JPS6327840A - Silver halide photographic sensitive material containing precursor of photographic useful group - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved sharpness of image and color reproducibility, and capable of reducing stain of the image after photographic processing by incorporating a combination of the precursor of a photographic useful group, and a compd. capable of releasing a reactive group which reveals the photographic effect by reacting with said precursor, to the titled material. CONSTITUTION:The titled material is mounted a photographic constituting layer contg. at least one of the silver halide emulsion layer on a substrate body. At least one layer of said photographic constituting layers contains the precursor of the photographic useful group and the compd. capable of releasing the reactive group (or a reactive reagent) by reacting with said precursor during the photographic treatment. Since, said precursor and compd. are chemically stable, unless contacting with the color developing agent, and said precursor and compd. have very small reactivity for the silver halide and various kinds of another additives contd. in the photosensitive material, the precursor and compd. are useful to improvements of shelf-life and photographic property, especially, desensitization and the generation of fog or stain of the photosensitive material.

Description

[Detailed Description of the Invention] CA Field of Application] The present invention relates to a photographic light-sensitive material, and in particular, a silver halide photographic light-sensitive material which has improved image sharpness and color reproducibility after photographic processing, and The present invention relates to a silver halide photographic light-sensitive material in which contamination of photographic processing solutions, especially developing solutions, is reduced.

[Background of the Invention] Conventionally, it is already known that photographic materials contain in advance a compound that releases a development inhibiting component in accordance with the image density during development. This compound generally undergoes a coupling reaction with the oxidation product of a color developing agent to release a development-inhibiting component, and representative examples include U.S. Pat. Nos. 3,148,062 and 3,227.
, No. 554, No. 3,701,783, No. 3,733゜201, etc., compounds that exhibit a development inhibiting effect on the active site of the coupler when released from the active site. Couplers are known in which a group is introduced to form a group.These couplers undergo a coupling reaction with the oxidation product of a color developing agent, and the coupler matrix forms a dye, while the free introduced group forms a development-inhibiting component. It is something to do.

Hereinafter, this type of coupler will be referred to as a DIR coupler. on the other hand,
U.S. Patent No. 3,632) No. 45, Specification No. 3.928.041, JP-A-49-77635, U.S. Pat.
No. 630, No. 50-36125, No. 50-15273
No. 51-6724 and No. 55-161237, in which a group is introduced into the active site of a certain compound that forms a compound exhibiting a development inhibiting effect when released from the active site. compounds are known. This is a compound that undergoes a coupling reaction with the oxidation product of a color developing agent to form a substantially colorless compound and release a development inhibiting component. Hereinafter, this type of compound will be referred to as DIR shopping.

Hereinafter, DIR couplers and DIR products will be collectively referred to as DIR compounds unless there is a particular need for distinction. These DIR compounds are generally used for the following purposes.

That is, the DIR compound is characterized in that it releases a development-inhibiting component corresponding to the density of the image during development, and the released development-inhibiting component affects the image in the photographic constituent layer when that layer is an emulsion layer. Since development is suppressed in accordance with the density, so-called intra-layer effects (intra-image effects) such as controlling image tone, making images finer, and improving image sharpness 1, etc.
When the development-suppressing component diffuses into other layers, for example, in color photographic materials, a so-called mask is used to suppress the development of other layers in accordance with the density of the image in the diffusion source layer. The main expected effects are the so-called inter-image effect, which is an improvement in color reproducibility caused by suppressing the development of other layers in the case of monochromatic exposure, etc. This is the reason.

However, none of these DIR compounds could satisfy all of the above effects. These D
Since IR compounds have a large development suppressing power and a low diffusivity of the compounds released by the coupling reaction, they mainly have the effect of improving graininess, but they do not have satisfactory effects on improving color reproducibility and sharpness. Therefore, in order to improve the interlayer effect, increasing the amount of the compound added will produce the glabellar effect and improve color reproducibility, but the desensitization will be large and it will still be impossible to obtain satisfactory results. There wasn't.

On the other hand, Japanese Patent Application Publication No. 55-135835, Japanese Patent Application No. 55-18
Mercapto-based DIR compounds having a xylophilic group in the coupling-off group described in each publication No. 8973 and Japanese Patent Application No. 1989-1
Mercaptooxadiazole DIR compounds described in Japanese Patent No. 70575 are known. This type of compound has a weaker development inhibitory power than a DIR compound that has a mercapto compound without a wood-philic group at the active site as a leaving group, has almost no desensitization, and has high diffusivity, so the interlayer effect is large. Even if the amount added is increased, desensitization does not occur, and the intralayer effect can be increased. However, if the diffusivity of the inhibitor is further increased when trying to emphasize the interlayer effect and sharpness, the inhibitor will essentially lose its effective suppressing power. Since there is a negative correlation between the suppressing power and the suppressing power, it is impossible to enhance the glabellar effect and sharpness by increasing the diffusivity of the suppressing agent because of its own limitations. Furthermore, when an inhibitor with increased diffusivity is used, the inhibitor diffuses and accumulates from the light-sensitive material into the processing solution during color development.
A defect arises in that the processing liquid exhibits a development inhibiting effect. As a solution, a method of limiting the amount of DIR compounds used,
Alternatively, there are methods of frequently replacing the color development processing solution with fresh ones, methods of installing a new fine grain silver halide layer, and IA described in JP-A-57-151944, etc.
Some method, such as a method using an inhibitor that is deactivated in the processing solution, must be taken, which is disadvantageous in terms of photographic performance and economically.

Furthermore, as an improved DIR coupler, JP-A-54-1
DIR couplers having a so-called timing group are disclosed in publications such as No. 45135 and JP-A No. 5E-114946. In these DIR couplers, the timing group releases the inhibitor in a protected form, making it possible for strong inhibitors to diffuse over long distances; however, after being released from the coupler, the timing group Because the time between the release of the inhibitor and the release of the inhibitor is relatively short,
A sufficient diffusion distance was not obtained, and it was difficult to say that a sufficient glabellar effect and sharpness were obtained.

The inventors of the present invention have completed the present invention as a result of various studies regarding the above-mentioned problems and defects in interlayer effects and sharpness in photographic light-sensitive materials containing photographically useful groups such as inhibitors. It is.

