JPS62178241A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material which has a high color forming density even if the material for quickly processed with a color developing soln. contg. no benzyl alcohol by incorporating the precursor of a color developing agent and compd. having specific structure into the photosensitive material. CONSTITUTION:The precursor of the color developing agent and at least one compd. selected from the compds. expressed by formula I, formula II and formula II are incorporated into the photosensitive material. R7, R8 are an alkyl group, R9 in an alkyl group, -NHR'9, etc., R11 is an H atom, hydroxyl group, etc., R12. R'12, R''12 are an alkyl group, R13, R14 are an H group, -OCOR'' group (R', R'' are monovalent org. group), R13, R14 may jointly form a heterocyclic group. n=0-4, R15, R16, R17 denote an H atom, halogen atom, etc. The photosensitive material which decreases desensitization and generation of fogging even after preservation is thus obtd.

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 kinds of silver halide photographic materials that are selectively sensitized on a support to be sensitive to blue light, green light, and red light. 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 can be provided in a different arrangement from the above, and each emulsion layer can be formed into a photosensitive layer consisting of two layers sensitive to substantially the same wavelength range for each color light. It is also known to use transparent 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, cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indasilones or A cyanoacetyl magenta coupler and an acylacetamide or benzoylmethane yellow coupler 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. 970, No. 2,515,147, No. 2,49
No. 6,903, No. 4,038.075, No. 4.1
No. 19,462, British Patent No. 1,430,998, No. 1
, No. 455,413, JP-A-53-15831, No. 5
No. 5-62450, No. 55-62451, No. 55-6
No. 2452, No. 55-62453, No. 51-1242
No. 2, Special Publication No. 51-12422, No. 55-49728
The compounds described in the above issues have been studied, but most of these compounds have insufficient development accelerating effects, and even those compounds that exhibit sufficient development accelerating effects often generate fog. It had drawbacks and was not practical.

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, and No. 58-50532.

The publication discloses that 1-arylpyrazolidones are added to a silver octagenide color photographic light-sensitive material and processed within an extremely 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, for example in amounts commonly used in color paper processing (10 nI2/
When used at 15tR/ffi or above,
Because of its low water solubility, diethylene glycol or triethylene glycol is required as a solvent. However, from the viewpoint 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. In particular, if the amount of benzyl alcohol used is 8 vQ / l or less, the amount of the solvent used will be reduced. This has the advantage that it is no longer necessary, and 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 81Q/i
If the concentration is reduced to below, the color density will be significantly reduced and the various color development accelerators mentioned above (for example, U.S. Pat. No. 2.95
No. 0.970, No. 2,515,147, No. 2.4
No. 96.903, No. 2.304.925, No. 4.
0381075, British Patent No. 4,119,462, British Patent No. 1.430.998, British Patent No. 1,455,413, Japanese Patent Application Publication No. 53-15831, Japanese Patent Application Publication No. 55-62450, British Patent No. 5
No. 5-62451, No. 55-62452, No. 55-6
No. 2453, No. 58-50536, Special Publication No. 51-12
Even when compounds described in publications such as No. 422 and No. 55-49728 were used in combination, sufficient color density could not be obtained.

In particular, in rapid processing using a color developing solution with a benzyl alcohol content of 8111 or less (for example, rapid processing with a development time of about 1 minute at a processing temperature of 33°C), the photosensitive silver halide emulsion closest to the support is Layer development is 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, in addition to the processing temperature, a method of color development has been proposed by increasing the pH of the color developer by 11 degrees.
If H is 10.5 or more, the oxidation of the color developing agent may be significantly accelerated, or it may be inappropriate! Since there is no i-box solution, the color developing agent is susceptible to pH changes, which makes it difficult to obtain stable photographic performance and increases the dependence on processing time.

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 compatibility with 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 No. 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 the reaction product of a color developing agent and a metal complex, British Patent No. 803.783 Mei 1 describes a phthalimide compound of an aromatic primary amine color developing agent and phthalic acids, and US Pat. No. 4,060,
No. 418 and JP-A-53-135,628, No. 54
Publication No. 79,035 describes urethane compounds with aromatic primary amine color developing agents.

However, the above 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, and to prevent desensitization and fogging even when the photosensitive material is stored. It is an object of the present invention to provide a silver halide color photographic light-sensitive material in which less generation of .

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer containing a coupler on a support, wherein the silver halide photographic material contains a color developing agent. and the following general formulas [I], [
This is achieved by a silver halide color photographic light-sensitive material containing at least one compound selected from compounds represented by [1] and [111].

In the general formula [Eco-chest formula, R7 and R8 each represent an alkyl group. R9 is an alkyl group, -N, HR's group, -8R' 9
group (R'9 represents a monovalent organic group), or -〇〇R''9 group (R''s represents a hydrogen atom or a monovalent organic group -).

m does not represent an integer from 0 to 3.

General formula [I[] (wherein, R11 is a hydrogen atom, a hydroxyl group, an oxyradical group, -8OR'n group, -302R'++M(R'
++ represents an alkyl group or an aryl group. ), an alkyl group, a hydroxyalkyl group, an alkenyl group, an alkynyl group, a benzyl group, or a 100R″n group (R″++ represents a hydrogen atom or a monovalent m group). R
I2, R'12, and R''12 each represent an alkyl group. R+3 and R13 each represent a hydrogen atom or 10 CORM (represents an R''/i-valent organic group). Alternatively, R13 and R+4 may jointly form a heterocyclic group. n represents an integer from 0 to 4. ) General formula [■co (wherein, R15, R+s and R+7 may be the same or different, and each is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or (represents an alkynyl group) [Specific structure of the invention] The color developing agent precursor used in the present invention is a compound that generates a color developing agent under alkaline conditions, for example,
Examples include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex type precursors, phthalic acid imide derivative type precursors, phosphoric acid amide derivative type precursors, sugar amine reactant type precursors, and urethane type precursors. It will be done.

Precursors of these color developing agents may be used, for example, in U.S. Pat.
．． 342.599, 2,507,114, 2,695,234, 3.719.492, British Patent No. 803.783, JP-A-53-13
Publications No. 5628 and No. 54-79035, Japanese Unexamined Patent Publication No. 5
No. 9-81643, No. 58-200233, No. 58
-192031, 59-13239, 56-1
No. 0723, No. 58-9534, Research Disclosure Magazine No. 15, No. 159, No. 12,146, No. 1
3.924. Specifically, the following compounds may be mentioned.

