JPS62178242A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high color forming density even if a photosensitive material is quickly processed with a color developing soln. contg. no benzyl alcohol by incorporating the precursor of a color developing agent and specific compd. into said material and using a specific coupler. CONSTITUTION:The precursor of the color developing agent and at least one compd. selected from the compds. expressed by formula I, formula II, formula III and formula IV are incorporated into the photosensitive material. The coupler dispersed and incorporated by using a high boiling point org. solvent having <=6.0 dielectric constant is used. R1, R2, R3, R4 are an alkyl group, R6, R7 are an H atom, alkyl group, R1 and R2, R3 and R4, R6 and R7 may bind with each other to form a nitrogenous heterocycle together with an N atom. R5, R6 are a halogen atom, etc., n1, n2 are 0-4. R5, R6 may be the same or different when n1, n2 are 2-4. X is an H atom or hydrolyzable group. R9 is an aryl group, R10, R11, R12, R13 are an H atom, alkyl group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material which has improved coupler color development, desensitization, and storage stability over time such as fogging.

[Background of the Invention] Generally, silver halide color photographic light-sensitive materials consist of three types of silver halide photographic materials that are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on a support. An emulsion layer is coated. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and there is a layer between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion layer. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. Furthermore, for example, in light-sensitive materials for color photographic paper, the layers are generally coated in the order of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer from the exposed side, and each layer has a special coating, similar to the light-sensitive material for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanoacetyl couplers are used to form cyan, magenta and yellow dye images, respectively. Magenta couplers and acylacetamide-based or benzoylmethane-based yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer solution. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, various measures have been taken to speed up color development. As one method, it is known to use a color development accelerator when developing an exposed silver halide color photographic light-sensitive material using an aromatic primary amine color developing agent. For example, as such a color development accelerator, U.S. Pat.
No. 0, No. 2,515.147, No. 2.496.90
No. 3, No. 4,038,075, No. 4.119,46
2, British Patent No. 1.430.998, British Patent No. 1,455.
No. 413, JP-A-53-15831, JP-A No. 55-624
Compounds described in Japanese Patent Publication No. 50, No. 55-62451, No. 55-62452, No. 55-62453, No. 51-12422, Japanese Patent Publication No. 12422-1982, No. 55-49728, etc. were investigated. Most of these compounds have insufficient development accelerating effects, and even those compounds that exhibit sufficient development accelerating effects often have the drawback of producing fog, making them impractical.

Furthermore, JP-A-56-64339 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and JP-A-57-64339 describes
No. 144547, No. 58-50532, No. 58-50
No. 533, No. 58-50534, No. 58-50535
No. 58-50532 discloses that 1-arylpyrazolidones are added to a silver halide color photographic light-sensitive material and processed within a short development time. .

However, the techniques described in these publications are not necessarily satisfactory in terms of obtaining dye images with sufficient color development speed and high color density, and there is still room for improvement. .

In addition, various penetrants have been studied to promote the penetration of color developing agents into silver halide photosensitive materials, and among these, a method of accelerating color development by adding benzyl alcohol to a color developer is widely used. It is being

However, benzyl alcohol is, for example, used in amounts widely used in color paper processing (10 vN/f
fi or 15112/2 or higher),
Because of its low water solubility, diethylene glycol or triethylene glycol is required as a solvent. However, from the perspective of reducing the pollution load, it is desirable to reduce the amount of benzyl alcohol and glycols used because they have high BOD and COD, and in particular, if the amount of benzyl alcohol used is 81Q/l or less, the solvent is unnecessary. This has the advantage that the pollution load can be further reduced.

Furthermore, when benzyl alcohol is brought into a bleach bath or a bleach-fixing bath which is a bath after the color developing bath, it becomes a factor in the formation of a leuco form of the cyan coupler, resulting in a decrease in the color density of cyan. Furthermore, when benzyl alcohol is carried into the post-washing bath, the storage stability of color images is deteriorated.

Therefore, the concentration of benzyl alcohol in the color developer is
For this reason as well, fewer is more desirable.

However, the concentration of benzyl alcohol is 81 (1/
When it is reduced to 1 or less, the color density is significantly reduced, and the various color development accelerators mentioned above (for example, U.S. Patent No. 2.
950.970, 2.515.147, 2.4
No. 96, 903, No. 2,304,925, No. 4,
No. 038,075, No. 4, 119.462, British Patent No. 1,430,998, British Patent No. 1,455.413, Japanese Patent Application Publication No. 15831/1983, No. 55-62450, British Patent No. 55
-62451, 55-62452, 55-62
No. 453, No. 58-50536, Special Publication No. 51-124
No. 22, No. 55-49728, etc.) were used in combination, but sufficient color density could not be obtained.

Especially when the content of benzyl alcohol is 8 ij2/Q
In rapid processing using the following color developing solutions (for example, rapid processing with a development time of about 1 minute at a processing temperature of 33° C.), the light-sensitive silver halide emulsion layer closest to the support develops the slowest. Furthermore, in color papers, it is necessary to significantly increase the sensitivity of the blue-sensitive silver halide emulsion layer, which is generally coated closest to the support, due to the required spectral sensitivity distribution. For this reason, it is necessary to make the silver halide grains in the emulsion used in this layer larger than the silver halide grains in other layers, which also causes the inconvenience of further accelerating development delays. be.

Furthermore, the technology of incorporating an aromatic primary amine color developing agent into a silver halide color photographic light-sensitive material and performing color development in an alkaline activation bath has been studied for some time, and numerous reports have been made. When incorporating an aromatic primary amine color developing agent, it is often used in the form of a precursor, taking into account its influence on silver halide and various additives.

As a precursor of such an aromatic primary amine color developing agent, for example, U.S. Pat. No. 3,342,599, Res
arch D 1 closure 14,850,
No. 15.159, JP-A-54-9924 describes a Schiff base of an aromatic primary amine color developing agent and an aromatic aldehyde, and U.S. Patent No. 3.719.492 describes an aromatic primary amine. Regarding reaction products between color developing agents and metal complexes, British Patent No. 803.783 describes phthalimide compounds between aromatic primary amine color developing agents and phthalic acids, and U.S. Pat.
No. 418 and JP-A-53-135628, JP-A No. 54-
Publication No. 79035 describes urethane compounds with an aromatic primary amine coloring agent.

However, the above-mentioned methods are known to have problems such as increased desensitization, fogging, and staining when silver halide color photographic materials are stored. Furthermore, this may be due to unreacted products in the precursors and free aromatic primary compounds during the process of incorporating the precursors reported above into silver halide color photographic light-sensitive materials, or during storage after incorporating them. It is known that amine color developing agents or their oxidized products have an adverse effect on silver halide, non-diffusible couplers, or various additives in silver halide color photographic light-sensitive materials.

Furthermore, it is known to accelerate development by lowering the silver bromide content and increasing the silver chloride content of the silver halide used, but even with this, it is difficult to obtain the required sensitivity.

