material characterized by being a silver halide emulsion, and have failed to complete the present invention.

General formula (1) % formula % In the formula, Zl is an atomic group necessary to form a nitrogen-containing heterocyclic nucleus, R1 represents a hydrogen atom, a halogen atom, or an alkoxy group. R2 is: COO1h+, C00Rzz-Coo!
h+NHCORzzSOJz+, NHCOR21
represents a group.

Here, RZI represents a diffusion-resistant group having 6 to 30 carbon atoms.

R2□ represents an alkylene group, and R23 represents a hydrogen atom, an alkyl group, or an aralkyl group.

[Specific structure of the invention]

Examples of the halogen atom represented by R1 in the general formula (1) include a chlorine atom and a bromine atom, with a chlorine atom being preferred. The alkoxy group represented by R6 is preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, isopropyloxy group).

The alkylene group represented by R2□ has 1 to 1 carbon atoms.
6 alkylene groups (eg, methylene group, ethylene group, isopropylene group, isobutylene group) are preferred.

The alkyl group represented by RZ3 has 1 to 1 carbon atoms;
2 alkyl groups (eg, methyl, ethyl, butyl, etc.) are preferred. Examples of the aralkyl group represented by R23 include a benzyl group.

Examples of the nitrogen-containing heterocyclic nucleus represented by Zl include an imidazole nucleus, a triazole nucleus, a thiadiazole nucleus, a hydantoin nucleus, and a urazole nucleus.

Specific examples of the compound of general formula (1) are shown below.

(I-13) The compound of general formula N) used in the present invention is dissolved in a high boiling point organic solvent and contained in the silver halide emulsion layer,
The high-boiling solvent is used as a mixture of at least two compounds.

In the present invention, a high boiling point organic solvent refers to an organic solvent having a boiling point of 150°C or higher, preferably a high boiling point organic solvent having a vapor pressure of 0.5 m+sHg or lower at 100°C.

Examples of high-boiling organic solvents include phthalic acid esters, phosphoric acid esters, cyclohexane-containing esters, hydrocarbons, organic acid amides, ketones, etc., but preferred compounds include the following general formula (II )～(Vl
) is a compound represented by

General formula (II) In the formula, R, , R, and t each represent an alkyl group, an alkenyl group, or an aryl group.

The alkyl group represented by Roll and R5t is linear or branched, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group,
Decyl group, undecyl group, dodecyl i, tridecyl group,
These include a tetradecyl group, a bentatecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and the like. The aryl group represented by R31 and R1 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. , an alkenyl group, an alkoxycarbonyl group, etc., and examples of substituents for the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. . Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.

(Exemplary compounds) (n-1) (n-2) (II-3
) (II-4) (II-5)
(n-6>(■-7)
(II-8) 1l-9 II-10CJs C, HS II-14CH3CH.

■-15 ■-17 -t8 ■-20 R41P -R-s R4 In the formula, Ra I+ Ra and R43 each represent an alkyl group, an alkenyl group, an aryl group, or a cycloalkyl group.

The alkyl group represented by R4, R4□ and R43 is
For example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. be. Examples of the alkenyl group include an allyl group, examples of the aryl group include a phenyl group and tolyl group, and examples of the cycloalkyl group include a cyclohexyl group.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R41, R4t and R41 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3
．． 5.5-) Limethylhexyl group, n-nonyl group, n-
Decyl group, 513C-decyl group, 5ec-dodecyl group,
Examples include t-octyl group.

(IIl-1) (I
II-2) (III-7)
(I[l-8)1[[-9III-10 m-ii I[[-
120-CJ+w(n) 0-
C+zHzs(i)0=P OCJtw(n)
0-P-OC+Jzs(t)0
CJ+*(n)
OC+ tHts(i)III-1311
I-14 General Formula (IV) In the formula, R3l+ Rat represents an alkyl group having 3 to 20 carbon atoms, and n4□ n4□ represents an integer of O to 4.