0OH (CD-8) CH3 (CD-9) CH3:CD-11)
. Speed: CD-12) CD-15) (CD-19) CHa C 几 OCH3 2H5 zHs OCOCH2CL (CD-30).几OCOCHs OCOCH2C1 (CD-33) czH, CzHsNH2 The amount of these color developing agent precursors to be added varies depending on the type 4 of the photographic light-sensitive material, but in general the photosensitive silver halide 1 in the photographic light-sensitive material of the present invention. A range of between 0.1 and 5 mol, preferably between 0.5 and 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 present invention is
It consists of a single emulsion layer or multiple emulsion layers that are 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 alkyl M (especially (-butyl group)), and R2 is an aryl group (preferably phenyl group)
The alkyl group and aryl group represented by R7 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 (8) or (C
) are preferable, and of general formula (B), groups represented by general formula (B') are particularly preferable.

In the formula, zl represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula (C) 10 -R+1 In the formula, R11 represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General Formula (B') 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, RN represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferred.

In addition, Rts, R1616 and R17 are each a hydrogen atom,
Represents a halogen atom, alkyl group, alkenyl group, alkoxy group, aryl group, carboxy group, alkoxycarbonyl group, carbamyl group, sulfone group, sulfamyl group, alkylsulfonamide group, acylamido group, ureido group, or amino group, R15 and R113 are each a hydrogen atom, and R17 is preferably an alkoxycarbonyl group, an acylamido group, or an alkylsulfonamide group. Further, X represents a group having the same meaning as that represented by the general formula (A>), and is preferably the group represented by the general formula (B) or (C), or (8), and more preferably the group represented by the general formula (B). ' ) can be mentioned.

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.

(Y-1) (Y-2) (Y-3) SaH3 (Y-4) ('Y-5) r/.

(Y-6) ('1 (Y-7) ('1 (Y-8) (Y-9) (Y-10) I″l1 (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.
No. 77, 874, Japanese Patent Publication No. 45-40757, Japanese Patent Publication No. 4
7=No. 1031, No. 47-26133, 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.
356.258, 4,386,155, 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 [a] Ar [wherein Ar represents an aryl group, Ra1 represents a hydrogen atom or a substituent, and Ra2 represents a substituent. Y is a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent, and W is -NH-1-N HCO-(N
Atomic IL Hiraso O bonded to the carbon atom of the nucleus) or -N
l-I CON H-, and m is an integer of 1 or 2. ) Specific example of [a) m -4C1 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, The Za
The ring formed by may have a substituent.

X represents a hydrogen atom or a substituent that can be separated 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,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, sulfonyl group, carbamoyl group, sulfamoyl group, cyan group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group , sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

General formulas [a] and [aI] used in the present invention
The magenta coupler shown in, for example, US Pat.
No. 600.788, No. 3,061,432, No. 3
, 062,653, 3,127,269, 3.3111476, 3,152,896, 3,419,391, 3,519,429,
Same No. 3,555,318, Same No. 3.684.514, Same No. 3.888.68σ, Same No. 3,907,571
No. 3.928.044, No. 3.930.86
No. 1, No. 3,930.866, No. 3,933,5
00, etc., JP-A-49-29639,
No. 49-111631, No. 49-129538, No. 50-13041, No. 52-58922, No. 55-
No. 62454, No. 55-118034, No. 56-38
No. 043, No. 51-35858, No. 60-23855
British Patent No. 1.247,493, Belgian Patent No. 769.116, Belgian Patent No. 792.525, and West German Patent No. 2,156,111. , Special public school 4th year
No. 6-60479, JP-A-59-125732, JP-A No. 5
No. 9-228252, No. 59-162548, No. 59
-171956, 60-33552, 60-4
No. 3659, West German Patent No. 1,070,030, and US Patent 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.

In the formula, RlE does not represent an aryl group, cycloalkyl group or heterocyclic group. R2E represents an alkyl group or a phenyl group. R3E represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Z+E is a hydrogen atom,
Represents a halogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

In the formula, R4F represents an alkyl group (eg, methyl group, ethyl group, propyl group, 7tyl group, nonyl group, etc.). Rs.
F represents an alkyl group (eg, methyl group, ethyl group, etc.). Rs F represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.) or an alkyl group (eg, 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 coloring agent.

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

-I t C-11CsHtt(t) The couplers represented by the general formulas [E] and [F] of the present invention are described, for example, in JP-A-59-146050 and JP-A-1988-60.
-117249 and 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, No. 2,367.531, No. 2,369.929, No. 2,423,730, No. 2,474,293 ,
Same No. 2,476.008, Same No. 2,498, 466, Same No. 2,545,687, Same No. 2,728,660
No. 2,772,162, No. 2,895,82
No. 6, No. 2,976, 146, No. 3,002, 8
No. 36, No. 3,419,390, No. 3,446,
No. 622, No. 3,476.563, No. 3,137
, No. 316, No. 3.758.308, $ 3,
839,044, British Patent No. 478,991, British Patent No. 945□542, British Patent No. 1,084, 480, British Patent No. 1.377,233, British Patent No. 1,388,024 and British Patent No. 1. , 543,040, and JP-A No. 4
No. 7-37425, No. 50-10135, No. 50-2
No. 5228, No. 50-112038, No. 50-117
No. 422, No. 50-130441, No. 51-6551
No. 51-37647, No. 51-52828, No. 51-108J341, No. 53-109630, No. 54-48237, No. 54-66129, No. 5
Examples include those described in publications such as No. 4-131931 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 generally contain from 2 x 10-3 moles to 1 mole, preferably from ix i O-2 moles to 8 moles of silver per mole of silver in the emulsion layer.
It is used in the range of X 10'' moles.

In order to incorporate the magenta coupler yellow coupler and cyan coupler used in the present invention into the emulsion, for example, phthalate esters (diptylphthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, triphenyl phosphate, trioctyl phosphate, etc.) phosphate, etc.) or N,N-dialkyl-substituted amides (N
, N-diethyllaurinamide, etc.) and low-boiling organic solvents such as ethyl acetate, butyl acetate or butyl propionate, respectively, or optionally in a mixture of these solvents. After dissolving the couplers individually or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer, colloid mill, or ultrasonic disperser, and then halogenated. In addition to silver, silver halide emulsions can be prepared.

The high boiling point organic solvent used in the present invention is not particularly limited, but is preferably a compound having a dielectric constant of 6.0 or more. The upper limit is not particularly limited, but the dielectric constant is preferably 20 or less. Examples include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or more.

Note that the organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture may be 6.0 or more. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C. Examples of high-boiling organic solvents that can be used in combination in the present invention include dioctyl phthalate, dinonyl phthalate, trioctyl phosphate, and trinonyl phosphate, which have a dielectric constant of less than 6.0. The above-mentioned high boiling point organic solvent having a dielectric constant of 6.0 or more used in the present invention is preferably a dialkyl phthalate or phosphoric acid ester represented by the following general formula [M] or [N].