[Objective of the Invention] The object of the present invention is to have a high color density even when rapidly processed with a color developing solution containing very little or no benzyl alcohol, to preserve the sensitivity, and to desensitize, An object of the present invention is to provide a silver halide color photographic light-sensitive material that exhibits less fogging.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material in which a silver halide emulsion layer containing a coupler is coated on a support at least once, the silver halide photographic light-sensitive material comprising a precursor of a color developing agent and a silver halide emulsion layer containing a coupler. The following general formula rI], [
1, [■] and [IV], and the coupler is dispersed in a high-boiling organic solvent having a dielectric constant of 6.0 or less. R with silver color photographic material
R4 (wherein R+, R2, R3 and R4 each represent an alkyl group, R1 and R2 and/or R3 and R4
may be bonded to each other to form a nitrogen-containing heterocycle with a nitrogen atom. R5 represents a halogen atom, an alkyl group or an alkoxy group, and nl represents an integer of O to 4. n
When l is an integer of 2 to 4, R5 may be the same or different. ) General formula [] (In the formula, R6 and R7 each represent a hydrogen atom or an alkyl group, and R6 and R1 may be combined with each other to form a window-containing heterocycle. R8 is a halogen atom, an alkyl group, or It represents an alkoxy group, and R2 represents an integer of O to 4. When R2 is an integer of 2 to 4, R8 is the same and 6
May be different. ) General formula [Il[] (wherein, X represents a hydrogen atom or a hydrolyzable group, R9 represents an aryl group, Rho, R11, R12
and R+3 each represent a hydrogen atom, an alkyl group or an aryl group. ) General formula [IV] (In the formula, A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom, and Y represents a sulfur atom or an oxygen atom.) [Specifics of the invention Configuration 1 The color developing agent precursor used in the present invention is a compound that produces a color developing agent under alkaline conditions, for example,
Schiff base type precursor with aromatic aldehyde derivative, polyvalent metal ion complex type precursor, phthalic acid imide derivative type precursor, phosphoric acid amide derivative type precursor, Shugo amine reactant type precursor, urethane type precursor Can be mentioned. Precursors of these color developing agents are described, for example, in U.S. Pat.
, No. 599, No. 2.507.114, No. 2,69
No. 5,234, No. 3.719, 492, British Patent No. 8
03.783, Mei III, JP-A-53-135
Publications No. 628 and No. 54-79035, Japanese Unexamined Patent Publication No. 1983
-81643, 58-200233, 58-
No. 192031, No. 59-13239, No. 56-10
No. 723, No. 58-9534, Research Disclosure Magazine No. 5,159, No. 12,146, No. 13
, No. 924. Specifically, the following compounds may be mentioned.

Below margin (CD-1) OH[
CD-12) (CD-15) (CD-19) CH3 CH2OCH3 2H5 2H5 Area 2H5 0COCH2CL (CD-30). H3OCOCH30COCH2CL (0D-33). 2H5o2H5 H2 NH2 The amount of these color developing agent precursors to be added varies depending on the type of photographic light-sensitive material, but is generally from 0.1 mole to 1 mole of photosensitive silver halide in the photographic light-sensitive material of the present invention. A range of between 5 mol and preferably 0.5 mol to 3 mol should be aimed at.

These color developing agent precursors can be used alone or in combination. When added to the photographic material of the present invention, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, dimethylformamide, etc., and dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. It can also be added as an emulsified dispersion using a high boiling point organic solvent;
They can also be added by impregnating latex polymers as described in Research Disclosure No. 14850.

When the color developing agent precursor described above is incorporated into the silver halide color photographic light-sensitive material of the present invention, the layer to be incorporated can be appropriately selected depending on the type of the color developing agent precursor and the processing method. Or a silver halide-free layer, preferably a silver halide-free layer.

Each structural unit forming a dye image in the silver halide color photographic light-sensitive material of the present invention consists of a single-pore agent layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The layers necessary for silver halide color photographic materials, including the layers of image-forming units described above, can be arranged in various orders as known in the art.

A typical multicolor silver halide color photographic light-sensitive material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer with a cyan coupler forming at least one cyan dye image, at least one magenta dye image-forming unit; A magenta dye image forming unit consisting of at least one green sensitive silver halide emulsion layer having a magenta coupler forming a dye image, at least one blue sensitive silver halide emulsion having a yellow coupler forming at least one yellow dye image. It consists of a layer of yellow dye image forming structural units supported on a support.

Yellow couplers preferably used in the present invention include those represented by the following general formula (A).

General formula (A> In the formula, R1 represents an alkyl group or an aryl group, and R
2 represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction.

R1 is a linear or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially butyl group), and R2 is an aryl group (preferably a butyl group). phenyl group)
The alkyl group and aryl group represented by R1 and R2 include those having substituents, and the aryl group of R2 is preferably substituted with a halogen atom, an alkyl group, etc. X is the following general formula (B) or (C
) is preferable, and roughly speaking, groups represented by formula (B)
A group represented by the general formula (B') is particularly preferred.

General Formula (B) In the formula, Zl represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula (C) 10 -Rn In the formula, R++ represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General formula (B') vinegar It does not represent a group of nonmetallic atoms that can be formed.

A preferred yellow coupler according to the present invention in the general formula (A) is represented by the following general formula (A').

General Formula (A') In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable.

R15, R+s and R17 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamide group, It represents a ureido group or an amino group, R+s and R+s are each a hydrogen atom, and RI7 is preferably an alkoxycarbonyl group, an acylamido group, or an alkylsulfonamide group. Further, X represents a group having the same meaning as that shown in the above general formula (A), preferably the above general formula (B) or (C
), or (B), a group represented by the general formula (B') is particularly preferred.

Next, preferred specific examples of the yellow coupler of the present invention represented by the general formula (A) are shown below, but the yellow coupler of the present invention is not limited thereto.

Below margin (Y-1) (Y-2) (Y-3) H3 (Y-4) (Y-5) (Y-6) (Y-7) (Y-8) (Y-9) (Y -10) (Y-11) (Y-12) t (Y-13) (Y-14) Specific examples of yellow couplers that can be used include British Patent Nos. 1 and 0.
77,874, Japanese Patent Publication No. 45-, 40757, Japanese Patent Publication No. 1031-1977, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-
No. 94432, No. 50-87650, No. 51-36
No. 31, No. 52-115219, No. 54-9943
No. 3, No. 54-133329, No. 56-30127
No. 2,875,057, U.S. Patent No. 3.253.
No. 924, No. 3, No. 265.506, No. 3.408.
No. 194, No. 3.551.155, No. 3.551.
No. 156, No. 3.664.841, No. 3,725.0
No. 72, No. 3.730.722, No. 3.891.44
No. 5, No. 3,900.483, No. 3.929.484
No. 3,933,500, No. 3,973.968, No. 3,990,896, No. 4,012,259
No. 4,022,620, No. 4.029.508, No. 4.057.432, No. 4,106,942,
4,133,958, 4.269°936, 4,286,053, 4.304.845, 4
．． No. 314,023, No. 4,336,327, No. 4,
No. 356,258, No. 4,386,155, No. 4.4
01.752, etc.

In the silver halide photographic light-sensitive material of the present invention, the magenta dye image-forming coupler has the following general formula [a
] and [aI] can be preferably used.

General formula [acoAr] [where Ar represents an aryl group, Rat represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y is m by reaction with a hydrogen atom or an oxidized product of a color developing agent.
W is -NH-1-, NHCO-(N
the atom is bonded to the carbon atom of the pyrazolone nucleus) or -NH
CON +- (Represents -, m is an integer of 1 or 2.) Specific examples of the following margin [a] "-4ct Ct General formula [aI] In the magenta coupler represented by the general formula [aI] , Za represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the za
The ring formed by may have a substituent.