The alkyl group represented by R5I+ Rsz is,
Examples include pentyl group, -ethylpentyl group, nonyl group, and dodecyl group.

Specific examples of the compounds are shown below.

(IV-4) H3 (■~6) (IV-7) (IV-8) General formula (V) R&I÷0CHHzCHz +h50RhzIn the formula, R1+
represents an alkyl group, and R6□ represents a hydrogen atom or an alkylcarbonyl group. n represents an integer from 1 to 10.

The alkyl group represented by R61 has 1 to 20 carbon atoms.
Straight chain or branched alkyl groups (butyl group, 2-ethylhexyl group, nonyl group, etc.) are preferred.

The alkylcarbonyl group represented by Rht is preferably an alkylcarbonyl group having 1 to 20 carbon atoms (acetyl group, propylcarbonyl group, etc.).

Specific examples of the compounds are shown below.

(V l ) CaH*0CHzCHzOCHz
C) ItOCOCHi('V 2) CsH+J
CHzCHzOC1hCHzOCOC1h(V 3
) C41(*0C)l*cHtOc)IzCll
zOCHtCHzOCOCHi(V-4) c
ztt.

CJ*CCH*0CHzCHzOC1bCIbOCOC
zHs(V −5) CJ*CHOCHtC)bO
cHtcHzOcOcHsCH3 (V 6) CsH+tOCHzCHzOCHz
CHzOCOCCHCHsCH.

(V 7 ) CaH*0CHzCHtOCHt
CHtOCOCHCnH*2H General formula (Vl) H R? ! During the ceremony, R? l+R? ! represents an alkyl group or a hydrogen atom.

Rt++ R? Examples of the alkyl group represented by g include a butyl group, a nonyl group, and a dodecyl group.

Specific examples of the compounds are shown below.

(Vl-1) (VI-2) CsH+
+ (t) CJ+*(t) (Vl
-3) (Vl-4) (Vl-5) H c+Jzs.

The compound of general formula (1) is dissolved in a high boiling point organic solvent and emulsified and dispersed. At this time, if necessary, a low boiling point and/or water-soluble organic solvent is used to dissolve the gelatin, and a surfactant is used in a hydrophilic binder such as water-soluble gelatin using a stirrer, a homogenizer, a colloid mill, or a flow It can be emulsified and dispersed using a dispersion means such as a jet mixer or an ultrasonic device, and then added to the desired hydrophilic colloid layer.
A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

When carrying out the present invention, the ratio of high boiling point organic solvent to low boiling point organic solvent is preferably 1:0.1 to 1:50, more preferably 1:1 to 1:20.

Examples of low-boiling or water-soluble organic solvents that can be used together with or in place of high-boiling solvents include those described in US Pat. No. 2,801.171 and 2,949,360. Organic solvents with low boiling points that are substantially insoluble in water include egylacetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone. , methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, and the like.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

The silver halide emulsion used in the present invention may be any of silver chlorobromide, silver iodochloride, silver chloroiodobromide, and silver chloride, but a high chloride halide emulsion containing 80 mol% or more of silver chloride may be used. It is a silver emulsion.

The silver iodide content is preferably 1 mol % or less, more preferably 0.5 mol % or less, and most preferably contains no silver iodide. The silver bromide content is preferably 5 mol% or less, more preferably 1 mol% or less, most preferably pure ichloride.

The grain size of the silver halide grains used in the color photographic light-sensitive material according to the present invention is determined by the length of the side in the case of cubic silver halide grains, and the length of the side of the grains in the case of cubic silver halide grains, and the particle size of grains with shapes other than cubes such as spherical shapes. In this case, the particle size is the length of one side when converted to a cube having the same volume, and the average particle size 7 is defined as the individual particle size r7 and the number n1 of particles having the particle size r,
Σn.

Expressed as

The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse, but a monodisperse emulsion is more preferable. Here, monodisperse refers to an emulsion in which the coefficient of variation in the grain size distribution of silver halide grains contained in the emulsion is 22% or less, preferably 15% or less.

The coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

The above particle size can be measured by various methods commonly used in the technical field for the above purpose. Typical methods include Loveland's "Particle Size Analysis Method" A, S, T, M, and Symposium.
On Right Microscopy, 1955, 94-
122, or Chapter 2 of ``Theory of Photographic Processes'' by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966).

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Also, while considering the critical growth rate of silver halide crystals, adjust the pH in the mixing vessel of halide ions and silver ions.

It may be produced by sequentially and simultaneously adding pAg while controlling it.

By this method, monodisperse silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

Any apparatus known in the photographic industry can be used as the production apparatus for the silver halide emulsion used in the present invention. Excess soluble salts and water in the hydrophilic colloid solution in the mixing vessel are removed by methods such as introducing the solution through a nozzle immersed in the colloid solution, continuously changing the concentration of the additive solution, and exit filtration. However, it is preferable to use an apparatus that applies a method of preventing the interparticle distance from increasing.

When producing the silver halide emulsion of the present invention, halogenated l! Solvents can be used to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (complex salts containing) and iron salts (complex salts containing) to contain these metal elements inside the particles and/or on the particle surfaces, and By placing the particles in a suitable reductive cloud environment, reduction-enhancing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, research, disclosure
1) Isclosure) It can be carried out based on the method described in No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. There may be.

Silver halide grains of high chloride silver halide emulsions are easily obtained in cubic shapes, but cubic, octahedral, and
These particles may have a regular crystal shape such as a tetradecahedron, or may have an irregular crystal shape such as a spherical or plate shape.
Any surface ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Preferably, cubic particles are used in the present invention.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

Also, for example, British Patent No. 618.061, British Patent No. 1.3
No. 15゜755, No. 1.396.696, Special Publication No. 4
No. 4-15748, U.S. Pat. No. 1,574,944
No. 1.623.499, No. 1.673,52
No. 2, No. 2.278.947, No. 2.399.0
No. 82, No. 2,410.689, No. 2.419,
No. 974, No. 2.448.060, No. 2.487
．． No. 850, No. 2,518.698, No. 2.52
No. 1,926, No. 2,642,361, No. 2.6
No. 94.637, No. 2,728,668, No. 2.
No. 739.060, No. 2.743.182, No. 2
, 743.183, 2.983.609, 2,983,610, 3,021,215, 3.026.203, 3.297.446 ,
3.297.447, 3.361.564, 3.411.914, 3,554,757
No. 3.565,631, No. 3, 565.63
3, 3.591.385, 3.656.9
No. 55, No. 3.761.267, No. 3,772,
No. 031, No. 3.857.711, No. 3,891
．． No. 446, No. 3.901.714, No. 3,90
No. 4.415, No. 3.930.867, No. 3,
984, No. 249, No. 4,054,457, No. 4,067.740, Research Disclosure 1200
No. 8, No. 13452, No. 13564, T. H. James “The Theory of the Photographic Process” (T. H. Jatmes,
The Theory of the Potogra
phicProcess,) (4rh Ed, Ma
It is preferable to carry out sensitization using a chemical sensitizer or sensitization method described in, for example, Cmillan, 1977), pp. 67-76.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As the sensitizing dye used in the silver halide emulsion used in the present invention, cyanine dyes, merocyanine dyes, composite cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus , quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Examples of dyes that do not themselves have spectral enhancement effects or substances that do not substantially absorb visible light and exhibit supersensitization that can be used with the above-mentioned sensitizing dyes include, for example, aromatic organic acid formaldehyde. Folded metal products (e.g., those described in U.S. Pat. No. 3,437°510),
Examples include cadmium salts, azaindene compounds, and aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. No. 2,933,390 and U.S. Pat. No. 3,635,721).

U.S. Patent No. 3.615.613, U.S. Patent No. 3.615.6
No. 41, No. 3.617.295, No. 3.635.
The combinations described in No. 721 are particularly useful.