[Objective of the Invention] The first object of the present invention is to improve the sharpness and color reproducibility of images after photographic processing of silver halide photographic materials, and to produce silver halide materials with reduced staining after photographic processing. An object of the present invention is to provide photographic materials.

A second object of the present invention is to provide a silver halide color photographic material with improved color reproducibility.

A third object of the present invention is to provide a silver halide color photographic material with excellent color image sharpness.

Furthermore, a fourth object of the present invention is to provide a silver halide color photographic material in which contamination of photographic processing solutions, particularly color developing solutions, is reduced.

[Structure of the Invention] The above aspects of the present invention include a photographically useful group precursor and a reactive group (or This was achieved by including a novel combination with a compound that releases a reactive reagent). That is, the present invention provides a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, in which at least ll'jl of the photographic constituent layer is coated with a photographically useful group precursor and A silver halide photographic light-sensitive material characterized in that it contains a compound that releases a reactive group (or a reactive reagent) that reacts with the photographically useful group precursor to produce a photographically useful group during photographic processing. .

To describe the present invention in more detail, the photographically useful group precursor contained in the photographic constituent layer of the present invention is one in which a photographically useful group is formed by photographic processing, and specifically, the photographically useful group is formed by the following general formula [1 ].

General formula [I R, -X, -X2-R.

In the formula, R1 and R2 are R, -X, or R1-XI H or R after the bond between X 1X 2 is cleaved.
A substituent that produces 2-X or R2X2H, at least one of which acts as a photographically useful group, and is represented by R1 and R2,
May be the same or different* XI and x2 represent sulfur atoms which may be the same or different. Further, a compound that acts on the photographically useful group precursor to imagewise release a reactive group or a reactive reagent that causes the photographically active group to exhibit its photographic effect is specifically represented by the following general formula [n].

General formula [l! ] C0UP-(L) 11-1 nt In the formula, C0UP reacts with the oxidation product of the developing agent, and then -
(L) n-I n tel! ! ! Represents a component that can leave Int, L is a group that connects the coup and Int, and when n = 1, L represents a component that can leave Int after leaving the coup or at the same time as leaving the coup, After leaving Int from (L), the general formula [
(2) represents a reactive group (or reactive reagent) that acts on the photographically useful group precursor shown in [2] to develop its photographic effect.

As mentioned above, the object of the present invention is specifically achieved by a silver halide photographic light-sensitive material containing the compounds represented by the above general formula [I] and general formula [11]. Layers include, of course, silver halide-containing layers, developing agent and/or coupler-containing layers,
Subbing layer, intermediate layer, filter layer, antihalation layer,
It is clear that the term is used to include auxiliary layers such as back layers and protective layers. And in this case, the general formula [1
] and the combination of the two compounds represented by the general formula [11] may be arbitrarily determined depending on the purpose, and one compound may be used in combination with several of the other compound, and they may be placed in the same layer. They may be contained in separate layers, or they may be contained in either the emulsion layer or the intermediate layer, and they may be added after being mixed and emulsified and dispersed. The photographically useful group precursor represented by the general formula [1], which may be separately emulsified and dispersed and added in the form of a separate emulsion, binds the active site of the photographically useful group to X + X 2
It is a compound that is blocked by forming a bond so that it does not exhibit photographic properties in that form, and also has the general formula [Summer!
] In the compound represented by the formula, the X, -X, and bonds are cleaved by the reaction reagent fnt, which is generated imagewise from the compound, and a photographically useful group is generated, thereby exhibiting photographic action imagewise (Image Quiz). ).

Specific examples of photographically useful groups include development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, developers, fixers, silver halide solvents, silver complex forming agents, hardeners, Examples include tanning agents, toning agents, fogging agents, antifoggants, chemical or optical sensitizers, desensitizers, photographic dyes or their precursors, and couplers. Among these photographically useful groups, particularly preferred are development inhibitors, bleaching inhibitors, and fogging agents.

When the photographically useful group is a development inhibitor, typical examples include U.S. Pat.
No. 14,657, No. 3,615,508, No. 3,81
No. 7,291, No. 3,733,201 and British Patent 1
, 450, 479, and JP-A-57-93344, such as mercaptotetrazole, selnotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, and selenobenzimidazole. Particularly preferred development inhibitors in the present invention include the following examples.

General formula [1a-1] General formula [1a-2] General formula [Ia-3] In the above formula, G 1 % G 2 is JP-A-57-151
944, 60-218644, 60-221750
1, No. 60-233650, No. 1, No. 61-11743, etc., after leaking into the developing processing solution, the development is inhibited.
G1 may have such properties that the agent no longer exhibits development inhibiting properties in commercial terms, and G1 is a hydrogen atom, an alkyl group (for example, an ethyl group, an i-propyl group, a 2-chloroethyl group, a 2-
G2
is a hydrogen atom, a halogen atom, an alkyl group (e.g. methyl convex, ethyl group, 2-(phenoxycarbonyl)ethyl group, etc.) 4 (e.g. vinyl group, etc.), an aryl group (e.g. phenyl group, 4
- (phenoxycarbonyl) phenyl group, etc.), alkoxycarbonyl group, (e.g. ethoxycarbonyl group, -
Cox CH2CH2CN group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, 4-methoxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, benzyloxy group, etc.), aryloxy group (e.g., phenoxy group, naphthoxy group, etc.), hydroxy basis,
Alkylamino groups (e.g. dimethylamino group, cyclohexylamino group, etc.), anilino group (e.g. anilino group, 4-methoxycarbonylanilino group, etc.), acylamino group (e.g. benzamide group, hexaneamide group, etc.), amino group, sulfone Amide groups (e.g., methanesulfonamide group, paratoluenesulfonamide group), thioamide groups (e.g., butanethioamide group, benzenethiocarbonamide group, etc.), ureido groups (e.g., ureido group,
N-butylureido group, etc.), carbamoyl group (e.g. carbamoyl group, N-phenylcarbamoyl group, etc.),
Sulfamoyl groups (e.g. sulfamoyl group, N-phenylsulfamoyl group, etc.), alkylthio groups (e.g. methylthio group, octylthio group, etc.), acyloxy groups (e.g. acetyl group, benzoyl group, etc.), sulfonyl groups (e.g. butanesulfonyl group, pen (Zersulfonyl group, etc.), nitro group, and cyano group, and has the same meaning as the above G, and may be the same or different from other Gs present in the molecule), and v2 is oxygen atom, sulfur atom or -N- group (Gt has the meaning already explained), f represents 1 or 2 (if f is 2);
, the two substituents may be different from each other).