X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent.

Moreover, Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a sulfonyl group, and a carbamoyl group. group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine group, acylamino group, sulfone Amide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include an alkylthio group, an arylthio group, and a heterocyclic thio group.

Next, specific examples of the magenta coupler represented by the general formula [aI] are shown below, but the present invention is not limited thereto.

The magenta couplers represented by the general formulas [a] and [a] used in the present invention are described in, for example, U.S. Pat.
．． 600.788, 3.061, 432, 3.062.653, 3,127,269,
3.311.476, 3,152,896, 3.419.391, 3,519,429
No. 3゜555,318, No. 3.684.51
No. 4, No. 3,888,680, No. 3,907,5
No. 71, No. 3,928,044, No. 3,930.
8Ei No. 3,930, 866, No. 3.93
3.500, etc., 111m, JP-A-49-2963
No. 9, No. 49-111631, No. 49-129538
No. 50-13041, No. 52-58922, No. 55-62454, No. 55-118034, No. 56
-38043, 57-35858, 60-23
Publications No. 855, British Patent No. 1.247,493,
Belgian Patent No. 769.116, Belgian Patent No. 792.525
No. 11I of West German Patent No. 2.156.111,
Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 59-125732
No. 59-228252, No. 59-162548, No. 59-171956, No. 60-33552, No. 60-43659, West German Patent No. 1, 070.
No. 030 and US Pat. No. 3,725,067.

As the cyan image forming coupler used in the present invention, couplers represented by the following general formulas [E] and [F] can be preferably used.

General Formula [E] In the formula, R+E represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2ε represents an alkyl group or a phenyl group. R2H represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

Z+a represents a hydrogen atom, a halogen atom, or a group that can be eliminated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General formula [F] 2F In the formula, R4F represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R5
F represents alkyl M (eg, methyl group, ethyl group, etc.). R6F is a hydrogen atom, a halogen atom (e.g. fluorine,
) or alkyl 1! ! (For example, methyl group, ethyl group, etc.)

22F represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Typical examples of cyan image forming couplers used in the present invention are described below, but the present invention is not limited thereto.

The following margin (n) CI 2H25S 02NH 2n5 The couplers represented by the general formulas [E] and [F] of the present invention are, for example, JP-A-59-146050, JP-A-Sho 59-146050;
-117249, No. 59-31953@.

Examples of the cyan coupler used in the Ikemi invention include U.S. Pat. Nos. 2,306,410 and 2
, No. 356, 475, No. 2, 362, 598,
2,367,531, 2,369,929
No. 2,423,730; No. 2,474,29
No. 3, No. 2,476,008, No. 2.498, 4
No. 66, No. 2,545,687, No. 2, 728
, No. 660, No. 2, 772, 162, No. 2
, No. 895,826, No. 2,976, No. 146, No. 3,002,836, No. 3,419,390,
3,446,622, 3,476,56
No. 3, No. 3,737, 316, No. 3,758, 3
No. 08, No. 3.839, 044, British Patent No. 47
No. 8,991, No. 945,542, No. 1, 084
, No. 480, No. 1, No. 377, No. 233, No. 1
, 388,024 and 1,543,040, as well as JP-A-47-37425 and JP-A-50-
No. 10135, No. 50-25228, No. 50-
No. 112038, No. 50- 117422, No. 50-
No. 130441, No. 51-6551, No. 51-
No. 37647, No. 51-52828, No. 51-
No. 108841, No. 53-109 (No. i30, No. 5
No. 4-48237, No. 54-66129, No. 54-1
Examples include those described in publications such as No. 31931 and No. 55-32071.

Two or more of the above yellow, magenta and cyan couplers may be contained in the same blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, respectively. Also, the same coupler may be included in two or more different layers having the same color sensitivity.

These yellow, magenta and cyan couplers are generally present in an amount of 2.times.10@-3 mole to 1 mole, preferably 1.times.10@-2 mole to 8.times.1 mole per mole of silver in the emulsion layer.
It is used in a range of 0-1 mol.

In order to incorporate the coupler used in the present invention into the emulsion, a high boiling point organic solvent with a dielectric constant of 6.0 or less and a low boiling point organic solvent such as ethyl acetate, butyl acetate or butyl propionate may be used alone, or If necessary, couplers are dissolved individually or in a mixture of these solvents, and then mixed with an aqueous gelatin solution containing a surfactant, and then subjected to high-speed rotation mixer, colloid mill, or ultrasonic dispersion. After emulsifying and dispersing using techniques,
In addition to silver halide, silver halide emulsions can be prepared.

Examples of high boiling point organic solvents with a dielectric constant of 6.0 or less include esters such as phthalates and phosphoric esters, ester amides, ketones, and hydrocarbon compounds with a dielectric constant of 6.0 or less. . Preferably dielectric constant 6.0 or less 1.9
With the above, the vapor pressure at 100℃ is 0.511IIIH!
It is a high boiling point organic solvent of J or less. More preferably,
These are phthalic acid esters or phosphoric acid esters in the high boiling point organic solvent. Note that the organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture is 6. It is sufficient if it is below Q. In addition, the dielectric constant in the present invention is 30"C
It shows the dielectric constant at .

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [V].

General Formula [V] In the formula, R4 and R5 each represent an alkyl group, an alkenyl group or an aryl group. However, R4 and R
The total number of carbon atoms in the groups represented by 5 is 8 to 32. More preferably, the total number of carbon atoms is 16 to 2.
It is 4.

In the present invention, the alkyl group represented by R4 and R5 in the general formula [V] is a linear or branched one, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group. group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. The aryl group represented by R4 and R5 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, aryloxy groups, and alkenyl groups. and alkoxycarbonyl groups, and examples of substituents for aryl groups include halogen atoms,
Examples include an alkyl group, an alkoxy group, an aryl group, an alkoxy 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.

Phosphate esters advantageously used in the present invention include those represented by the following general formula [VI].

General formula [VI] l Ra0-P-ORs R7 In the formula, R6, R7 and R8 are each an alkyl group,
Represents an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by R6, R7 and R8 is 24 to 54.

The alkyl group represented by R6, R7 and R8 in the general formula [VI] is, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group. group, pentadecyl group, hexadecyl group, heptadecyl group,
These include octadecyl group and nonadecyl group.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably Rs, R7 and R8 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3.5.
Examples include 5-trimethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.

Specific examples of the organic solvent according to the present invention are shown below, but the present invention is not limited thereto.

Exemplary meaningful solvent Cz Hs'! -12CzHs 0C*H+*(i) 0C*H+*(n) 0-C9゜H,, (i) 0-C6゜Hu(n) H-17 0C+1Hz(ri0Cl2Hz-(i) These organic solvents is used in an amount of 25 to 150% by weight, preferably 50 to 100% by weight, based on the coupler of the invention.

As the combination of the coupler and the high-boiling organic solvent used in the present invention, any combination of high-boiling organic solvents with a dielectric constant of 6.0 or less can be used, but preferably the general formula [V
] and [VI].

Next, the general formulas [I] and [I] used in the present invention
The compounds represented by [], [I[] and [IV] will be explained.

General formula [I] RgR4 (wherein R+, R2, R3 and R4 each represent an alkyl group,
4 may be bonded to each other to form a nitrogen-containing heterocycle with a nitrogen atom. R5 represents a halogen atom, an alkyl group or an alkoxy group, and nl represents an integer of 0 to 4.