In addition to the yellow dye-forming coupler represented by formula [I], aromatic primary amine developers (such as p-phenylenediamine mHL, aminophenol derivatives, etc.)
A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized form of. The dye-forming coupler is usually selected for each emulsion layer so that a dye is formed which absorbs light in the sensitive spectrum of the emulsion layer, and for the blue-sensitive emulsion layer it is represented by the general formula CI). The yellow dye-forming coupler (and other yellow dye-forming couplers used in combination if necessary) is a magenta dye-forming coupler in the green-sensitive emulsion layer and a cyan dye-forming coupler in the red-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions are reduced and the neck is reduced. It can be either diisomeric or diisomeric. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, and chemical sensitizers by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments can be included, such as spectral sensitizers, spectral sensitizers, and quenching agents. These dye-forming couplers may also be used in combination with DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess. At this time, DIR
It is preferable that the dye formed from the coupler be of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be formed. It can be anything. D.I.R.
Instead of the coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction. (referred to as timing DIR couplers and timing DIR compounds). Furthermore, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination depending on the purpose. A colorless coupler that undergoes a coupling reaction with an oxidized aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers, and open-chain acylacetonitrile couplers can be preferably used. A specific example of a magenta coupler that can be advantageously used is disclosed in Japanese Patent Publication No. 40-603.
No. 1, No. 40-6035, No. 45-40757, No. 49-37854, JP-A-50-13041, No. 5
No. 1-105820, No. 52-42121, No. 53-
No. 123129, No. 53-125835, No. 53-1
No. 29035, No. 54-48540, No. 56-292
No. 36, No. 56-75648, No. 57-17950, No. 57-35858, No. 57-146251, U.S. Patent No. 2,600,788, No. 3.005.712
No. 3,062.653, No. 3,127゜269, No. 3,214,437, No. 3,253,924,
3,311゜476, 3,419.391, 3,519,429, 3.558゜319, 3
．． No. 582.322, No. 3,615.506, No. 3,
658゜544, 3,823.156, 3,8
No. 34,908, No. 3,891゜445, No. 3,90
No. 7.571, No. 3,926.631, No. 3,928
No. ゜044, No. 3,935.015, No. 3,960.
No. 571, No. 4,133゜686, No. 4,264.7
No. 23, No. 4,301,235, No. 4,310゜62
This is what is described in No. 3, etc.

As the cyan dye-forming coupler, naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1.038.331, British Patent No. 1,543.040, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 48-59838, British Patent Publication No. 50-137137, No. 51-146828, 5
No. 3-105226, No. 54-115230, No. 56
-29235, 56-104333, 56-1
No. 26833, No. 57-133650, No. 57-15
No. 5538, No. 57-204545, No. 58-118
No. 643, No. 59-31953, No. 59-31954
No. 59-59656, No. 59-124341,
No. 59-166956, U.S. Patent No. 2.369.92
No. 9, No. 2,423.730, No. 2,434.272
No. 2,474,293, No. 2.698, 794, No. 2.772.162, No. 2,801.171,
2.895.826, 3,253.924, 3,311.476, 3.458.315, 3
．． 476, 563, 3,591.383, 3,
737.316, 3,758.308, 3,7
No. 67.411, No. 3,790.384, No. 3.88
No. 0.661, No. 3,926.634, No. 4,004
．． No. 929, No. 4,009.035, No. 4,012.
No. 258, No. 4,052,212, No. 4,124.3
No. 96, No. 4,134,766, No. 4,138.25
No. 8, No. 4,146.396, No. 4,149,886
No. 4.178.183, No. 4,205.990, No. 4,254,212, No. 4, 264, 722
No. 4,288.532, No. 4,296.199, No. 4,296.200, No. 4,299,914,
4,333.999, 4,334.011, 4,386.155, 4,401.752, 4
, No. 427.767, etc.