When the photographically useful group is a bleaching inhibitor, typical examples include U.S. Pat. Nos. 3,705,801 and 3.7.
15.20f1 and German Patent Application Publication No. 2, 4
There are compounds described in No. 05.279, etc., and the following examples can be cited as preferred bleaching inhibitors.

General formula [1b-1] General formula [Ib-2] General formula [rb-3] General formula [Ib-4] H In the formula, G is an alkyl group having 6 to 20 carbon atoms (e.g. octyl group, dodecyl group etc.).

When the photographically useful group is a group that substantially exhibits a fogging effect on the silver halide emulsion in a developing solution, such a fogging agent has conventionally been used as a fogging agent that acts reductively on silver halide grains and can initiate development. Compounds that form fog nuclei (e.g. hydrazine, hydrazone, hydrazide, hydroxamic acid, hydroxylamine, hydroquinone, catechol,
p-aminophenol, enediol and its tautomer, or a compound having a reducing group as a partial structure such as polyamine, aldehyde, acetyl, etc.) and fog nuclei that can initiate development by acting on silver halide grains. Compounds that form silver sulfide nuclei such as thiourea, thioamide,
Thiocarbonyl compounds such as thiocarbamate, thiohydantoin, and rhodanine, and compounds having partial structures of tautomers thereof, etc.) are known, but preferred are JP-A-59-157638 and JP-A-59-170.
840, No. 60-128446, etc., fogging agents incorporating a hydrophobic group of appropriate size or a group that moderates adsorption to silver halide grains are preferred.
More preferably, it is a compound that has the property of changing into a compound having substantially no fogging effect by the action of components in the developer or intramolecular reaction, as described in JP-A No. 61-51141.

In addition, the photographically useful group precursor represented by the general formula [I] is R
, -X+ - may be a photographically useful group, so R, -X, - are photographically useful groups and R2-X
, - may be a protective layer that does not exhibit a photographic effect, in which case R2 is an optionally substituted alkyl group (e.g. i
-propyl group, t-dodecyl group, methoxymethyl group, etc.) and optionally substituted aryl groups (e.g. 4-
t-butylphenyl group, 2-butoxy-4-t-octylphenyl group, etc.).

The group represented by C0UP in the general formula [II] is
Coupler residues (specifically yellow, magenta, cyan coupler residues), non-coloring coupler residues, black coloring coupler residues, hydroquinone, catechol, 0-aminophenol or ? -(L) has an aminophenol skeleton, undergoes a redox reaction with an oxidized developing agent, and subsequently undergoes alkaline hydrolysis. -Int group releasing group, when C0UP represents a yellow image-forming coupler residue, e.g., U.S. Pat.
, No. 407.210, No. 2.1175.057, No. 3
, 048° No. 194, No. 3,265,506, No. 3,
No. 447,928 FarbkupplaraineL
Itaraturubarsicht'Agfa Mi
tteilung (Band II) 112-11
6 (1961), benzoylacetanilide type, pivaloylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type, benzothiazoli Yellow coupler residues such as those of the acetate type, benzoxacylylacetate type, and imidazolylacetate type may be used.

When C0UP represents a magenta image-forming coupler residue, for example, U.S. Pat.
No. 3.703, No. 2,311.0112, No. 2.6G
o, No. 788, No. 2.908,573, No. 3,062
, No. 653, No. 3,152,896, No. 3,519.
429 Special Publication No. 47-27411, Japanese Patent Publication No. 60-98
434, 60-55343, patent application No. 60-70197
, 60-70198 and the above ^gfa Mitt
ailung (Band II) 126-156
(1961) etc., various magenta coupler residues such as pyrazolone pyrazoloazole (pyrazolotriazole, pyrazoloimidazole, pyrazolopyrazole, pyrazolotetrazole, etc.) and indacylon magenta coupler residues are used. Can be used.

When C0UP represents a cyan image-forming coupler residue, for example, U.S. Pat.
．． No. 730, No. 2.474.293, No. 2,772.
No. 162, No. 2,895,826, No. 3,002.1
No. 136, No. 3,034,892, No. 3,041,2
No. 36, No. 4,333,999, JP-A-56-993
No. 41, No. 57-155538, No. 57-2045'
No. 45, No. 58-118643, No. 58-1879
No. 28, No. 58-189154, No. 5B-21374
No. 8, No. 59-31953 and the above ^gfa old t
teilung (Band II) pages 156-175 (1
Naphtholic or phenolic coupler residues such as those described in 961) can be used.

In addition to these coupler residues, West German Patent Publication No. 2,644.
The black dye-forming couplers described in No. 914 may also be used.

On the other hand, when coup represents a coupler residue (non-color forming coupler residue) which reacts with the oxidized form of a color developing agent such as a cyclic carbonyl compound but does not form a color forming dye, with respect to these compounds, For example, US Patent 3,
No. 832,345, No. 3,912゜513, No. 3,9
No. 28,041, No. 3,958,993, No. 3.96
No. 1.959, No. 4,204,867, and British Patent No. 861.138.

General formula [! The linking group represented by L in [2]] is a group that adjusts the coupling rate or the diffusivity of the group connected to L, and is preferably a group described in JP-A No. 52-90932.
The atomic group represented by R 0CH- (e.g. -OCH, -, etc.) described in No. 53-29717, the intramolecular group after being released from the coupler described in JP-A-54-145135. An atomic group that releases a compound with photographic activity through a nucleophilic substitution reaction (for example, as described in Japanese Patent Publication Nos. 56-114946, 57-154234, 57-188035, 58-98728, etc.) After being released from the coupler, the atomic group releases a compound with useful photographic activity by electron transfer along the conjugated system (e.g., etc.) and the atomic group described in JP-A No. 60-7429 (
For example, O may or may not be used in the present invention depending on the purpose.
Further, the reactive group or the reactive reagent represented by Int in the general formula [I+], after C0UP or L is separated, becomes
X, any group may be used as long as it is a group that can cleave a bond, preferably a cyano group, a straight or branched chain, or a cyclic optionally substituted alkylthio group;
Represents an alkoxy group and an alkylamino group, an optionally substituted arylthio group, an aryloxy group and anilino group, an optionally substituted heterocyclic thio group and a heterocyclic oxy group, a mercapto group, a halogen atom, an SCN group, etc. .