When nl is an integer of 2 to 4, R5 may be the same or different. ) In the general formula [I], R1, R2, R3
The alkyl group represented by group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), sulfonamide group (e.g. alkylsulfonamide group such as methanesulfonamide group, arylsulfonamide group such as benzenesulfonamide group, etc.), aryl group (e.g. phenyl group, etc.) ) etc. Examples of the alkyl group represented by R1, R2, R3 and R4 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 5ec-
Examples include butyl group, hydroxymethyl group, β-hydroxymethyl group, β-methoxyethyl group, methanesulfonamidoethyl group, and the like. The nitrogen-containing heterocyclic nucleus formed by R1 and R2 and/or R3 and R4 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., such as a pyrrolidine nucleus, a piperidine nucleus, a morpholine nucleus, etc. I can do it.

Examples of the halogen atom represented by R5 in general formula [I] include a bromine atom and a chlorine atom, examples of an alkyl group include a methyl group and an ethyl group, and examples of an alkoxy group include a methoxy group. , ethoxy group, etc. The alkyl group and alkoxy group represented by R5 include those having a substituent.

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.

Margin below ■-13 Margin below These compounds, except for some, are known (for example, described in JP-A-50-15554, JP-A-58-120248, etc.), and those skilled in the art can Can be easily synthesized. The synthesis of these compounds can be carried out by, for example, [Bent, Deslotsch, Fassett, James, Laby, Sterner, Pittam, Heasberger; Journal on American Chemical Society, (Be
nt, Dessloch.

Fassott, James, Ruby, 5t
erner, Vittum.

Weissberger; J, Am, Che
m, Soc, )]73,3100 (195
1), [Bent, Brown, Gressmanes, Harnisch; Photo 1 Niens Engineering, (3en
t, 3 rows.

Glesmaness, Harnish: Pho
t, Sci, Eng, ) 8, 125 (196
4) etc. can be referred to.

General formula [I] (In the formula, R6 and R7 each represent a hydrogen atom or an alkyl group, and R6 and R7 may combine with each other to form a nitrogen-containing heterocycle. R8 is a halogen atom, an alkyl group, or represents an alkoxy group, and R2 represents an integer of O to 4. When R2 is an integer of 2 to 4, R8 may be the same or different.) In general formula [II], an alkyl group represented by R6 and R7. may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms, and these alkyl groups include those having substituents, such as hydroxy groups, alkoxy groups (e.g. methoxy group, ethoxy group, etc.), sulfonamide group (for example, alkylsulfonamide group such as methanesulfonamide group, arylsulfonamide group such as benzenesulfonamide group), and the like. Examples of the alkyl group represented by R6 and R7 include methyl group, ethyl group, butyl group, hexyl group,
Examples include hydroxymethyl group, β-hydroxyethyl group, methoxymethyl group, β-methanesulfonamidoethyl group, and the like. The nitrogen-containing heterocyclic nucleus formed by R6 and R7 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., and examples thereof include a pyrrolidine nucleus, a piperidine nucleus, a piperazine nucleus, a morpholine nucleus, and the like.

Examples of the halogen atom represented by R8 include a bromine atom and a chlorine atom, examples of the alkyl group include a methyl group and an ethyl group, and examples of the alkoxy group include a methoxy group and an ethoxy group. It will be done.

The alkyl group and alkoxy group represented by R8 include those having a substituent.

When R2 is 2 to 4, R8 may be the same or different.

Specific examples of the compound represented by the general formula [U] used in the present invention are shown below, but the present invention is not limited thereto.

Margin below u-i 1l-2I
t-311-4 11-71l-8 n -11n -12 It -15n -16 II -17II -18 0HIJI-1 These compounds are described, for example, in U.S. Pat.
No. 2,483.374, No. 2,776.31
No. 3, No. 3.060,225, British Patent No. 928.
No. 671 statement, Berichte der Deutschen Chemischen Gesellschaft, Volume 16, page M724 (B Q
Richte der Qeutschen Chem
ischen Qesellschaft) for the same magazine 3
2.125 pages for Spring 4, Chemische Berichte Vol. 92, No. 3, 223 pages.
e), Photographic Science and Engineering Vol. 12, p. 41 (photograph
phtc, 3 science and Eng.
inering) and Journal on the Chemical Society No. 1947i1'J182 (Jo
urnal or the Chemical 3oc
It can be synthesized according to the method described in et al.

General formula [I[1] (wherein, X represents a hydrogen atom or a hydrolyzable group, R9 represents an aryl group, Rlo, R+1, R12
and R13 each represent a hydrogen atom, an alkyl group or an aryl group. ) In the general formula [1[[], X represents a hydrogen atom or a hydrolyzable group, and the hydrolyzable group represented by X is preferably an acetyl group. X is preferably a hydrogen atom.

As the aryl group represented by R9 in general formula [1],
For example, phenyl group, naphthyl group, etc. can be mentioned, but phenyl group is preferable. This aryl group includes those having substituents, such as alkyl groups (e.g. methyl group, ethyl group, propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.), alkoxy M (methoxy group, ethoxy group, etc.), a sulfonyl group, and an amide group (methylamide group, ethylamide group, etc.).

Rto, R++, RI2 and R1 of the general formula [I[[]
The alkyl group represented by 3 is preferably an alkyl group having 1 to 10 carbon atoms! (e.g. methyl group,
ethyl group, butyl group, etc.). This alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, an amino group, and an acyloxy group. Further, examples of the aryl group of R+o1R++, R12 and Rt3 include a phenyl group and a naphthyl group. This aryl group includes those having substituents, such as alkyl groups (methyl group, ethyl group, propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.)
, an alkoxy group (methoxy group, ethoxy group, etc.), a hydroxyl group, and the like.

Typical specific examples of the compound represented by the general formula [II[] used in the present invention are shown below, but the compound of the present invention is not limited thereto.

Margin below III -13III -14 10-15III -16 --1-19 I[1-2
0I[1-21III -22 I[1-231-24 H3 III -25III -26 I[1-27III -28 I[1-29III -30 t[I -31111-32 II[-33I[1-34 III -35I[1-36 nl -37Ill -38 H3 III -41III -42 CH,3 111-43I[1-44 t III -45111-46 t III-47III -48 General formula [IV] Y (wherein, A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom, and Y represents a sulfur atom or an oxygen atom.) In the general formula [IV],
The secondary amino group bonded to the carbon atom of the mother nucleus represented by A and B with a nitrogen atom can contain various aliphatic or aromatic components, and A and 8 may be the same or different from each other. good.

Specifically, the above A and B are -N H-R14 and -
Each can be expressed as N H−R+s, where R
14 and Rts are each an aliphatic or aromatic group, and R++ and R+s are preferably electron donating groups. Specifically, the groups represented by R14 and R15 are:
Examples include alkyl groups, alkenyl groups, aryl groups, etc.
These alkyl groups, alkenyl groups, and aryl groups include those having substituents.

Examples of these substituents include alkoxy groups (eg, methoxy group, ethoxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, etc.), and the like. RI4 and R15 are, for example, methyl group, ethyl group, propyl group, butyl group, methoxymethyl group, β-methoxyethyl group, β
-Ethoxyethyl group, methylthioethyl group, ethylthiomethyl group, allyl group, phenyl group, methoxyphenyl group, ethoxyphenyl group, methylthiophenyl group, ethylthiophenyl group and the like.