Among dye-forming couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds can be used by solid dispersion method, Various methods can be used, such as latex dispersion method and oil-in-water emulsion dispersion method.
This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method is
Conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
If necessary, the solvent may have a low boiling point and/or water solubility. '8
It can be dissolved using a medium and emulsified and dispersed in the same manner as in the case of the compound of formula (1). After emulsification and dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point oils include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Examples of high-boiling organic solvents that can be used in combination with various couplers and the above-mentioned high-boiling organic solvents in carrying out the present invention include U.S. Pat. 2,835.579, 3
, 287.134, 2,353.262, 2.
852.383, 3,554.155, 3,6
No. 76, 137, No. 3,676, No. 142, No. 3,70
No. 0,454, No. 3,748.141, No. 3,779
．． No. 765, No. 3,837,863, British Patent No. 958
, No. 441, No. 1,222,753, OLS 2,5
38,889, JP-A-47-1031, JP-A No. 49-90
No. 523, No. 50-23823, No. 51-26037
No. 51-27921, No. 51-27922, No. 51-26035, No. 51-26036, No. 50-
No. 62632, No. 53-1520, No. 53-1521
No. 53-15127, No. 54-119921,
No. 54-119922, No. 55-25057, No. 5
No. 5-36869, No. 56-19049, No. 56-8
1836, Japanese Patent Publication No. 48-29060, etc.

The low boiling point or water-soluble organic solvent that can be used together with or in place of the high boiling point solvent may be the same as in the case of the compound represented by general formula [I].
The oxidized form of the developing agent or the electron transfer agent may migrate due to the same color-sensitivity layer weight and/or different color-sensitivity layer weight and/or different color-sensitivity layer weight, causing color turbidity, deterioration of sharpness, and noticeable graininess. A color antifoggant can be used to prevent this.

The antifogging agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

The light-sensitive material of the present invention may contain an image stabilizer that prevents deterioration of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

In the light-sensitive material of the present invention, a fluorescent whitening agent can be used for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation agent, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

The photographic emulsion and/or other hydrophilic colloid layer of the light-sensitive material of the present invention may include improved coating properties, antistatic properties, improved slipperiness, emulsion dispersion, prevention of adhesion, and photographic properties (development acceleration, hardening, sensitization, etc.). ) Various surfactants can be used for the purpose of improvement.

Gelatin is preferably used as a binder in the color photographic light-sensitive material of the present invention, but some or all of the gelatin may be substituted with gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, a derivatives, cellulose, etc. Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as derivatives, monopolymers, or copolymers can be substituted.

Polyol compounds such as ethylene glycol and glycerin can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer according to the present invention for the purpose of increasing flexibility.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
flexible reflective supports such as synthetic paper, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
Examples include films made of semi-synthetic or synthetic polymers such as polycarbonate and polyamide, flexible supports prepared by providing reflective layers on these films, glass, metals, ceramics, and the like.

In preparing the light-sensitive material of the present invention, the silver halide emulsion layer and other protective colloid layers were prepared using Research Disclosure + - (Research Disclosure).
) No. 17463, applied by the method described in XV A, and
It can be dried by the method described in .

The photosensitive material of the present invention can be processed by various methods. For example, as a color development process, a color development process,
A bleaching process, a fixing process, a water washing process, and/or a stabilizing process are performed as necessary, but instead of the process using a bleaching solution and the process using a fixing solution, a one-bath bleach-fixing process is performed. A bleach-fixing process can be carried out using a solution, or a monobath process can be carried out using a one-bath development, bleach-fixing solution that allows color development, bleaching and fixing to be carried out in one bath.

In addition to these processing steps, a pre-hardening process, a neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. Representative treatments among these treatments are shown below. (These treatments are carried out as the final step, which is either a water washing process, a stabilization process, a water washing process, or a stabilization process.)・Color development process - Bleaching process Constant fixation process ・Color development process Processes - Bleach-fixing process/Pre-hardening process - Neutralizing process - Color development process - Stop-fixing process - Washing process - Bleaching process Constant fixing process - Washing process - Post-hardening process Color development process - Water washing process - Supplementary color development process - Stop process - Bleaching process Constant coloring process/monobath process The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent. This includes aminophenol and p-fuynylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, and benzenesulfonate.