The reasons why photographic performance is improved by using the photographically useful group precursor and the compound that releases the reactive group (or reactive reagent) of the present invention will be described below.

(1) R+-X +-X z-R2 (hereinafter the two points are A)
) and C0UP-(L)n-Int (hereinafter referred to as B) are added to the same layer, In
If t is made diffusive, the concentration distribution of the photographically useful group will occur in accordance with the concentration distribution of Int, and the sharpness based on the edge effect will be improved. In general, sharpness can be improved even when diffusive DIR is used, but since there is a negative correlation between the diffusivity of the inhibitor and the suppressing power, it is necessary to It is necessary to provide the inhibitor with a certain diffusion distance, and this causes disadvantages such as the need to use a large amount of DIR because the suppressing power decreases. On the other hand, in the case of the present invention, Int is −
It acts as a cleavage agent for the XI X2 bond, and is not expected to have any photographic effect. Therefore, any diffusible material can be selected, so it has a great effect of improving sharpness.

(2) When A and B are added to separate layers, if the Int generated from B is made diffusive, the addition of A can be done in accordance with the information of the layer to which B is added (for example, the image exposure amount). The degree of photographic effect of the applied layer can be varied. For example, in a color photographic light-sensitive material using a DIR compound, if an attempt is made to increase the interaction effect from the first layer to the N2 layer, the first layer will naturally also be affected by the suppressing effect, so it is optional to increase the interaction effect from the first layer to the N2 layer. It was not possible to emphasize interlayer effects.

On the other hand, in the present invention, for example, the first layer contains diffusible Int.
If B, which releases B, is added to the second layer, and A, which generates a non-diffusible photographically useful group, is added to the second layer, only the second N can exhibit photographic action without affecting the first layer. Can be done. In this way, in the present invention, it is possible to freely apply the interaction effect from any layer to a specific layer, which increases the degree of freedom in designing the photosensitive material, and allows for color photographs with excellent color reproducibility. This is advantageous in making photosensitive materials.

(3) Several types of A (AIA2...) and several types of B
When (B, B, ...) are used in combination,
For example, if 81 is added to the first layer, A1 is added to the second layer, and A2 is added to the third layer, if Int generated from B1 is diffusive, information from the first layer is transmitted to the second and third layers. However, the concentration of Int is lower in the third layer than in the second layer. However, if the photographic effect is made stronger than that of the photographically useful group generated from A2, it is possible to obtain a photographic effect comparable to or greater than that of the third layer.

The photographically useful groups derived from A and A2 can also be selected so that each exhibits a different type of photographic action.

Furthermore, when B1, A, and A2 are added in the same layer, for example, if A is a development accelerator and A2 is a precursor that produces a development inhibitor, by changing the diffusivity of each, various colors can be produced. You can control the shape of snowmaking.

(4) When B, which releases diffusible fnt, and A, which produces a non-diffusible photographically useful group, are used in combination, the present invention basically provides Int as explained in (1) and (2). Due to the diffusivity of , color reproduction and sharpness can be improved. This does not matter whether the photographically useful group generated from A is diffusible or non-diffusible.
In particular, if the photographically useful group generated from A is non-diffusible, Int is the only non-diffusible group in this system.

Therefore, even if this Int leaks out from the sensitive material into the processing solution, the problem of contamination of the processing solution will not arise because Int, which basically has no photographic effect, is selected.

(5) R+-X 1-X 2-R1, R, X, and R2
When X2 exhibits different photographic effects, the photographic effects exhibited by R, X, and R2 may be of the same type or different types depending on the purpose. In some cases, it is possible to lower gamma without causing 1lfi feeling by adjusting the degree of diffusivity and photographic strength of both.

General formula [11 and - general formula [Summer!] used in the present invention are shown below. ] Specific examples of the compounds shown are shown below, but the present invention is not limited only to these compounds.

(Margin below) Compound i of general formula [I] l CaHo (1) C4HO(t)4 H9 A-11 A-12 C2H.

-2O -23HH A-28 A-29 Examples of compounds with general formula [+1] rt H song lJ +13 Cσ GfL B-10 ft. teeth 0 ■ A C.O.

B-21 B-22 The compound represented by the general formula [11] can be synthesized by the method introduced in "Organic Sulfur Chemistry - Synthesis Reactions Volume 1" edited by Shigeru Otoki, Kagaku Doujin pages 95-105. Further, the compound represented by the general formula [n] can be synthesized according to the synthesis examples described in the patent specifications and the like regarding the DIR compounds mentioned above.

Specific synthesis examples of the compounds of the present invention are shown below.

Synthesis Example 1 Synthesis of Illustrative Synthesis A-211 8.91 g of 1-phenyl-5-mercaptotetrazole was mixed with benzene 5
The solution was suspended to 0 cc, and 6.75 g of sulfuryl chloride was added dropwise while cooling with water. Stir once at room temperature! This gives a yellow solution. To this, 9.11 g of t-
Dodecyl mercaptan was added dropwise and stirring was continued at room temperature. After completion of the reaction, the mixture was washed with water, and the organic layer was dried with ri over anhydrous magnesium sulfur. Magnesium sulfate was filtered off, the filtrate was concentrated under reduced pressure, and the resulting residue was separated and purified by silica gel chromatography using ethyl acetate-hexane as a developing solvent to obtain a yellow candy-like compound A-28.