Specific examples of the compound represented by the general formula [IV] used in the present invention are shown below, but the present invention is not limited thereto.

IV-12,5-bis(methylamine)-1゜3.4-
Thiadiazole IV-22-methylamino-5-ethylamino-1,3
,4-thiadiazole EV-32,5-bis(ethylamino)-1゜3.4-
Thiadiazole rV-42,5-bis(n-butylamino)-1,3,
4-thiadiazole IV-52-allylamino-5-methylamino-1,3
,4-thiadiazole IV-62-(2-ethoxyethylamino)-5-methylamino-1,3,4-thiadiazole IV-72,5-bis(phenylamino)-1,3,4
-Thiadiazole IV-82,5-bis(2-methoxyethylamino)-
1,3,4-thiadiazole rV-92-(2-ethoxyethylamino)-5-(2
-methoxyethylamino) -1,3,4-thiadiazole TV-102,5-bis(2-ethoxyethylamino)
-1,3,4-thiadiazole rV-112-(2-methoxyethylamino)-5-phenylamino-1,3,4-thiadiazole IV-122-(p-methoxyphenylamino)-5-
(2-methoxyethylamino)-1,3,4-thiadiazole IV-132-(3-methylthiopropylamino)-5
-(2-methoxyethylamino)-1,3,4-thiadiazole TV-142,5-bis(methylamino)-1°3.4
-Oxadiazole IV-152,5-bis(nibruamino)-1°3.4
-Oxadiazole An example of a method for producing a diazole compound represented by the above general formula [rV] is given in JP-A-53-61334 specification m [
B.C., Journal of the American Chemical Society, (P.C.).

Quha, Journal or Ameri
can Chemical Society) ],
±5, p, 1036 (1928), and [Journal on Medical Chemistry, (J o
Urnal or Medical Chemistry
), vol, l5.

No. 3, p. 315 (1972), etc.

In order to add the compounds represented by the general formulas [I] to [IV] of the present invention to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material, the compounds represented by the general formulas [I] to [IV] of the present invention can be added directly into the hydrophilic colloid solution forming the photographic constituent layer. Dispersed or dissolved in one or a mixture of two or more suitable solvents such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, dimethyl formamide, dioxane, ethyl acetate, etc. before addition to the hydrophilic colloid solution. You may. Alternatively, after dissolving in one or a mixed solvent of two or more high boiling point organic solvents such as dioctyl phthalate and trioctyl phosphate, it may be emulsified and dispersed in a hydrophilic colloid solution. Furthermore, when the photographic constituent layer is a photosensitive silver halide emulsion layer, this compound can be emulsified and dispersed simultaneously with the coupler and then added to the coating solution.

The timing of adding the compounds represented by general formulas [11 to [■]] of the present invention to the coating solution is after the preparation of the photosensitive silver halide emulsion when this compound is added to the photosensitive silver halide emulsion layer. Any time is fine. When the photosensitive silver halide emulsion is a surface-part @ type emulsion that mainly forms an m-image on the grain surface, it may be prepared at any time after chemical ripening and optical sensitization. Further, when the photosensitive silver halide emulsion is an internal latent image type emulsion that mainly forms latent images inside the grains, it may be carried out at any time after the silver halide emulsion has been prepared and optically sensitized. Further, when the photographic constituent layer is a non-photosensitive layer, it may be added at any time before coating the non-photosensitive layer, but it is preferably added immediately before coating.

The compounds represented by formulas [I] to [IV] of the present invention can be added to the photographic constituent layers of the light-sensitive silver halide emulsion layer and/or the non-light-sensitive layer.

When added to a photosensitive silver halide emulsion layer, blue sensitivity,
It may be added to either of the green-sensitive and red-sensitive silver halide emulsion layers. In this case, it may be added to each of these layers, or even only to one layer.

When it is added to only one layer, it is preferably added to the precursor-containing layer of color development Inaba or its adjacent layer.

When the compounds represented by the general formulas [I] to [TV] of the present invention are added to the non-photosensitive layer, they may be added to any of the undercoat layer, intermediate layer, or retaining layer.

The addition m of the compounds represented by the general formulas [I] to [IV] of the present invention is in the range of 0.001 mol to 1 mol per mol of silver halide when added to the photosensitive silver halide emulsion layer. and is preferably in the range of o, oos to 0.5 mol. When the above compound is added to two or more photosensitive silver halide emulsion layers, the amount added is in the range of 0.001 mol to 1 mol, preferably o, oos mol to 0.5 mol.
It is in the molar range.

The silver halide grains used in the light-sensitive silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention preferably have an average grain size of 0.6 μm or less.

Although the lower limit of the average particle size is not particularly limited in the present invention, extremely small particles are not preferred since there is generally a close relationship between the average particle size and sensitivity.

Generally, silver halide grains of about 0.3 μm or more are used.

The average grain size here refers to the diameter of spherical silver halide grains, or the diameter when the projected image is converted to a circular image of the same area in the case of grains with shapes other than cubic or spherical. It is an average value, and when the individual particle size is "i" and the number is 01, 7 is defined by the following formula.

Note that the particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's "particle size analysis method" Δ.

S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122 or Chapter 2 of [Theory of the Photographic Process] by Mies and Ginimes, 3rd edition, Macmillan Publishing Co., Ltd. (1966). Are listed. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The silver halide grains used in the present invention with an average grain size of 0.6 μm or less can achieve the effects of the present invention regardless of whether the grain distribution is polydisperse or monodisperse, but monodisperse silver halide grains are more preferably It is.

Further, in these silver halide grains, any ratio of the (1oo) plane to the (111) plane can be used. or,
The particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. In the present invention, in particular,
Preferred are octahedral, tetradecahedral, and cubic particles with regular crystalline shapes, more preferred are cubic particles and/or cubic particles.
or tetradecahedral particles, more preferably JP-A No. 5
As measured by the X-ray diffraction analysis method described in No. 9-29243, = [Intensity of the diffraction line attributed to the (200) plane]/[Intensity of the diffraction line attributed to the (222) plane] When expressed, they are cubic grains and/or tetradecahedral silver halide grains satisfying 5≦, ≦s, and ooo.

The silver chlorobromide emulsion having monodisperse silver chlorobromide grains that is preferably used in the present invention can be produced using a known method, for example, the method described in JP-A-54-48521. can be manufactured by applying

The monodisperse silver halide grains referred to herein refer to those whose II (hereinafter referred to as coefficient of variation), which is obtained by dividing the standard deviation S (below) of the grain size distribution by the average grain size (hereinafter referred to as the coefficient of variation), is 0.20 or less. The value is 0.15 or less.

The silver halide grains having an average grain size of 0.6 μm or less used in the present invention may have any silver halide composition. Examples include silver chloride, silver chlorobromide, silver bromide, silver chloroiodobromide, and silver iodobromide.

Preferably, silver chlorobromide is used, more preferably silver chlorobromide containing 0 to 95 mol % of silver bromide.

Any crystal form may be used as the silver halide grains having an average grain size of 0.6 μm or less for use in the present invention.

For example, it may have a regular crystal shape, or it may have an irregular crystal shape such as a spherical or plate shape.