These compounds have the general formula color developer 1! about 0
．． Concentrations of 1 g to about 30 g, more preferably about 1 g to 15 g for color developer 11 are used. 0.1
If the amount added is less than g, sufficient color density cannot be obtained.

Further, the temperature of the processing solution in the color developing tank is 10°C to 65°C, more preferably 25°C to 45°C.

Examples of the aminophenol-based developer include O-aminophenol, p-aminophenol, 5-aminophenol,
2-oxy-toluene, 2-amino-3-oxytoluene, 2-oxy-3-amino-1,4-dimethyl-
Contains benzene, etc.

Particularly useful primary aromatic amine color developers include N, N
-Dialkyl-p-phenylenediamine type compounds, in which the alkyl group and phenyl group may be substituted or unsubstituted, among which N is a particularly useful example.

N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, 2-amino-5
-(N-ethyl-N-dodecylamino)-toluene, N
-ethyl-N-β-methanesulfonamidoethyl-3-
Methyl-4-aminoaniline miniic acid [,N-ethyl-N
-β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N,N-diethylaniline, 4-amino-
N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-1-luenesulfonate, etc. 1. f can be done.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may. Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

The pH of the color developing solution used is usually 7 or more, preferably about 9-13.

In addition, the color developing solution used in carrying out the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, and hydroxamic acid as necessary. Acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained.

In the color developing solution that can be used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, ■-hydroxyethylidene-1,1'-
Organic phosphonic acids such as diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenecyaminethi-1-laric acid, oxycarboxylic acids such as citric acid or glyconic acid, 2-phosphonobutane-1
, phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The color developer may contain a color development accelerator such as benzyl alcohol within a range that does not impair the effects of the present invention. The effects of the present invention are noticeable even in the absence of benzyl alcohol, and it is particularly useful for such treatments.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A 1 mol/l solution lβ of silver nitrate and a 1 mol/l solution of sodium chloride were added over 50 minutes to a 4% aqueous gelatin solution of 700a1 containing 6 g of sodium chloride using a metering pump. During this time, pAg was adjusted to maintain it at 7.7. Next, washing with water and desalting were performed by the following operations.

As a precipitant, a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate were added at a ratio of 10:9 until precipitation occurred. After the precipitate settled by standing still, the supernatant was decanted, and then distilled water 32 was added to redisperse the precipitate. Add 20% magnesium sulfate aqueous solution until precipitation occurs again, and after standing still, decant the supernatant, then add gelatin aqueous solution, stir at 40 ° C. for 20 minutes to redisperse, then add sodium chloride aqueous solution,
p and Ag were adjusted to 7.6, and at the same time distilled water was added to adjust the volume. The resulting emulsion had a gelatin concentration of 5% and a volume of 56
It was 0ml. This emulsion is hereinafter referred to as E,-1. As a result of electron microscopic observation, it was found that this emulsion had an average grain size of 0.4 μm.

4% gelatin containing 0.03 g of sodium chloride and 25 mg of 1,8-dihydroxy-3,6-cythiaoctane was prepared using a metering pump with a 1 mol/l silver nitrate solution 11 and a 1 mol/1 sodium chloride solution. Aqueous solution 35011
Il was added over 49 minutes during which pAg was increased to 7.
I kept it at 9. After the addition was completed, the mixture was desalted, washed with water, and redispersed in the gelatin solution in the same manner as described in the preparation of E and -1. The volume after re-dispersion was adjusted to 560ml It.

This emulsion is 17011! Then gelatin and distilled water were added to adjust the volume to 717+mf and the gelatin concentration to 3.9%. After adjusting the pAg to 7.1 by adding an aqueous sodium chloride solution, 970 ml of a 1 mol/l silver nitrate solution and 1 mol/l sodium chloride were added over 82 minutes, during which time the pAg was maintained at 7.1.