General Formula [M] In the formula, R5 and R6 each represent an alkyl group having 1 to 4 carbon atoms.

General Formula [N] In the formula, R7, Ra and R9 each represent an alkyl group or an aryl group having 1 to 4 carbon atoms (for example, a phenyl group).

Each group represented by R5, R6, R7, R8 and R9 above is
It may have a substituent.

Typical specific examples of the high boiling point organic solvent represented by the general formula [M] or [N] are listed below, but the present invention is not limited thereto.

The following margins (exemplary compounds) (M-1), (M-2) (M-31(
M-4) (M-5) (M-6) (M-7)
(M-8) (M-9) (N-1) (N-2n (N-
3) (N-4) (1'J-
5) l-61 The "high boiling point organic solvent" used in the present invention refers to a solvent with a boiling point of 175°C at normal pressure.
The above refers to a substantially water-insoluble organic solvent. Among such organic solvents, in addition to the organic solvents represented by the general formulas [M] and [N] of the present invention, examples of high-boiling organic solvents having a dielectric constant of 6.0 or more include diethyl malonate. , diethyl maleate, γ-butyrolactone, methyl benzoate, benzyl alcohol, 1-octatool, and the like.

These high boiling point organic solvents according to the present invention can also be used in combination with known low boiling point organic solvents such as ethyl acetate.

The high boiling point organic solvent according to the present invention is 0.01 mol to 10 mol, preferably 0.05 mol per mol of silver halide.
It can be used in a mole to 5 mole range.

As a method for incorporating the high boiling point organic solvent according to the present invention into the silver halide emulsion layer, for example, at least one kind of the high boiling point organic solvent, or at least one kind of the high boiling point organic solvent and a coupler, if necessary, a low boiling point Mixing using an organic solvent
After being dissolved, it can be mixed with an aqueous gelatin solution containing a surfactant, and then added to a silver halide emulsion that has been emulsified and dispersed using a high-speed rotating mixer, colloid mill, or ultrasonic dispersion vessel.

In the present invention, the alkyl group represented by R7 and R8 in the general formula [I] is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms and branched at the α-position. It is.

Particularly preferred for R7 and R8 is a monobutyl group or a t-pentyl group.

The alkyl group represented by R9 is linear or branched, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, nonyl group, dodecyl group,
Such as octadecyl group.

When this furkyl group has a substituent, these substituents include a halogen atom, a hydroxyl group, a nitro group, a cyan group, an aryl group (e.g., a phenyl group, a hydroxyphenyl group, a 3,5-di-1-butyl- 4-hydroxyphenyl group, 3,5-di-t-pentyl-4-hydroxyphenyl group, etc.), amino group (e.g. dimethylamino group,
diethylamino group, 1.3.5-triazinylamino group, etc.), alkyloxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), carbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, heptyl group) Alkylcarbamoyl groups such as carbamoyl groups, arylcarbamoyl groups such as phenylcarbamoyl groups, cycloalkylcarbamoyl groups such as cyclohexylcarbamoyl groups, etc.), isocyanurine groups, 1.3.5
- Heterocyclic groups such as triazinyl groups are mentioned. The amino group represented by R9 is, for example, an alkylamino group such as a dimethylamino group, a diethylamino group, or a methylethylamino group, an arylamino group such as a phenylamino group or a hydroxyphenylamino group, a cycloalkylamino group such as a cyclohexyl group, 1 , 3,5-triazinylamino group, isocyanuryl group, and other heterocyclic amino groups. R
The monovalent organic group represented by /9 and R″9 is, for example, an alkyl group (such as a methyl group, an ethyl group, a propyl group,
butyl group, amino group, decyl group, dodecyl group, hexadecyl group, octaacyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), cycloalkyl group (e.g. cyclohexyl group, etc.), heterocyclic group (e.g. 1.3 .5-triazinyl group, isocyanuryl group, etc.). When these organic groups have a substituent, the substituent may be, for example, a halogen atom (e.g. fluorine, chlorine, bromine, etc.)
, hydroxyl group, nitro group, cyan group, amyl alkyl group (e.g. methyl group, ethyl group, 1-propyl group, t-butyl group, t-amino group, etc.), aryl group (e.g. phenyl group, tolyl group, etc.) , alkenyl groups (e.g. allyl group, etc.), alkylcarbonyloxy groups (e.g. methylcarbonyloxy group, ethylcarbonyloxy group,
benzylcarbonyloxy group, etc.), arylcarbonyloxy group (eg, benzoyloxy group, etc.), and the like.

In the present invention, compounds represented by the general formula [I] are preferably compounds represented by the following general formula [IV].

General formula [IV] [wherein R25 and R26 each have 3 carbon atoms]
˜8 straight-chain or branched alkyl groups, especially °C -butyl group, [-pentyl group. R27 represents a divalent organic group. k represents an integer from 1 to 6. ] Examples of the monovalent organic group represented by R27 include methyl group, ethyl group, propyl group, butyl group, pentyl group,
Alkyl groups such as octyl group, hexadecyl group, methoxyethyl group, chloromethyl group, 1,2-dibromoethyl group, 2-chloroethyl group, benzyl group, phenethyl group, alkenyl groups such as allyl group, propenyl group, butenyl group,
polyunsaturated hydrocarbon groups such as ethylene, trimethylene, propylene, hexamethylene, 2-chlorotrimethylene,
Unsaturated hydrocarbon groups such as glyceryl, diglyceryl, pentaerythrityl, and dipentaerythrityl, alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, and cyclohexenyl groups, phenyl group, p-octylphenyl group, 2.
Ari, -, such as 4-dimethylphenyl group, 2.4-di[-butylphenyl group, 2.4-di-t-pentylphenyl group, p-chlorophenyl group, 2.4-dibromophenyl group, naphthyl group, etc. group, 1,2-11,3- or 1.
4-phenylene group, 3,5-dimethyl-1,4-phenylene group, 2-1-butyl-1,4-phenylene group, 2-
Examples include arylene groups such as chloro-1,4-phenylene group and naphthalene group, and 1,3.5-trisubstituted benzene group.

R27 further includes, in addition to the above groups, a divalent organic group bonded to any group among the above groups via a 10-1-S-1-8O2- group.

More preferably R27 is a 2,4-di[-butylphenyl group, 2,4-di-t-pentylphenyl group, p-octylphenyl group, p-dodecylphenyl group, 3,5-
di-t-butyl-4-hydroxyphenyl group, 3,5-
It is di-t-benzene-4-hydroxyphenyl group.

k is preferably an integer of 1 to 4.