Synthesis Example 2 Synthesis of Exemplified Compound B-9 -9 JZ (I) (o) The above compound (I'I 3.Og and mercaptoethanol 0.38g 1tDMF 20 an) was dissolved in this solution under N hot water. Bromine 0.25 + D of aj!
MF (5+nIL) solution was added dropwise. After stirring at room temperature for 6 hours, the mixture was drained and the crystals were collected by filtration and washed with water. After extraction with ethyl acetate and drying over anhydrous magnesium sulfate, the magnesium sulfate was filtered off, and the filtrate was dried under reduced pressure. The residue was recrystallized with a mixed solvent of ethyl acetate and hexane to obtain 1.7 g of crystals. (Melting point 84-85°C) Compounds represented by the general formulas [1] and [I+] (
When applying the compound of the present invention (hereinafter referred to as the compound of the present invention) to a color photographic light-sensitive material, it is preferable to use it in combination with an ordinary photographic coupler (hereinafter referred to as the main coupler). 1xlO- for 1 mole
' to 1 mol is preferable, more preferably I X 10
-' to 0.2 mol. Moreover, the compound of the present invention is DIR
It may be used in combination with other compounds.

When the compound of the present invention is applied to materials other than coupler one-type color light-sensitive materials, the amount added is 5X per mole of silver halide.
1G-' to 1X10-' moles are preferred, and more preferably 1X10-' to 5 X 10-2 moles.

When the compounds of the present invention are synthesized in a hydrophilic colloid solution, they are kept dispersed in a hydrophilic colloid mill and can be used as is. ! #If it is in a separated state, it is dissolved in a hydrophilic organic solvent such as methyl alkaol, ethyl alcohol, or acetone, and added to and dispersed in the hydrophilic colloid solution. Other methods of dispersion include:
A method using latex dispersion or other polymers, or a method of dispersing the compound of the present invention in a hydrophilic colloid solution using, for example, a tri-cresyl phosphate or dibutyl phthalate solution used in oil-protected photosensitive materials. can be used. When dispersing these oil phases in an aqueous phase, commonly known anionic, nonionic, cationic, and other surfactants may be used. Hydrophilic colloids that can be widely used include gelatin, gelatin derivatives known as photographic binders, gelatin graft polymers, various cellulose conductors, polyvinyl alcohol partial oxides, sodium alginate, and poly-N-vinylpyrrolidone. Can be done.

Various photographic antioxidants or stabilizers can also be added to these emulsions.

More specifically, the method of incorporating the compound of the present invention into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention is as follows: When the compound of the present invention is alkali-soluble, it is added as an alkaline solution. If it is oil-soluble, it may be added, for example, U.S. Pat. No. 2,322,027, U.S. Pat. Same No. 2゜304.9
It is preferable to dissolve the compound of the present invention in a high-boiling point solvent, optionally in combination with a low-boiling point solvent, according to the methods described in No. 40, disperse it on fine particles, and add it to the halogen emulsion. At this time, other hydroquinone derivatives, if necessary,
There is no problem even if an ultraviolet absorber, an anti-fading agent, etc. are used in combination, and two or more compounds of the present invention can be used in combination.

Further, in the present invention, to describe in detail a preferred method of adding the compounds of the present invention to a silver halide emulsion, one or more fffi compounds of the present invention are added as necessary to other main couplers, hydroquinone derivatives, fading agents, etc. In addition to inhibitors and ultraviolet absorbers, organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tricresyl phosphate, triphenyl phosphate, Di-isooctyl azelate, di-n-butyl sebacate, tri-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl High boiling point solvents such as phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2.5-di-5ec-amylphenylbutyl ether, monophenyl-di-0-lylorophenyl phosphate or fluoroparaffin, and/or methyl acetate, Ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate,
Dissolved in low boiling point solvents such as nitromethane carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethyl formamide, dioxane, methyl ethyl ketone, and anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquis. The mixture is mixed with an aqueous solution containing a nonionic blush active agent such as oleic acid ester and sorbitan monolauric acid ester and/or a hydrophilic binder such as gelatin, and emulsified and dispersed using a high-speed rotary mixer, colloid mill, or ultrasonic dispersion device. Added to silver oxide emulsion.

In addition, the above-mentioned latex dispersion method and its effects are disclosed in JP-A-49-74538, JP-A-51-59943, and JP-A-54.
-32552 Specification Publication and Research Disclosure 1
No. 1485, 0, pp. 77-79, August 976.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, n-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)) acrylamide, 2-acrylamide-2
- Many homopolymers, copolymers and terpolymers such as methylpropanesulfonic acid and the like.

The compound of the present invention is contained in at least one of the constituent layers provided on the support of a silver halide photographic light-sensitive material, such as a silver halide emulsion layer, a medium-sensitive layer, a protective layer, and a subbing layer. It is. Although it depends on the type of the compound, it is generally preferable to include it in the silver halide emulsion layer or a layer adjacent thereto.

In addition, the general formula [! When the compound represented by I] is contained in a red-sensitive silver halide emulsion layer, Coup is preferably a cyan coupler residue, and when it is contained in a green-sensitive silver halide emulsion layer, coup is a magenta coupler residue. , when contained in a blue-sensitive silver halide emulsion layer, C0up is preferably a yellow coupler residue, and when coup is a colorless coupler residue,
It can be contained in any color-sensitive silver halide emulsion layer. Furthermore, the compounds represented by the general formulas CI] and [1■] can be used in the same layer, or in different layers (for example, layers with different sensitivities of the same color-sensitive layer or layers with different color sensitivities, etc.). ), or two or more types of compounds may be combined with each other.The compounds of the present invention incorporated into the photosensitive material according to the present invention are:
As long as they do not come into contact with color developing agents, they are chemically stable and have extremely low reactivity with silver halide and other various additives in light-sensitive materials, so they have a significant impact on the storage stability and photographic properties of light-sensitive materials. This can be useful in improving the appearance, fogging, staining, etc.

Silver halide compositions preferably used in the present invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Additionally, a mixture of these may be used, and silver iodobromide is particularly preferred.

Further, the crystals of these silver halide grains may be normal crystals, twin crystals, or other crystals, and have [1,O,O] planes and [1,1
, 1] Any ratio can be used for the plane.

Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. These silver halides may be of a type that forms a latent image primarily on the surface. In addition, tabular silver halide grains (JP-A No. 58-11393-4, Japanese Patent Application No. 59-1)
70070) can also be used.

Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

For example, when growing silver halide grains, p) 1. It is preferable to control pAg, etc., and to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in, for example, JP-A No. 54-48521.