After desalting, washing with water, and redispersing in an aqueous gelatin solution using the method described in the preparation of El-1, the volume was adjusted to 560 ml, and the pA
, g was adjusted to 7-16. This emulsion is hereinafter referred to as El-2. As a result of electron microscopy, the average grain size of this emulsion was 0.
．． It turned out to be 7 μl.

E, -1,2 were taken, 2.6 x 10-6 mol of sodium thiosulfate was added per 100 ml of the emulsion, and chemical ripening was carried out by a conventional method. El-1 5 minutes before the end of chemical ripening
was divided into two parts, and a green-sensitive sensitizing dye was added to one, a red-sensitive sensitizing dye was added to the other, and a blue-sensitive sensitizing dye was added to E and -2. At the end of chemical ripening, a stabilizer (ST
-1) was added in an amount of 1 g per mole of silver halide.

Next, a multilayer sample was prepared in the following manner.

A silver halide color photographic material was prepared by sequentially coating the following seven layers on a paper support coated with polyethylene. Here, the amount of each compound is expressed as a value per 1 d of color photographic material.

(Layer 1) Yellow coupler 1 shown in Table 1. I x 10
−'mol and 0.015 g of color layer inhibitor dissolved in 0,
4 g of high-boiling organic solvent dispersion (if used in combination, in a 1:1 ratio).

Silver halide emulsion layer containing front window photogenic emulsion (0.45 g as silver) and 2 g of gelatin.

(Layer 2) 0.03g dissolved in 0.02g color layer inhibitor
an intermediate layer containing a dibutyl phthalate dispersion of 1 g and 1 g of gelatin. A hardening agent was contained here at 0.04 g/mff1.

(Layer 3) Magenta coupler (M-1) 0.63g and 0
．． A silver halide emulsion layer containing 0.34 g of tricresyl phosphate dispersion in which 0.15 g of color layer inhibitor was dissolved, a green-sensitive emulsion (0.40 g as silver) and 2 g of gelatin.

(Layer 4) 0.03g of color layer inhibitor and 0.8g of UV absorber
An interlayer containing 0.5 g of dibutyl phthalate dispersion and 0.15 g of gelatin dissolved in g. hardener 0.04
g/m.

(Layer 5) Cyan coupler (C-1) 0.35g and 0.0
0.2 g of dioctyl phthalate dispersion in which 15 g of color layer inhibitor is dissolved and a red-sensitive emulsion (0.30 g as silver)
g) and a silver halide emulsion layer containing 1.5 g of gelatin.

(Layer 6) Intermediate layer containing 0.3 g of dibutyl phthalate dispersion dissolved in 0.4 ga of UV absorber and 1 g of gelatin.

(Ji7) Layer containing 1 g of gelatin.

(M-1) C12 Comparative compound A Color layer inhibitor H R Ultraviolet absorber 2:3 After exposing the sample thus obtained according to a conventional method,
The following development treatment was performed. Check the density of the formed image on the PDA
The sensitivity and rl+γ2 were measured using a -65 to 11 degree meter (manufactured by Konishiroku Photo Industry Co., Ltd.).

Sensitivity is expressed as relative sensitivity with sample 1 as 100, T is the leg gradation of reflection density 0.2 to 0.7, T2 is reflection density and shoulder gradation of 0.7 to 2.0. represent.

As shown in Table 1, B? As for the characteristic value of M degree, when a high boiling point solvent is used alone, the contrast of the toe (TI) is markedly increased. At the same time, a softening of the shoulder area (T2) is observed. This tendency is observed in the compound of general formula (1), (1-
13) was more remarkable in the case of Comparative Compound A. When the high boiling point solvent compound of the present invention was used, when the yellow coupler (1-13) was used, both showed equivalent performance and good gradation reproducibility, but compared to Comparative Compound A. In some cases, even the combination of high boiling point organic solvents of the present invention did not solve the gradation problem.