Specific compounds represented by general formula [I] are listed below, but are not limited thereto.

Below margin U41-19ft) I-9 Knee 11 Knee 13 Knee 14 Knee 15 Knee 17 ■-18 Knee 19 C7H+s (sec) Knee 21 Knee 23 03Hy (i) ■-25 ■-26 ■-27 ■-28 4 Ms (t)
C4H9f t)■-33 ■-35 ■-36 C4H9(t,) C4H9ft)■-37 C4H9(t) Cs Hn (t)■-38 ■-39 ■-41 ■-42 C4H'+(t) Book In the invention, the alkyl group represented by R11 in general formula [n] has 1 to 12 carbon atoms, the alkenyl group or alkynyl group has 2 to 4 carbon atoms, and R
Preferred groups represented by 11 include a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a hydroxymethyl group, a benzyl group, etc.), an alkenyl group (for example, a vinyl group, an allyl group). , isopropenyl group, etc.), an alkynyl group (e.g., ethynyl group, propynyl group, etc.), or -CoR"11 group, and R"11 is, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group). , benzyl group, etc.), alkenyl group (e.g. vinyl group, allyl group, impropenyl group, etc.), alkynyl group (e.g. ethynyl group, propynyl group, etc.), aryl group (e.g. phenyl group, tolyl group, etc.)
, is.

The alkyl group represented by R12, R'12 and R"12 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group.

In R13 and R14, the monovalent organic group represented by R includes, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, dodecyl group, octadecyl group, etc.), alkenyl group (
(e.g. vinyl group, etc.), alkynyl group (e.g. ethynyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.)
, an alkylamino group (e.g., ethylamino group, etc.), an arylamino group (e.g., anirim 1, etc.).Heterocyclic groups formed jointly by R13 and Rn include, for example, etc. (R28 is a hydrogen atom, an alkyl group, cycloalkyl group, phenyl group), etc.

In the present invention, compounds represented by the general formula [n] are preferably represented by the following general formula [v].

General formula [V] R29 is an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, benzyl group, etc.), alkenyl group (e.g., vinyl group, allyl group, isopropenyl group, etc.), alkynyl group (e.g. ethynyl group, propynyl group, etc.), acyl group (e.g. polmyl group, acetyl group, etc.),
It represents a propionyl group, a butyryl group, an acryloyl group, a progoroyl group, a methacryloyl group, a crotonoyl group, etc.

More preferred groups for R29 are a methyl group, an ethyl group, a vinyl group, an allyl group, a propynyl group, a benzyl group, an acedel group, a propionyl group, an acryloyl group, a methacryloyl group, and a chloro].noyl group.

Specific compounds represented by the general formula [II] are listed below, but are not limited thereto.

Margin below H3 f-5 f-6 H3 ■-8 H3 ■ -10 CH3 ■-11 ■-12 ■-13 l-14 ■-15 ■-16 ■-17 II-19 II-20 CH.

・・・－・澾－・・0 0 CH3 CH.

°+1. -gu H (g) ≧ 2) Hi CH2CN CH2CH2 ρr/''! Sweet 71- ■ -21 ■ -22 ■ -24 ■ -25 ■ -26 ■ -27 ■ -28 In the above general formula [I [[], R15, R+6, R4
7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, or a hydroxyl group, respectively.

Examples of the halogen atom represented by R15, R+s, and R17 include a fluorine atom, a chlorine atom, a bromine atom, and the like, with a chlorine atom being particularly preferred.

an alkyl group represented by R+5, R+s and R17,
The alkoxy group preferably has 1 to 20 carbon atoms, and the alkenyl group preferably has 2 to 20 carbon atoms, and may be linear or branched.

Moreover, these alkyl groups, alkenyl groups, and alkoxy groups may further have a substituent. Examples of substituents include aryl, cyano, halogen atom, petero ring, cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, as well as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl. Those substituted via a carbonyl group, such as those substituted via a carbonyl group, and those substituted via a heteroatom (specifically, hydroxy, alkoxy, aryloxy, peterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido Substituents via the nitrogen atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
Examples include those substituted via a sulfur atom such as sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl.

Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a butyl group, a 5ec-butyl group, an n-butyl group,
n-amino group, 5ec-amino group, [-amyl group, α,
α-dimethylbenzyl group, octyloxycarbonylethyl group, methoxy group, ethoxy group, octyloxy group,
Examples include allyl group.

an aryl group represented by R+5, RI6 and R17,
As the aryloxy group, for example, a phenyl group and a phenyloxy group are particularly preferable, and they may have a substituent (eg, an alkyl group, an alkoxy group, etc.). in particular,
For example, phenyl group, 4-t-butylphenyl group, 2.
A 4-di-t-amylphenyl group is mentioned.

Among the groups represented by R16 and R17, a hydrogen atom,
Alkyl groups, alkoxy groups and aryl groups are preferred, and hydrogen atoms, alkyl groups and alkoxy groups are particularly preferred.

Among the groups represented by R15, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

Specific compounds represented by the general formula [1 [[] are listed below, but are not limited thereto.

r-1 H3 C4H9(t) し4H9(t,) C4H9(t) I-7 ■-8 1[-9 ■-10 ll-11 ■-12 ■-13 C4H9(see) ■-14 ■-16 (,: 12H +17 ■-17 Below margin The compounds represented by the general formulas [I], [■] and [I[[] of the present invention may be used alone or in combination, and their addition The amount is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the color developing agent precursor.
~200 mol%. The compounds represented by the general formulas [I], [II] and [1] are contained in at least one of the silver halide emulsion layer and the non-silver halide emulsion layer, but are preferably contained in the precursor of the color developing agent. The layer containing the body or its adjacent layer.

In addition, the same method as for adding the coupler can be used to add the compounds represented by the above general formulas [11 to [1] to the emulsion layer and/or non-emulsion layer of the present invention. for example,
Phthalate esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, triphenyl phosphate, trioctyl phosphate, etc.) or N,N-dialkyl substituted amides (
A high boiling point organic solvent such as N,N-diethyllaurinamide, etc.) and a low boiling point organic solvent such as ethyl acetate, butyl acetate or butyl propionate, respectively, or as necessary, a mixture of these solvents. General formula [I]
After dissolving at least one of the compounds represented by ~[111], mixing with an aqueous gelatin solution containing a surfactant, and then emulsifying and dispersing using a high-speed rotary mixer, colloid mill, or ultrasonic disperser, etc. , silver halide emulsions can be prepared in addition to silver halide.