Preferably, the silver halide grains used in the present invention are prepared as described above. A composition containing the silver halide grains is herein referred to as a silver halide emulsion.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these They act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a sensitizer).

The silver halide emulsion used in the present invention is chemically ripened by adding a sulfur-containing compound, and before and during this chemical ripening,
Alternatively, after aging, at least one hydroxytetrazaindene and at least one nitrogen-containing heterocyclic compound having a mercapto group may be added.

The silver halide used in the present invention is prepared by adding an appropriate sensitizing dye in moles of 5XIO-' to 3X10-' per mole 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 in combinations of 1 fffi or 221 or more. Examples of sensitizing dyes advantageously used in the present invention include the following: can be mentioned.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231,458, US Pat. , No. 2,519,001,
Same No. 2,912.329, Same No. 3,556,959, Same No. 3,672,897, Same No. 3,694,217
No. 4,025,349 No. 4,046,572, British Patent No. 1,242,588, Special Publication No. 14-14
Examples include those described in No. 030, No. 52-24844, and the like. Further, as a sensitizing dye used in a green-sensitive silver halide emulsion, for example, US Pat.
No. 39,201, No. 2,072,908, No. 2,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 739.149, No. 2,945,763, British Patent No. 505,979, and the like. Furthermore, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 378, No. 2.442,710, No. 2,454
．． Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 629 and No. 2,776.280.

Furthermore, U.S. Patent Nos. 2,213.995 and 2,49
No. 3.748, No. 2.519,001, West German Patent 9
Cyanine dyes such as those described in No. 29,080, etc.
Merocyanine dyes or complex cyanine dyes can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optically sensitized in a desired wavelength range by the spectral enhancement pA method using a cyanine or merocyanine dye or a combination thereof, if necessary.

Representative examples of particularly preferred spectral sensitization methods include Japanese Patent Publication No. 4936/1983, which concerns the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine;
No. 43-22884, No. 45-18433, No. 47
-37443, 48-28293, 49-62
No. 09, No. 53-12375, JP-A No. 52-2391
No. 1, No. 52-51932, No. 54-80118,
Examples include the methods described in No. 58-153926, No. 59-116646, and No. 116647.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-1
No. 1114, No. 47-25379, No. 48-3840
No. 6, No. 48-38407, No. 54-34535,
No. 55-1569, JP-A No. 50-33220, No. 5
No. 0-38526, No. 51-107127, No. 51-
No. 115820, No. 51-135528, No. 52-1
No. 04916, No. 52-104917, and the like. In addition, benzoxazolocarbocyanine (oxa・
For example, Japanese Patent Publications No. 44-32753, Japanese Patent Publication No. 46-11627, and Japanese Patent Application Laid-Open No. 57-1483 are related to combinations of carbocyanine) and other carbocyanines, and Japanese Patent Publication No. 4B-384 is related to merocyanine.
No. 08, No. 48-41204, No. 50-40662, JP-A-56-25728, 5a-t.

No. 753, No. 58-91445, No. 59-11664
No. 5, No. 50-33828, and the like.

Furthermore, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 49-6207 using gelatin, dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye can be advantageously used. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or
It is used by dissolving it in a hydrophilic organic solvent such as a fluorinated alcohol described in No. 40659. The silver halide emulsion according to the present invention may be added at any time such as at the start of chemical ripening, during ripening, or at the end of ripening. Each layer can contain a primary coupler, a compound that reacts with the oxidized form of the color developing agent to form a dye. As the main couplers that can be used in the present invention, yellow couplers, magenta couplers and cyan couplers can be used without any particular limitations. These main couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing coupler or the like in combination with these main couplers. The yellow couplers include open chain ketomethylene compounds, active point -〇-aryl substituted couplers called so-called two-equivalent type couplers, active point -〇-acyl substituted couplers, active point hydantoin compound substituted couplers, and active point urazole compound substituted couplers. Couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -0-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Specific examples of such vine yellow couplers used include U.S. Pat.
No. 5,057, 3.2 [i5.506, 3.40]
No. 8,194, No. 3,551,155, No. 3.582
, No. 322, No. 3,725,072, No. 3,891.
445, West German Patent No. 1,547,868, West German Patent Application No. 2゜219.917, West German Patent Application No. 2,261,361, West German Patent No. 2,414,006, British Patent No. 1,425,0
No. 20, JP 51-107133, JP 47-2
No. 6133, No. 48-73147, No. 51-1026
No. 36, No. 50-6341, No. 50-123342, No. 50-130442, No. 51-21827, No. 50-87650, No. 52-82424, No. 52-
Examples include those described in No. 115219 and No. 58-95346.

Examples of the magenta coupler used in the present invention include pyrazolone, pyrazolotriazole, pyrazolone, raimidazole, and indasilone compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Pat. Nos. 2,800,788 and 2,983.
．． No. 6011, No. 3゜082.653, No. 3,127
, No. 269, No. 3,311,476, No. 3,419,
No. 391, No. 3,519.429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,50
No. 6, No. 3,834゜908, No. 3,891,445
No. 1,810.464, West German Patent Application (O
L S ) No. 2,408,665, 2°417.9
No. 45, No. 2,418,959, No. 2,424,46
No. 7, Special Publication No. 40-6031, Japanese Patent Publication No. 51-2082
No. 6, No. 52-58922, No. 49-129538, No. 49-74027, No. 50-159336, No. 52-42121, No. 49-74028, No. 50-
No. 60233, No. 51-26541, No. 53-551
22, Japanese Patent Application No. 55-110943, and the like.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like yellow couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2.
, No. 434,272, No. 2.474,293, No. 2,
．． 521, '908, '908, '2,895,826, '3,034,892, '3,311.476, '3
, 458,315, 3,476.563, 3,
No. 583,971, No. 3,591.3H, No. 3,76
No. 7.411, No. 3,772,002, No. 3.933
, No. 494, No. 4.004,929, West German patent application (
OL S) No. 2,414,830, No. 2,454,
No. 329, JP-A-48-59838, JP-A No. 51-260
No. 34, No. 4B-5055, No. 51-146827, No. 52-69624, No. 52-90932, No. 5
Examples include those described in Japanese Patent Publication No. 8-95346 and Japanese Patent Publication No. 49-11572. Non-diffusible DIR compounds, colored magenta or cyan couplers are contained in the silver halide emulsion layer of the present invention and other photographic constituent layers. Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, which may be used in combination with couplers such as , polymer couplers, and diffusible DIR compounds, the present applicant's patent application No. 50-1
For the polymer couplers, reference can be made to the description in Japanese Patent Application No. 172151/1983 filed by the present applicant.