Further, the structure of the silver halide grains of the present invention may be uniform from the inside to the outside, or may have a layered structure consisting of different silver halide grains inside and outside.

Further, it may be of a type in which the latent image is mainly formed on the surface or a type in which the latent image is formed inside the particle.

The emulsion used in the present invention can be used during or after grain formation,
It may be further doped with platinum, palladium, iridium, rhodium, ruthenium, bismuth, cadmium or copper.

Furthermore, unnecessary soluble salts may be removed from the emulsion used in the present invention after grain formation, or they may be left as they are contained. In the case of removing the salts, any method such as the Nudel water washing method, the dialysis method, or the coagulation water washing method, which has been known for a long time, can be used.

Furthermore, the emulsions used in the present invention can be sensitized by chemical sensitization. Specifically, allylthiocarbamide, N
, N-diphenylthiourea, sodium thiosulfate, sulfur sensitizers such as cystine, selenium sensitizers such as tetramethylselenurea, noble metals such as gold compounds, palladium compounds, platinum compounds, ruthenium compounds, rhodium compounds, and iridium compounds. Sensitization can be achieved using a sensitizer or a combination of such sensitizers. Alternatively, reduction sensitization can be performed using a reducing agent such as hydrogen gas or stannous chloride.

The emulsions used in the present invention are prepared by adding a suitable sensitizing dye in an amount of 5 x 10-3 to 3 x 10-3 mol per mol of silver halide in order to impart photosensitivity to the desired wavelength range. It may be optically sensitized. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as sensitizing dyes used in green-sensitive emulsions, for example, U.S. Pat.
No. 8, No. 2,739,149, No. 2,945,763
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 505.979. In addition, examples of sensitizing dyes used in red-sensitive emulsions include, for example, U.S. Pat.
No. 2.442,710, No. 2.454.629
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2.776, No. 280, and the like. Furthermore, U.S. Patent No. 2,213,995, U.S. Pat.
No. 48, No. 2,519,001, West German Patent No. 929,0
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 80 can be advantageously used in green-sensitive emulsions or red-sensitive emulsions.

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

Representative examples are U.S. Pat. No. 2,688,545 and U.S. Pat.
No. 977.229, No. 3.397.060, No. 3
．． No. 522.052, No. 3.527,641, No. 3
, No. 617,293, No. 3,628,964, No. 3
．． 666, 480, 3.672.898, 3,
No. 679,428, No. 3,703,377, No. 3.7
No. 69.301, No. 3.8-14.609, No. 3.8
No. 37.862, No. 4.026.707, British Patent 1
, No. 344,281, No. 1.507.803, Japanese Patent Publication No. 43-4936, No. 53-12375, Japanese Unexamined Patent Publication No. 1973-1237.
-110618, No. 52-109925, etc.

Further, the silver halide color photographic light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or other purposes.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent Nos. 584,609 and 1,
No. 177.429, JP-A-48-85130, JP-A No. 49
-99620, 49-114420, 52
-108115, U.S. Patent No. 2,274,782, U.S. Patent No. 2.533.472, U.S. Patent No. 2,956,879, U.S. Patent No. 3
．． No. 148.187, No. 3,177.078, No. 3,
No. 247,127, No. 3,540,887, No. 3,5
No. 75.704, No. 3,653,905, No. 3,
No. 718,472, No. 4.071,312, No. 4,
No. 070,352.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives, such as antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure No. 17643. Agents, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used.

In the silver halide color photographic material used in the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, casein, etc. , cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a transparent support provided with a reflective layer or a reflective material, such as a glass plate. , polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2,761.791;
．． It is also possible to use a simultaneous coating method of two or more layers according to the method described in No. 941.898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily, but for example, in the case of a full-color photosensitive material for printing, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a green-sensitive emulsion layer, It is preferable to arrange the red-sensitive emulsion layer.

Furthermore, in the photosensitive material used in the present invention, it is optional to provide an intermediate layer of an appropriate thickness depending on the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer, an antihalation layer, etc. They can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may similarly be included.

The treatment method of the present invention can be used particularly effectively in the following four treatment steps.

(1) Color development → bleach fixing → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development → bleach fixing → water washing → stable (4) color development → bleach fixing → stable An alkaline activation bath (hereinafter referred to as an activator) is used instead of the color developing bath in 1) to (4), and other processing steps such as stopping, bleaching, fixing, bleaching, fixing, etc.
For water washing, stabilization, etc., methods known in the photographic industry can be used as they are, in an appropriate combination, or with some of them omitted, depending on the purpose.

The processing liquid in the aqunavator used in the present invention is basically an alkaline aqueous solution, and is an aqueous solution of inorganic in groups such as sodium hydroxide, potassium hydroxide, and sodium carbonate. These activators include color development accelerators such as benzyl alcohol, dimethylformamide, etc.
Preservatives such as hydroxylamine, triethanolamine, and free and paid antifoggants such as potassium bromide and 5-methylbenztriazole may also be included. However, for benzyl alcohol, as mentioned above in the Background of the Invention, 8 to 11 parts of the color developer is used.
vQ or less, preferably at all.

Furthermore, inorganic or organic salts can be included in order to provide the activator with a buffering effect and appropriate ionic strength.

The pH of the processing solution in the aqunavator may be alkaline, but I)H is preferably 9 or more in order to promptly develop the silver halide. The temperature of the activator varies depending on the type of coupler, the characteristics of the silver halide, etc., but is usually 15 to 50°C, preferably 20 to 40°C.

Furthermore, the washing with water in the treatment process refers to Japanese Patent Application Laid-Open No. 57-854.
This method includes the multistage countercurrent water washing method described in Publication No. 3 and the like.

The processing temperature in the method for processing silver halide photographic materials of the present invention may be within the range generally used in the development of silver halide photographic materials, and is preferably in the range of 28 DEG C. to 45 DEG C. The color developing agent contained in the color developer of the present invention is an aromatic primary amine compound, especially p-
Preferably, phenylenediamine-based ones include N,N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-p
-phenylenediamine hydrochloride, N,N-dimethyl-p-
Phenyldiamine hydrochloride, 2-amino-5-(N-ethyl-N-doacylamino)-toluene, N-ethyl-
N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β- and droxyethylaminoaniline, 4-amino-N-(2
-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-3-
Methyl-4-aminoaniline, N-ethyl-N-(β-
Examples include human oxyethyl)-3-methyl-4-aminoaniline. These color developing agents may be used alone or in combination of two or more.

Other than this 1. F, A, Na5on@Photograp
hicp processing chemistry
22 of (Foca! Press, 1966)
pp. 6-229, U.S. Pat. No. 2.193.013, 2.
592. '364, JP-A-48-64933, etc. may be used.

The color developing agent used in the color developer in the present invention is generally about 0.1q to about 30g per color developer 11.
, preferably from about 1 g to about 15 a per color developer.

The color developing solution used in the invention development step of the present invention includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, and tertiary sodium phosphate, sodium bromide, and potassium bromide. Development inhibitors such as methanol, ethanol, acetone, butanol, benzyl alcohol, phenoxybutanol, diethylene glycol, ethylene glycol,
Various organic solvents such as NlN-dimethylformamide, preservatives such as hydroxylamine and sodium sulfite, surface additives such as citrazic acid, polyethylene glycol, and polyvinylpyrrolidone, water-soluble optical brighteners such as diaminostilbene compounds, Various known additives such as heavy metal ion masking agents such as ethylenediaminetetraacetic acid and alkyliminodiacetic acid, and development accelerators can be included as necessary. However, as mentioned above, benzyl alcohol is used in an amount of 8 nj2 or less per liter of color developing solution, preferably in the absence of it at all.