At this time, the coupler used in the present invention may be added at the same time. In addition, in order to contain the precursor of the color developing agent and the compound represented by the general formulas [I] to [III'l of the present invention in the same layer, the precursor of the color developing agent may be mixed with water, methanol, ethanol, acetone, dimethyl An emulsified dispersion prepared by dissolving it in a suitable solvent such as formamide or using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., and applying the emulsion coating liquid to the above general formulas [I] to [11] It may be added simultaneously or separately with the emulsified dispersion containing the compound represented by.

Furthermore, in the present invention, at least one compound represented by the following general formulas [VI], [VI It is preferable that it contains.

RgR4 (wherein R+, R2, Ra and R4 are each an alkyl group which may have a substituent having 1 to 4 carbon atoms, R5
represents an alkyl group or an alkoxy group, and nl represents O or a positive integer from 1 to 4. ) In the general formula [, Vl], R+, R2, R3
Examples of the alkyl group represented by R4 include methyl group, ethyl group, butyl group, hydroxymethyl group, β
Examples of the aralkyl group represented by R1, R2, R3, and R4 include a -hydroxyethyl group and a β-methoxyethyl group, such as a tolyl group. R1 and R
Examples of the nitrogen-containing heterocyclic nucleus formed by R2, R3, and R4 include a pyrrolidine nucleus and a morpholine nucleus.

In the general formula [VI], among the substituents represented by R5, examples of the alkyl group include a methyl group, an ethyl group,
Examples of the alkoxy group include a hydroxymethyl group, a β-hydroxyethyl group, an ethoxymethyl group, and the like. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the halogen atom include a bromine atom and a chlorine atom.

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

Margin below 71-1 vl-2
Vl-3vI-4 H3CCH2CH20CH3 Shoulder-12 These compounds, except for some, are known (for example, described in JP-A-50-15554, JP-A-58-120248, etc.); It can be easily synthesized by a commercial person. For the synthesis of these compounds, e.g.
nt, [)essloch, Fassott,
JamesS.

Ruby, Sterner, Vittum
, Weissberoer: J.

Am, Chem, Soc, 73, 3100
(1951), 3ent, 3rown, Gl
esmaness, )(arnish; Photo
, Sci, Er+a, 8. 125 (1964)
etc. can be referred to.

General formula
7 may be connected to form a nitrogen-containing heterocycle. R8 is an alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms.
represents an alkoxy group or a halogen atom. R2 represents O or a positive integer from 1 to 4. ) In the general formula [VI], the alkyl groups represented by R6 and R7 include methyl group, ethyl group, butyl 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 and a sulfur atom. Examples of the nitrogen-containing heterocyclic nucleus include a pyrrolidine nucleus, a piperidine nucleus, a piperazine nucleus, a morpholine nucleus, and the like.

Examples of the alkyl group represented by R8 in the general formula [■] include methyl group, ethyl group, and hydroxymethyl group, and examples of the alkoxy group include methoxy group,
Examples of the halogen atom include an ethoxy group, and examples of the halogen atom include a bromine atom and a chlorine atom.

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

Margin below vll-I VII-2
■-3■-4 vn -5VII -6 0H0H i-7Vll-8 ■-15■-16 ■-17Vll -ts OH (JM
No. 2.483.374, No. 2.776, 31
No. 3, No. 3, 060.225, British Patent No. 928.
No. 671, Perichte der Deutschen Chemitsien Gesellschaft, Vol. 16, p. 724 (Ber
Chemistry
chen Ge5ellschart) Same magazine tube 34
Volume 2.125 pages, Chemisier Berichte Volume 92, No. 3
, 223 pages (Chew+1sche Bericht
e), Photographic Science and Engineering Vol. 12, p. 41 (Photoara
phicScience and E nineer
ina) and Journal on the Chemical Society, Vol. 1941, p. 182 (Journal o
It can be synthesized according to the method described in F the Chemical Society.

General formula [■] Formula 9 (wherein, X represents a hydrogen atom or an acetyl group, R9
represents an aryl group, Rlo, Ru, R12I
3 and R+3 each represent a hydrogen atom, an alkyl group or an aryl group. ) In the general formula [■], the acetyl group represented by X may have a substituent. Examples of the substituent include alkyl groups (methyl group, ethyl group, etc.).

X is preferably a hydrogen atom.

As the aryl group represented by Rs in the general formula [■],
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 (for example, methyl, ethyl, propyl, etc.), halogen atoms (chlorine, bromine, etc.), alkoxy groups (methoxy, ethoxy, etc.). group, etc.), a sulfonyl group, and an amide group (methylamide group, ethylamide group, etc.).

The alkyl group represented by Rtl, R+2 and R13 of the general formula [■] is preferably an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a 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 for RloIRll, R+2 and R13 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.), alkoxy groups (methoxy group, ethoxy group, etc.). groups, etc.) and hydroxyl groups.

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

Below margin CH3CH3 ■-7N publication-8 VI[l-19VI[l-20 VT[l-21v'0I-22 VI[1-23VIII-24 Hs vIII-25v111-26 vIlI-27V11I-28 ■-291-30 VTII-43TI[l-44 Ct vIII-45VIII-46 t vIII-47■-48 Compounds represented by the general formula [■] are commercially available, but US Pat. No. 2,688,024, Same second
．． It can be synthesized according to No. 704.762, JP-A-56-64339, and JP-A-57-211147.

General formula [IX] (In the formula, R14-N H- and -N H-R+s each represent a primary amino group, and Y represents a sulfur atom or an oxygen atom.) R represented in general formula [IX] 14-NH
- and R1s -N H- can contain various aliphatic or aromatic components and may be the same or different from each other.

The above-mentioned secondary ano groups can contain various aliphatic or aromatic components, and may be the same or different from each other. Preferably R+q and R+s are electron donating groups or groups containing an electron donating group. typical R
The group represented by 14 and R+s is an alkyl group containing 1 or 4 carbon atoms such as methyl, ethyl, or propyl (this alkyl group is unsubstituted or alkylthio having an alkyl having 1 or 2 carbon atoms, or aryl groups (preferably phenyl groups), alkoxy- or alkylthio-substituted aryls (the substituent alkyl contains 1 or 2 carbon atoms), and alkeni groups (preferably allyl groups)
It is.