For the method of adding the main coupler that can be used in the present invention into the photographic constituent layer of the present invention, reference can be made to the method of adding the compound of the present invention, and the amount added is not limited, but
It is preferably txto-'' to 5 moles per mole of silver, more preferably 1X10-'' to 5X10-' moles.

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

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydrophilic colloids used to prepare the emulsion. Any of these may include derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch conductors, 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 of the present invention include baryta paper, polyethylene-coated paper, polypropylene paper, transparent supports with a reflective layer or with a reflector, such as glass plates, cellulose acetate,
Examples include polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc. Further, ordinary transparent supports may also be used, and these supports are appropriately selected depending on the intended use of the photosensitive material. .

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, U.S. Patent No. 2,76
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1,791 and No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined.For example, in the case of a full-color photographic light-sensitive material, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer are sequentially applied from the support side. The arrangement of blue-sensitive silver halide emulsion layers is preferred, and each of these light-sensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective HUWJ layer, and an antihalation layer 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 be included.

Although the amount of silver (silver deposition amount) in the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not limited,
0.3 to 1 g/l in the entire photosensitive silver halide emulsion layer
2, that is, in order to obtain excellent image quality, the amount of silver is preferably 1 g 7 m'' or less,
On the other hand, in order to obtain a high maximum density and a high sensitivity, it is preferable that the amount of silver is 04g7m'' or more.

As a method for processing the photographic material of the present invention, for example, a color developing bath containing a color developing agent can be used. In addition, various other methods including bath processing, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, and a developing method using a viscous processing liquid, are also available. Processing schemes can be used.

There are no particular limitations on the method of processing the photographic material of the present invention, and any processing method can be applied.

For example, typical methods include a method in which after color development, a bleach runner treatment is performed, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are performed separately after color development, followed by further washing if necessary. and/or a method of stabilizing; or a method of prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, supplementary color development , stopping, bleaching, fixing, washing, and stabilizing in this order. After applying halogenation bleach to the developed silver produced by color development,
Any method may be used for processing, such as a development method in which color development is carried out again to increase the amount of produced dye.

The color developing solution that may be used for processing the light-sensitive material of the present invention contains a color developing agent and preferably has a pH of 8 or more;
More preferably, it is an alkaline aqueous solution having a pH of 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop exposed silver halide. Precursors that form chemical compounds may also be added.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-dimethylaniline, N-ethyl-N-β-(β-(β-methoxyethoxy)ethoxy)ethyl-3-methyl-4-aminoaniline, N-ethyl-N -β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Furthermore, for example, JP-A-48-64932, JP-A-50
No. 131526, No. 51-95849 and Bent et al.'s Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951
The one described in 2010) is also cited as a representative example.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used, and the amount used is 0. It is used in a range from .0002 mol/1 to 0.7 mol/7 ft. Furthermore, two or more compounds may be used in appropriate combination depending on the purpose. For example 3-
Methyl-4-amino-N,N-diethylaniline and 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-
Combinations such as hydroxyethyl aline can be used in any combination depending on the purpose. The color developing solution used in the present invention further includes various commonly added components such as alkalis such as sodium hydroxide and sodium carbonate. agents, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides,
Benzyl alcohol, water softeners, thickeners, development accelerators, and the like can also be optionally included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc. Bleaching during the bleaching process Bleaching at night or bleaching theorem (Bleaching agents used at night are generally known to be those prepared by coordinating metal ions such as iron, cobalt, copper, etc. with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. The following are representative examples of the above aminopolycarboxylic acids.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidtetylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleach solution is used together with the above bleaching agents. It may contain various additives, and when a bleach-fix solution is used in the bleaching process,
A solution containing a silver halide fixing agent in addition to the bleaching agent is applied. In addition, the bleach-fix solution may further contain a halogen compound such as potassium bromide, and may also contain various other additives, such as pH buffers, antifoaming agents, etc. agent, surfactant, preservative,
A chelating agent, a stabilizer, an organic solvent, etc. may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
From the viewpoint of rapid processing, the processing temperature of the bleaching theorem (or bleaching, fixing) and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably 30° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 5B-105145, 58-1
Stabilization treatment as an alternative to washing may be performed as shown in Japanese Patent Application No. 34634 and No. 58-113631, Japanese Patent Application No. 58-2709 and No. 59-89288, and the like.

Example-1 1-Hydroxy-N-(4
1006 g of -(2,4-di-tert-acylphenoxy)butyl]-2-naphthamide was dissolved in 1 mf of tricresyl phosphate and 30 ml of ethyl acetate, and this was dissolved in Alkanol B (alkylnalthalene sulfonate, manufactured by DuPont) (7 )10% water soluble? r! 120III
It was mixed with 200 mjl of IL Oyohi 5% gelatin aqueous solution and emulsified and dispersed in a colloid mill to obtain an emulsion. This dispersion was added to 1 kg of red-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide).
A 2% aqueous solution of 1,2-bis(vinylsulfonyl)ethane 40111JZ was added as a hardening agent, and the coating was dried. (Coating night view 12 mg/100 cm', coupler mol/Ag mol = 0.1) The silver halide color photographic light-sensitive material thus obtained is designated as sample No. 1O1.

For this control sample No. 101, compounds of the present invention shown in Table 1 or the following DIR coupler (W-t
) in the same amount (0.2 mol% relative to Ag) 1! A
In addition, samples NoI O2 to NoI O7 were prepared.

DIR coupler (W-t) IJ Each of these samples was subjected to wedge exposure using an intensity scale sensitometer, and then subjected to color development according to the following processing steps to obtain the results shown in Table 1.

[Processing process] (38℃) Processing time Color development
Bleach for 3 minutes and 15 seconds Wash with water for 1 minute and 30 seconds Set for 3 minutes and 15 seconds
Arrive: Wash for 6 minutes and 30 seconds
Stable bath for 3 minutes and 15 seconds
The composition of the treatment liquid used in each treatment step for 1 minute and 30 seconds was as follows.