The pH value of the color developer is usually greater than 7, most commonly from about 10 to about 13. Preferably from about 10,5
It is 12.

Regarding the temperature, the processing time of the color development process can be shortened as the temperature increases, but if the processing temperature is too high, problems such as increased fog and decreased stability of the processing solution will occur, so it is generally not recommended to set the temperature above 40°C. Undesirable.

The processing time in the color development step of the present invention may be 100 seconds or less, preferably between 90 and 45 seconds.

The bleaching and fixing treatments performed to leave the dye image of the present invention are carried out simultaneously from the viewpoint of rapid processing.

Bleach agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (IF), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, loaded salts of iron(I[) or cobalt(III), aminopolymers such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, etc. Complex salts of carboxylic acids or organic acids such as citric acid, tartaric acid, malic acid, etc.: persulfates, permanganates: nitrosophenols, etc. can be used.

Among the bleaching agents used in the bleach-fixing process of the present invention, metal complex salts of organic acids are particularly preferred.

A metal complex salt of an organic acid has the effect of oxidizing metallic silver produced by development and converting it into silver halide. Its structure is an organic acid such as aminopolycarboxylic acid, oxalic acid, or citric acid, which contains iron, cobalt, It is coordinated with metal ions such as copper. The most preferred organic acid used to form such a metal complex salt of an organic acid is, for example, an aminopolycarboxylic acid represented by the following general formula [■] or [■].

General formula [VI] HOCO-A+ -Z' -A2 C00H general formula [■] [In each of the above general formulas, A+, A2, A3, A4, A
5 and A6 are each a hydrocarbon group, 2' is a hydrocarbon group, an oxygen atom, a sulfur atom, or N-A? (A7 represents a hydrocarbon group or a lower aliphatic carboxylic acid). These aminopolycarbons may be alkali gold Km, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [VI] or [■] include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidethylenediamine-N-(β-hydroxyethyl)-
N,N,N'-Triacetic acid propylene diamine tetraacetic acid nitrilotriacetic acid cyclohexane diamine tetraacetic acid iminodiacetic acid methyliminodiacetic acid ethyl imino diacetic acid hydroxyethylimino diacetic acid propyliminodiacetic acid butyliminodiacetic acid dihydroxyethyl glycine ethyl ether diamine tetraacetic acid glycol ether diamine tetraacetic acid ethylene diamine Tetrabrobion Shun Phenylene diamine Tetraacetic acid Ethylenediamine Tetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediamine Tetraacetic acid tetrasodium diethylenetriamine Pentaacetic acid pentasodium salt Ethylenediamine-N-(β-hydroxyethyl)-
N,N,N'-triacetic acid sodium salt propylene diamine tetraacetic acid sodium salt nitriloacetic acid sodium salt cyclohexanediamine tetraacetic acid sodium salt Kinsho in the metal complex salt of an organic acid used in the present invention is a compound capable of coordinating with an organic acid. Examples of metals include chromium, manganese, iron, cobalt, nickel, copper, etc., and iron is particularly preferred in the present invention.

The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned ia and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, such as sodium iron (Ir) ethylenediaminetetraacetate, ethylenediaminetetraacetic acid Iron (I[) ammonium acetate.

Further, metal complex salts of two or more organic acids having different structures may be used in combination.

The specific amount used is preferably about 5 to 4001 J per 11 treatment liquids, particularly about 10 to 200 g per 111 treatment liquids.

The bleach-fix solution used in the present invention contains as a bleaching agent a metal complex salt of an R acid as described above (15ilI is an iron complex salt), and also contains thiosulfate, thiocyanate,
A liquid having a composition containing a silver halide fixing agent such as thioureas is applied. In addition, a bleach-fix solution consisting of a composition in which a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a halogen compound such as potassium bromide is added in large quantities. It is also possible to use a bleach-fixing solution having a composition as well as a special bleach-fixing solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide.

As the halogen compound, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can also be used.

Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Thiosulfates such as, potassium thiocyanate, sodium thiocyanate, thiocyanine 1m such as ammonium thiocyanate, thioureas, thioethers, etc., high concentration bromides,
Iodide is a typical example.

In addition, the bleach-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, as in the case of bleaching solution.
pH buffering agents consisting of various salts such as acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained.

In addition, hydroxylamine, hydrazine, sulfites, isomeric bisulfites, preservatives of aldehydes and bisulfite adducts of compounds, organic chelating agents such as aminopolycarboxylic acids, a type of stabilizer such as nitroalcohol nitrates, alkanols, etc. Other soluble agents such as amines, stain inhibitors such as organic amines, organic solvents such as methanol, dimethylsulformamide, dimethylsulfoxide, etc. can be appropriately contained.

In general, it is known that metal complex salts of organic acids, in neutral or alkaline regions, have a decreased oxidizing power and diffusivity due to alkaline hydrolysis reactions and diassimilation reactions, resulting in a significant decrease in silver source Shirahama. ing. Therefore, in order to increase the silver bleaching ability of a treatment solution using a metal complex salt of an organic acid,
It is possible to lower the pH of the processing solution and use it as an acidic solution, but
A decrease in pH promotes the reduction reaction of coloring dyes, particularly cyan dyes, by reduced products of metal complex salts of organic acids produced by silver bleaching, etc., resulting in leuco formation, which causes a serious problem in that dye images appear red.

In general, the decrease in pl-1 is due to the oxidation-reduction reaction with sulfite ions used as fixing agents and fixing agent preservatives in order to increase the oxidizing power of metal complex salts of organic acids in bleach-fix solutions. It is known that the reaction rate increases and the disproportionation reaction due to protons of thiosulfate ion, which is commonly used as a fixing agent, tends to occur, resulting in a decrease in the storage stability of the bleach-fix solution. For this reason, the bleach-fix solution is practically
It is used within the range of -16 to pH8.

The bleach-fixing temperature of the silver halide color photographic light-sensitive material of the present invention is 50°C or less, preferably 30 to 40°C.

Further, the bleach-fixing treatment time is 72 seconds or less, preferably 60 seconds or less.

Color development of the silver halide color photographic light-sensitive material of the present invention,
Bleach-fixing, further washing with water as necessary, stabilization,
The processing temperature of various processing steps such as drying is preferably 30° C. or higher from the viewpoint of rapid processing.

[Specific Effects of the Invention] When the silver halide color photographic light-sensitive material of the present invention is applied for printing, it has a high color density even when rapidly processed with a color developing solution containing extremely low or no benzyl alcohol concentration. However, even when the photosensitive material is stored, desensitization and fogging are reduced.

[Example 1] A silver halide emulsion layer was coated on a polyethylene laminated support so as to have the structure shown in Table 1 to prepare a single layer sample. Next, the single layer sample was heated at a temperature of 40°C and a humidity of 80°C.
% atmosphere for 24 hours to undergo a strength deterioration storage test, and those that were not subjected to this test were subjected to light modeling in the usual manner using a photosensitive needle (model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.). After exposure, it was processed as shown in Table 1 according to the following processing steps.