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

ll-12,5-bis(methylamine)-1゜3.4-
Thiadiazole lX-22-methylamino-5-ethylamino-1,3
,4-thiadiazole lX-32,5-bis(ethylamino)-1゜3.4-
Thiadiazole rX-42,5-bis(n-butylamino), -1,3
,4-thiadiazole■-52-allylamino-5-methylamino-1,3,
4-thiadiazolerX-62-(2-ethoxyethylamino)-5-methylamino-1,3,4-thiadiazolerX-72,5-bis(phenylamino)-1,3,4
-thiadiazole lX-82,5-bis(2-methoxyethylamino)-
1,3,4-thiadiazolell-92-(2-ethoxyethylamino)-5”-(
2-methoxyethylamino)-1,3,4-thiadiazolerX-102,5-bis(2-ethoxyethylamino)
-1,3,4-Thiadiazole r
2-methoxyethylamino) -1,3,4-thiadiazole lX-132-(3-methylthiopropylamino')-
5-(2-methoxyethylamino)-1,3,4-thiadiazole lX-142,5-bis(methylamine)-1°3.4
-Oxadiazole lX-152,5-bis(ethylamino)-1°3.4
-Oxadiazole An example of the method for producing the diazole compound represented by the above general formula [rX] is described in JP-A No. 53-61334, P
, C. Guha, Journal or A.
mericanChemical 5ociety,
45, p. 1036 (1928), and J.
internal of medical hemist
ry, vol. 15.

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

In order to add the compound represented by the general formula rJ to [X] of the present invention to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material, it is necessary to add the compound represented by the general formula r■J to [X] directly into the hydrophilic colloid solution forming the photographic constituent layer. Dispersed or dissolved in one or a mixture of selected solvents such as methanol, ethanol, isobu-O-panol, acetone, methyl ethyl ketone, dimethyl formamide, dioxane, ethyl acetate, etc. to form a hydrophilic colloid solution. May be added. Alternatively, after dissolving in one or a mixed solvent of two or more high boiling point organic solvents such as dibutyl phthalate, dimethyl butarate, trilocresyl phosphate, trioctyl phosphate, etc., it is emulsified and dispersed in a hydrophilic colloid solution. It's okay. 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 the general formulas [VI] to [rX] of the present invention to the coating solution is as follows. It can be done at any time later. When the photosensitive silver halide emulsion is a surface latent image type emulsion that mainly forms a latent 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 the general formulas [VI] to [rX] 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 [VI] to [rX] of the present invention are added to the non-photosensitive layer, they may be added to any of the undercoat layer, intermediate layer, or protective layer.

The amount of the compound represented by the general formulas [VI] to CIX of the present invention, when added to a photosensitive silver halide emulsion layer, is from o, ooi mol per mol of silver halide.
It is in the range of 1 mol, 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
The range is 0.5 mol.

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 μl 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. As an average value, when the individual grain size is ri and the number is ni, r 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 JA.

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). The particle size can be measured using either the projected area of the particle or an approximation to the diameter.If the particle is of substantially uniform shape, the particle size distribution can be expressed as either the diameter or the projected area. This can be expressed quite accurately.

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 (100) 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, an octahedron having a regular crystal shape,
Dodecahedral and cubic particles are preferred, cubic particles and/or tetradecahedral particles are more preferred, and even more preferred as measured by the X1m diffraction analysis method described in JP-A-59-29243. −[(20
When expressed as [intensity of diffraction lines attributed to the (222) plane]/[intensity of diffraction lines attributed to the (222) plane], 5≦≦
These are cubic grains and/or tetradecahedral silver halide grains that satisfy s, 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 For example, it is produced by a method in which a potassium chlorobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. At this time, a highly monodisperse silver chlorobromide emulsion can be obtained by appropriately selecting the addition rate as a function of time, pAa, m degree, etc.

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 monodisperse silver halide grains referred to herein refer to those whose fill (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 r, is 0.20 or less, and preferably this 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.

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 known method such as Nudel water washing method, dialysis method, coagulation water washing method, etc. known from ancient times 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 an appropriate 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. SO5,979. 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. 9771229, No. 3.397.060, No. 3
, No. 522,052, No. 3.527,641, No.
No. 3,617,293, No. 3,628.964, No. 3,666.480, No. 3,672,898, No. 3
, No. 679,428, No. 3.703.377, No. 3,
No. 769,301, No. 3,814.609, If51
No. 3,1337.862, IA No. 4,026,707, British Patent No. 1,344,281, British Patent No. 1,507,80
No. 3, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Publication No. 110618/1982, Japanese Patent Publication No. 52-109925
It is stated in the number 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 various purposes such as preventing irradiation.

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 No. 584.609, British Patent No. 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.
247□127, 3,540,887, 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. Examples include proteins such as hydroxyethyl cellulose derivatives, cellulose derivatives such as 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. , cell 0-
Examples include polyester films such as suacetate, cellulose nitrate, and 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 by 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.

In addition, 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 → washing with a small amount of water → washing with water (3) color development → bleach-fixing → washing with water → stable (4) color development → bleach-fixing → stable Below the margins and above An alkaline activation bath (hereinafter referred to as activator) is used in place of the coloring image bath in (1) to (4), and other processing steps such as stopping, bleaching, fixing, bleaching, fixing,
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 treatment liquid in the aqunavator used in the present invention is basically an alkaline aqueous solution, and is an aqueous solution containing no ms groups such as sodium hydroxide, potassium hydroxide, and sodium carbonate. This activator includes benzyl alcohol,
Color development accelerators such as dimethylformamide, preservatives such as hydroxylamine, triethanolamine, and inorganic and organic antifoggants such as potassium bromide, 5-methylbenzotriazole, and the like may also be included. However, as mentioned above, benzyl alcohol is used in an amount of 8112 or less per 12 parts of the color developing solution, preferably in a state where it is completely absent.

Also an activator! Inorganic or organic salts can also be included to provide jar action and appropriate ionic strength.

The pl-1 of the processing solution in the aqunavator may be alkaline, but preferably pl-1 is 9 or more in order to promptly develop the silver halide. The temperature of the activator varies depending on the type of coupler, the type of cross-oxidizing agent, and even the characteristics of the silver halide.
The temperature is usually 15 to 50°C, preferably 20 to 40°C.

Roughly, the water washing in the above treatment process is described in 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-
Phenylenediamine-based ones are preferred, such as N,N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-p
-phenylenediamine hydrochloride, N,N-dimethyl-p-
Phenyldiamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-
N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N-(2
-methoxyethyl)-N-ethyl-3-methylaniline-D-toluenesulfonate, N,N-diethyl-3-
Methyl-4-aminoaniline, N-ethyl-N-(β-
Hydroxyethyl)-3-methyl-4-aminoaniline and the like can be mentioned. These color developing agents may be used alone or in combination of two or more.

In addition to this, F, A, Na5on's Photog
RAPHIC PROCESSING CHIAIIST
ry (Focal Press, 1966), pages 226-229, U.S. Patent No. 2,193,013, U.S. Pat. good.