Processing process Temperature Time (11 Color development 35℃ 50 seconds (2) Bleach fixing 35℃ 50 seconds (3) Water washing 30~
34℃ 2 minutes (4) Drying 60-90℃
- The composition of the treatment liquid used in each step is as follows.

Bleach-fixing solution Color developing solution (per lj?) (Example 2) The sample prepared in Example 1 was decomposed and exposed to blue light, and the G density at the B density part of 1.80 was measured. The results are shown in Table 2.

Table 2 As shown in Table 2, in all comparative samples, magenta coloration occurred due to development of the blue-sensitive layer, indicating that color turbidity occurred. Color turbidity is eliminated by using a high boiling point organic solvent. Although it is not unexpected that high-boiling organic solvents alter color development behavior, this effect is unexpectedly large.

(Example 3) According to the method of Example 1, silver chlorobromide emulsions E,-3 (0.4 μm) and E,-4 (0,65
μm) was prepared. Next, sulfur sensitization is carried out by a conventional method,
E, -3 to red-sensitive emulsion and green-sensitive emulsion, E,%-4
A blue-sensitive emulsion was prepared, a coated sample was prepared in the same manner as in Example 1, and after exposure and development, the maximum density was measured. The results are shown in Table 3.

Below margin ′,・) - Sample 11 whose silver halide emulsion has a silver bromide content of 25 mol%
It can be seen that in h18 to h22, the value of degree B'a is extremely low, and the suitability for rapid processing is poor. It can be seen that even in the samples using pure silver chloride, the B:a degree is low in samples other than N18 according to the present invention.

(Example 4) Samples were prepared in the same manner as in Example 1 with different yellow couplers and high boiling point organic solvents, and the B tH degree γ was evaluated.

Table 4 As shown in Table 4, even when the yellow coupler and the high-boiling point solvent were changed, the samples of the present invention did not exhibit high contrast in the legs and exhibited excellent gradation reproduction.

Representative Patent Attorney Toru Takatsuki Procedural Amendment July 24, 1986 Director General of the Patent Office Michibu Uga 1, Indication of the Case 1986 Patent Application No. 091137 3, Relationship to the Considered Case to be Amended Patent Application Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. 4, agent name (8397) Patent attorney Takatsuki
5. Date of amendment order June 1986
June 24th -] 6. Subject of amendment Full text of the specification 7. Contents of amendment Procedures as shown in the attached sheet Indication 1985 Patent Application No. 091137 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship to the person making the amendment case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment “Detailed description of the invention” in the specification
column.

7. Contents of the amendment As shown in the attached document, "Jit mixer" is corrected to "Flow jet mixer".

(2) "Antihalation agent" in line 14-15 of No. 52 of the same book is corrected to "antihalation layer."

(3) "Photographic emulsion" on page 52, line 20 of the same book is corrected to "photographic emulsion layer."

(4) In the third line of page 68 of the same book, the word ``remarkable'' is changed to ``authored'' and the following statement is added.

[Effects of the Invention] According to the present invention, it is possible to provide a silver halide color photographic material that can be processed quickly and that can produce high-quality images with excellent color turbidity and gradation reproducibility. I can do it.” That’s it.

Claims (1)

[Scope of Claims] A support has at least one silver halide emulsion layer, and a compound represented by the following general formula [I] is contained in the silver halide emulsion layer, and at least two types of high-boiling point organic The silver halide emulsion contained in the silver halide emulsion layer is a high chloride silver halide emulsion containing at least 80 mol% of silver chloride. Silver halide color photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1 is an atomic group necessary to form a nitrogen-containing heterocyclic nucleus, R_1 is a hydrogen atom, a halogen atom, or an alkoxy group. R_2 is , -COOR_2_1, -COOR_2_2-
COOR_2_1▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ -NHCOR_2_2SO_2R_2_1, -NHCO
Represents R_2_1 group. Here, R_2_1 represents a diffusion-resistant group having 6 to 30 carbon atoms. R_2_2 represents an alkylene group, and R_2_3 represents a hydrogen atom, an alkyl group, or an aralkyl group.