Processing solution composition (color developer [A1 composition) Benzyl alcohol 15% ethylene glycol 151g Potassium sulfite 2.0g Potassium bromide
0.7Q Thorium Chloride
0.2g potassium carbonate
30. OQ Hydroxylamine Sulfate 3.
0g polyphosphoric acid (TPPS) 2.59
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) i, og water Potassium oxide 2.0 (1) Add water to bring the total volume to 1 fl, and adjust the pH to 10.20.

(Color developer [B] composition) Ethylene glycol 5d Potassium sulfite 2.0g Potassium bromide
0.70 Sodium Chloride
0.2g potassium carbonate
50g hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS) 2
．． 5σ3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 8g Fluorescent brightener (4,4'-diaminostilbenzsulfone l!II conductor) 1. Oq
Potassium hydroxide (2.0 g) was added to bring the total volume to 11, and DHll was adjusted to 0.

(Color developing solution [C] composition) 5 benzyl alcohol per 1 i of the color developing solution [B]
- Contains (bleach-fix solution) Ethylenediaminetetraacetate ferric ammonium dihydrate 60Q Ethylenediaminetetraacetate M3 (1ammonium thiosulfate (70% solution) 100.Q Ammonium sulfite (40% solution) 27.5d carbonic acid Adjust to pl-17.1 with potassium or glacial acetic acid, and add water to bring the total volume to 111.

The concentration was measured using a densitometer (Model PD-+30, manufactured by Konishi Roku Photo Industry Co., Ltd.) on the sample treated as below the treatment temperature and treatment time, and after forced deterioration of the coated sample, The sensitivity reduction rate and minimum density increase rate of the exposed and processed samples were determined, and the results are shown in Table 1.

Mid-sensitivity reduction rate: A sample immediately after coating was subjected to color development. The rate of decrease in sensitivity of the sample after forced deterioration storage relative to the sensitivity of the sample at that time was expressed as follows.

* Minimum density increase rate: The minimum density of the sample after forced deterioration compared to the minimum density of the sample obtained by color development processing of the sample directly coated.
An increase of 1 degree is expressed as a percentage.

In Table-1 Values in parentheses are coating units g/12 DBP is dibutyl phthalate TCP is tricresyl phosphate The dielectric constants of high boiling point solvents are shown below.

As is clear from Table 1, in the case of yellow couplers, magenta couplers, and cyan couplers, in the rapid processing [8] and [C] without or with a small amount of benzyl alcohol, the samples of the present invention 6.7.10 to 16.19.23.
25.26 is comparative sample 2 to 5.8.9.18.20,2
Compared to 2.24, the maximum concentration is higher, and the decrease in sensitivity and increase in minimum concentration after the forced aging storage test are small, and the improvement is almost equivalent to that of comparison sample 1.17.21 subjected to normal processing [A]. I understand.

Example VA2 A silver halide color photographic material was prepared by sequentially coating the following eight layers on a corona discharge treated paper support whose both sides were treated with polyethylene resin (Comparative Sample 27).

Note that the addition m shown below indicates the amount per 1f unless otherwise specified.

Layer 1: Layer containing 1.0 g of gelatin.

Layer 2...1, 2. G gelatin, 0.4g (
Blue-sensitive silver chlorobromide emulsion (silver bromide composition 70 mol%: cubic crystal, average grain size 0.55 μm) of silver equivalent (same below), and
．． 88 (l) of the above-mentioned yellow coupler (Y-2) and oisg of 2,5-di-t-octylhydroquinone (referred to as HQ-1) were dissolved in 0.44 (l) of D
Layer containing BP or H-2.

Layer 3: Layer containing 0.7 g of gelatin.

Layer 4...1.25Q gelatin, 0.43(]
green-sensitive silver chlorobromide emulsion (silver bromide composition 70 mol %, cubic crystal, average grain size 0.41 μm), and 0.53 (J) with the above-exemplified magenta coupler (III-3) and o, ols
A layer containing 0.2 g of DBP or H-2 dissolved in g of HQ-1.

5...-1,28 (l of gelatin, and 0.
08g of HQ-1 and 0.5g of ultraviolet absorber (UV-1
layer containing 0,359 DBP or H-2 dissolved in ).

Layer 6...1.4 g of gelatin, 0.3117 red-sensitive silver chlorobromide emulsion (silver bromide composition 70 mol%, cubic crystal, average grain size 0.35 μm), 0.50 g A layer containing the above exemplary cyan coupler (C-5) and 0.182 DBP or H-2 in which 0.02 g of HQ-1 was dissolved.

III...1.0g of gelatin 1. And 0.
032111 HQ-1 and 0.2 g of ultraviolet absorber (U
Contains 0, 14Q DBP or To(-2) dissolved in V-1).

Layer 8: Layer containing 0.5 g of gelatin.

Ultraviolet absorber ('UV-1) 2,4-dichloro-6-hydroxy-
Sodium 8-triazine was added to Ji'f 11.3°5 and 8 at an amount of 0.017 (1) per gram of gelatin, respectively.

Color developing agent precursor CD using comparative sample 27 as the basic composition
-82,Oa, a compound represented by the general formula [■J to [■vJ] 10.04 (7) was added so as to have the composition shown in Table 2.

The samples prepared as described above were exposed, processed and tested in the same manner as in Example 1, and the results are shown in Table 2.

As is clear from Margin Table 2 below, samples 32 to 35 of the present invention had a higher maximum concentration than comparative samples 28 to 31 in the rapid treatment [B] without benzyl alcohol, and also after the forced deterioration storage test. The decrease in sensitivity and the increase in minimum density were small, and the improvement was almost equivalent to that of Comparative Sample 27 subjected to normal processing [A].

[Example-3] 3 in the color developer [B] used in Example-2 above
-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-3 instead of aniline sulfate
-Methyl-4-amino-N-N-ethyl-N-hydroxyedy-aniline sulfur Pi! I salt, 3-methyl-4-N
-ethyl-N-(2-methoxyethyl)-aniline p-
Samples 27 to 35 were tested in the same manner as in Example 2, except that the above color developing solutions [0] and [E] were used, and the results were almost the same as in Example 2.

Procedural amendment (method) heat May 21, 1986

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a coupler on a support, the silver halide color photographic light-sensitive material comprising: a precursor of a color developing agent; The following general formulas [I], [II],
It contains at least one compound selected from the compounds represented by [III] and [IV], and the coupler is dispersed in a high-boiling organic solvent having a dielectric constant of 6.0 or less. Silver halide color photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3 and R_4 each represent an alkyl group, and R_1 and R_2 and/or R_3 and R_4 are bonded together with A nitrogen-containing heterocycle may be formed.R_5 represents a halogen atom, an alkyl group, or an alkoxy group, and n_1 is 0 to 4.
represents an integer. If n_1 is an integer from 2 to 4, R_5
may be the same or different. ) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Good. R_8 represents a halogen atom, an alkyl group, or an alkoxy group, and n_2 represents an integer of 0 to 4. When n_2 is an integer of 2 to 4,
R_8 may be the same or different. ) General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a hydrogen atom or a hydrolyzable group, R_9 represents an aryl group, R_1_0, R_1_
1, R_1_2 and R_1_3 are each a hydrogen atom,
Represents an alkyl group or an aryl group. ) General formula [IV] (In the formula, A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom, and Y represents a sulfur atom or an oxygen atom.)