The color developing agent used in the color developer in the present invention is generally about 0.19 to about 30 a for the color developer 1y.
concentration, preferably 1 g of color developer.

at a concentration of about 1 g to about 15 CI.

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,
N.

Various organic solvents such as N-dimethylformamide, preservatives such as hydroxylamine and sodium sulfite, development regulators such as citradinic acid, polyethylene glycol, and polyvinylpyrrolidone, water-soluble optical brighteners such as diaminostilbene compounds, and ethylene diamine. Various known additives such as heavy metal ion masking agents such as tetraacetic acid and alkyliminodiacetic acid, and development accelerators can be included as necessary.

However, benzyl alcohol is used as described above (less than 8 vfl per 12 color developing solutions, preferably completely absent).

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 higher the temperature, the shorter the processing time in the color development process, but if the processing temperature is too high, problems such as increased fog and decreased stability of the processing solution will occur, so it should generally be set at 40"C or higher. is not desirable.

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, organic complex salts of iron (Ill) or cobalt (I[), aminopolycarbonates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, etc. Acids or complex salts of PII such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, diphenols, and the like 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 tionic 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 [X] or [XI].

General formula [X] HOCO-A + -Z' -A 2- C00J-
I General Formula [XI] [In each of the above general formulas, A+, A2, A3, A4, A
5 and A6 each represent a hydrocarbon group, and 2' represents a hydrocarbon group, an oxygen atom, a sulfur atom, or >N-A7 (A/ is a hydrocarbon group or a lower aliphatic carboxylic acid).

] These aminopolycarbons may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula EX] or [XI] include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidethylenediamine-N-(β-hydrooxyethyl)-
N,N,N'-triacetic acid propylene diamine tetraacetic acid nitrilotriacetic acid cyclohexane diamine tetraacetic acid iminodiacetic acid methyliminodiacetic acid ethyl imino diacetic acid hydroxyethyliminodiacetic acid propyliminodiacetic acid butyliminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid glycol ether diamine tetraacetic acid EthylenediaminetetrapropionatePhenylenediaminetetraacetic acidEthylenediaminetetraacetic acid disodium saltEthylenediaminetetraacetic acidtetra(trimethylammonium) saltEthylenediaminetetraacetic acidtetrasodium saltDiethylenetriaminepentaacetic acidpentasodium saltEthylenediamine-N-(β-hydroxyethyl)-
N,N,N'-1-diacetic acid sodium salt propylene diamine tetraacetic acid sodium salt nitriloacetic acid sodium salt cyclohexanediamine tetraacetic acid sodium salt The metal in the metal complex salt of am used in the present invention is a coordination bond with an organic acid. Examples of metals that can be used 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 organic acid and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, such as ethylenediaminetetraacetic acid iron(I[) sodium, ethylenediaminetetraacetic acid Iron (II) ammonium tetraacetate.

Moreover, two or more types of 11m metal complex salts having different structures may be used in combination.

The specific amount used is preferably in the range of about 5 to 400Q per 12 liters of treatment liquid, particularly about 10 to 2009Q per 11L of treatment liquid.

Bleach-fixing solutions used in the present invention include those mentioned above! A solution containing a metal complex salt of an acid (for example, an iron complex salt) as a bleaching agent and a silver halide fixing agent such as a thiosulfate, a thiocyanate, or a thiourea is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of 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 composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used.

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-fix solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, thio@ Thiosulfates such as ammonium acids, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thioureas, thioethers, etc., high concentrations of bromides,
Iodide is a typical example.

The bleach-fix solution contains boric acid, borax, and
Sodium hydroxide, potassium hydroxide, sodium carbonate,
DH buffers consisting of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, 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, aldehydes and ketone compounds such as bisulfite III
! ! Preservatives for acid adducts, organic chelating agents such as aminopolycarboxylic acids or a type of stabilizer such as nitroalcohol nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, methanol, dimethylsulformamide, etc. , dimethyl sulfoxide, and other solvents may be contained as appropriate.

In general, in organic acid metal lead salts, in neutral or alkaline regions, the oxidizing power and diffusivity decrease due to alkaline hydrolysis reactions and duplexing reactions, resulting in a significant decrease in silver source white blade. Are known. 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 DH of the processing liquid and use it as an acidic liquid, 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 the bleach-fix solution, the decrease in pH increases the oxidizing power of the metal complex salt of organic acid, which reduces the rate of redox reaction with the fixing agent and sulfite ion used as a preservative for the fixing agent. It is known that the storage stability of the bleach-fix solution decreases due to an increase in the number of bleach-fixing solutions and a disproportionation reaction caused by protons of thioate ions commonly used as fixing agents. For this reason, the bleach-fix solution has a pH of ~1
) used in the H8 range.

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,
From the viewpoint of rapid processing, the temperature of various processing steps such as drying is preferably 30° C. or higher.

[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 single layer sample was prepared by coating a silver halide emulsion layer on a polyethylene laminated support so as to have the structure shown in Table 1. Next, the single layer sample was heated at a temperature of 40°C and a humidity of 80%.
The specimens that were subjected to a strength deterioration storage test by being exposed to an atmosphere of After that, it was treated as shown in Table 1 according to the following treatment steps.

Processing solution composition (color developer [A1 composition) Benzyl alcohol 151β ethylene glycol 151g Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0 (+hydroxylamine l1ffi acid f
fi 3.0g polyphosphoric acid (TPPS)
2.5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4,4'-diaminostilbenzsulfone 1121 conductor) i, og
Add 2.0 g of potassium hydroxide water to bring the total amount to 12, and adjust 1) Hlo to 20.

(Color developer [B] composition) Ethylene glycol 5nN potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
500 hydroxylamine sulfur 1ffi
3. oQ Polyline 11 (TPPS)
2.503-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 8g Optical brightener (4,4”-diaminostilbenzsulfonic acid derivative) 1.0 ( 1
Potassium hydroxide (2.0 g) was added to bring the total amount to 1.0 g and adjusted to 1) H11.0.

(Composition of invention developer [C]) 5 parts of benzyl alcohol per 12 parts of the color developer [8]
Contains 1g (activator treatment liquid [D]) Potassium carbonate 20 (J Potassium bromide 0.1g Add water to make 11, and adjust the pH to 11.0 with potassium hydroxide.

(Activator treatment liquid [E-co)] Add a development accelerator to the activator treatment liquid [C].
Contains 0.1g of 4 per i.

(Bleach-fix solution) 60g ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylenediaminetetraacetic acid 3g thio(ii!ammonium chloride (70% solution) 100d ammonium sulfite (40% solution) 27. pH 7 with hffi potassium carbonate or glacial acetic acid , 1 and add water to make a total volume of 1 tl.

The blue density of the sample treated as shown in the margin below was measured using a densitometer (Model PD-60, manufactured by Konishiroku Photo Industry Co., Ltd.), and the maximum density immediately after coating was compared with the maximum density after forced deterioration of the coated sample, followed by exposure and the above treatment. The sensitivity reduction rate and minimum density increase rate were determined, and the results are shown in Table 1.

*Sensitivity reduction rate: Forced deterioration of the sensitivity of the sample when the sample is subjected to color development immediately after coating **Minimum density increase rate of the sample after storage **Minimum density increase rate: After forced deterioration to the minimum density of the sample after color development is applied to the sample immediately after coating The increase in the minimum concentration of the sample is expressed as a percentage.

As is clear from Margin Table 1 below, in the rapid processing [B], [C], [D] and [E] with a small amount or no benzyl alcohol, samples 5 to 17 of the present invention have a maximum concentration compared to comparative samples 2 to 4. It can be seen that the concentration is high, 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 Comparative Sample 1 subjected to normal processing [A].

[Example-2] A sample having the configuration shown in Table-2 was prepared in the same manner as in Example-1, and
A test similar to Example-1 was conducted. However, exposure and density measurements were performed using red light. The results are shown in Table 2 and were similar to those in Example 1.

The following margin [Example 3] A silver halide color photographic light-sensitive 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 (comparison). Sample 38)
Note that the amounts added below are per 1f unless otherwise specified.

Layer 1: A layer containing 1.0 (l) of gelatin.

Layer 2...1.2g gelatin, 0.49 (
Blue-sensitive silver chlorobromide emulsion (silver bromide composition: 70 mol% dicubic crystals, average grain size: 0.55 μ■), and
．． The above-mentioned yellow coupler (Y-2) of 88Q and 0
．． 0,441 in which 2.5-di-t-octylhydroquinone (referred to as 1-IQ-1) of 015CI was dissolved;
A layer containing l.

Layer 3: A layer containing 0.7Q gelatin.

Layer 4...1.25Q gelatin, 0.43tJ
green-sensitive silver chlorobromide emulsion (silver bromide composition 70 mol %, cubic crystal, average grain size 0.41 μm), and 0.53 g of the above-mentioned magenta coupler (11-3) and o, otsa HQ. A layer containing 0,2σ DIR in which -1 is dissolved.

B5...1.28 (l of gelatin, and 0
．． oag's HQ-1 and 0.5g of ultraviolet absorber (UV
A layer containing 0.359 DBP obtained by WJ analysis of -1).

wa6...1.4g gelatin, 031g red-sensitive silver chlorobromide emulsion (silver bromide composition 70 mol%, cubic crystal,
A layer containing DBP of 0.IQ in which the above-mentioned cyan coupler (C-5) having an average particle size of 0.35 μm) and 0.50Q and HQ-1 of 0.029 are dissolved.

1i7-・・・1.0g gelatin, and 0.0
320 HQ-1 and 0.2g ultraviolet absorber (UV-1
>0,14(l) of DBP dissolved in the layer.

M8: Layer containing 0.5 g of gelatin.

Ultraviolet absorber (UV-1) In addition, as a hardening agent, 2,4-dichloro-o-6-hydroxy-
Sodium 8-triazine was added to Ill, 3.5 and 8 at a concentration of 0.0170 per gram of gelatin, respectively.

Color developing agent precursor CD using comparative sample 38 as the basic composition
-80.8g, auxiliary developer V I -10,03Q and compounds represented by formulas [I] to [II[] ■-3
40,2! II was added so as to have the composition shown in Table 3.

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 3.

As is clear from Margin Table 3 below, samples 42 to 47 of the present invention had a higher maximum concentration than comparative samples 39 to 41 in the rapid processing [B] without benzyl alcohol, and there was also a decrease in sensitivity after the forced deterioration storage test. The minimum concentration increase was small, and the improvement was almost equivalent to that of Comparative Sample 38 subjected to normal treatment [A].

[Example-4] When the yellow coupler of sample 43 of the present invention in Example-3 was replaced with exemplary couplers Y-10 and Y-14,
Or the magenta coupler is an example coupler rl-1, m-
4, a-5, m-11 When replacing m-16 or cyan coupler, example couplers C-6, C-7, C-10,
Even when C-11 was used instead, similar results to Sample 43 were obtained.

[Example-51 3 in the color developer [B] used in Example-3 above
-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-3 instead of aniline sulfate
-Methyl-4-amino-N-N-ethyl-N-hydroxyethyl-aniline sulfate and 3-methyl-4-N-ethyl-N-(2-methoxyethyl)-aniline p-toluenesulfonate, respectively. Color developers [F] and [G] were prepared with the same composition except that equimolar amounts were used.

Sample 43 except that the above color developing solutions [F] and [G] were used.
When tested in the same manner as above, almost the same results as Sample 43 were obtained.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (method) % formula % 2. Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the person making the amendment Patent applicant address Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-26-2 Name (1
27) Konishi Roku Photo Industry Co., Ltd. Director Keio Benko 4, Agent 102 Address Kudan-Kuchita Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 (Shipping date) April 1988 June 22nd, 6th, engraving of the entire text of the specification subject to amendment (no change in content) - ~ Mimi -

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; A silver halide color photographic material containing at least one compound selected from the following general formulas [I], [II] and [III]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_7 and R_8 each represent an alkyl group. R_9 is an alkyl group, -NHR'_9 group, -SR
'_9 group (R'_9 represents a monovalent organic group) or -COOR''_9 group (R''_9 represents a hydrogen atom or a monovalent organic group). m represents an integer from 0 to 3. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_1 is a hydrogen atom, hydroxyl group, oxy radical group, -SOR'_1_1 group, -SO_2R'
_1_1 group (R'_1_1 represents an alkyl group or an aryl group), an alkyl group, a hydroxyalkyl group,
Alkenyl group, alkynyl group, benzyl group or -CO
R″_1_1 group (R″_1_1 represents a hydrogen atom or a monovalent organic group). R_1_2, R'_1_
2, R″_1_2 each represents an alkyl group.R_
1_3 and R_1_4 are each a hydrogen atom or -
It represents an OCOR''' group (R''' represents a monovalent organic group). Alternatively, R_1_3 and R_1_4 may jointly form a heterocyclic group. n represents an integer from 0 to 4. ) General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. (Represents an aryl group, alkoxy group, aryloxy group or alkenyly group.)