[Color developer composition] [Bleaching solution composition [Running solution composition] [Stabilizing composition] Table 1 In Table 1, samples No. 106 and 107 of the present invention
As is clear from the general formula [I] and general formula [11]
2f! The DIR effect was obtained using the compound j in combination, and moreover, the sample No. A-2
It can be seen that photographic performance is not substantially affected when 8, A-30, and B-11 are used alone.

Example 2 Samples No. 201 to No. 205 were prepared by adding the compounds of the present invention as shown in Table 2 or the following DIR couplers to the control sample N0IOI of Example-1.

Each of these samples was exposed to light in the same manner as shown in Example-1,
After the development process, the sharpness of the cyan image is checked using the conventional MT method.
F (10 trees/mm, 30 trees/mm) was used for evaluation. The results are shown in Table 2.

The structural formula of the DIR coupler used is as follows.

DIR coupler (W-2) 0 ■ DIR coupler (W-3) H The combined samples (No. 204, No. 205) are ordinary non-diffusive DIR (W-1) or diffusive DIR using diffusive suppression. (W-2), diffusivity D using timing group
It can be seen that the image shows superior sharpness compared to IR.

Example 3 A basic sample was prepared by performing multilayer coating on a triacetate base in the following order.

(1) As a yellow coupler, 2-(2,2-dimethylpropionyl)-2-N-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triacylidine-4-
yl)-2°-chloro-5′-(α-dodecyloxycarbonyl-ethoxycarbonyl)acetanilide 1.8
g/m2. Blue-sensitive silver iodobromide emulsion layer containing 2.4 g/+'' of gelatin and 1.6 g/m'' of silver halide.

(2) A medium-sensitive gelatin layer containing 0.5 g/m2 of gelatin and 0.1 g/m'' of 2.5-cm cutylhydroquinone.

(3) As a cyan coupler, l-hydroxy-N-[
4-(2,4-di-amylphenoxy)butyl-2-naphthamide 0.47g/m", gelatin 2.4g
/m2. Red-sensitive silver iodobromide emulsion layer containing 1.6 g/m2 of silver halide.

(4) Protective layer consisting of gelatin 0.8 g/m'.

Among the constituent layers of the ffi layer-coated light-sensitive material, the comparative DIR coupler (W-4) and a compound represented by the general formula [II] are added to the third layer containing the cyan coupler, and the first layer containing the yellow coupler contains the compound represented by the general formula [II]. The compounds represented by [I] were added as shown in the table below to prepare samples Nos. 301 to 305.

DIR coupler (W-4) u Each sample was divided into two parts, one sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with blue light. te38
C. for 2 minutes, bleached and fixed, and then washed with water.

[Color developer composition The pH, which is adjusted to 11 by adding water, is 11.0.

For each sample, the gamma value was determined from the characteristic curve of the yellow dye obtained by color development, and the gamma (γ3) due to blue exposure was measured by the gamma (1w) due to white exposure, and the values are shown in Table 3 below. (Left below) Table 3 Comparative sample No. 301 and inventive sample No. 304'
Comparative sample No. 302 and sample Na30 of the present invention
5, it can be seen that the sample of the present invention has large γ and I/γ1 values of the yellow dye characteristic curve. That is, it is shown that when the compound of the present invention is used, a larger interlayer effect (interimage effect) can be obtained than when the conventional DIR coupler is used. Furthermore, unlike the case using conventional DIR, sample No. 304.305 was used in the present invention.
Now, without changing the gamma of the cyan image characteristic curve,
It can be seen that a glabellar effect is occurring. That is, it can be seen that the present invention is a system that can produce a glabellar effect from one layer to any other layer, and has a large degree of freedom.

Example 4 In the following examples, the amount added in the silver halide photographic material is per 1 m2 unless otherwise specified.
In addition, silver halide and colloidal silver are shown in terms of silver.

Sample No. 401, which is a comparative example of a multilayer color photographic element, was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample No.4Q1 (Ratio: ¥1) First layer: Antihalation layer (l(C-1) Gelatin layer containing black colloidal silver.

2nd layer: Intermediate layer (■) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

37th'! l; Low sensitivity red-sensitive silver halide emulsion layer (RL
-1) Average particle size (r) 0.30 ttm, AgI 6
It consists of 8gBrl including MoIkk.

Monodisperse emulsion (emulsion I)...silver coating amount t, ag/m2 i! ! Sensitive pigment! ...il! 6 Xl0-' moles of sensitizing dye l per mole!
... 1 mole of silver. OXl0-'Morsian coupler (C-1)... 0.06 mol per mol of chairman Colored cyan coupler ((:C-1)... Silver 1
0.003 mol DIR compound per mole (D-1) 0.0015 mol DIR compound per 1 mol silver (D-2) 0.002 mol per mol silver 4 layers; high-sensitivity red-sensitive silver halide emulsion layer (RH-1)
Average particle size (r) 0.5 uts, Agl 7.0
Monodispersed emulsion (emulsion 11) consisting of A4Br1 containing mol%...silver coating amount 1.3g/
m' Sensitizing dye■... 3xlO-'mol sensitizing dye per 1 mole of silver! l... 1.0 per mole of silver. OXl0-'Morsian coupler (C-1)... 0.02 mol per mol of silver Color cyan coupler (CC-1)... o, -oots mol per mol of silver DIR compound (D -2) ... 0.001 mol 5th Fl per 1 mol of silver; middle Fl (1, L,) Same as M2 layer, gelatin layer.

6th layer; low? , 1 green-sensitive silver halide emulsion l (GL-
1) Emulsion - ■ Coated silver amount 1.5 g/m2 Sensitizing dye II+... 2.5 Xl0-' mole per t111 mol Sensitizing dye ■... 1. 2 x 10-' mol Magenta coupler (TR)... 0.050 mol per mol of silver Colored magenta coupler (CM-1)... 0.009 mol DIR compound (D) per mol of silver -1) ... 0.0010 mol DIR compound (D-3) for 1 mol of silver... iI! 0.0030 mol per 1 mol 7th layer: Highly sensitive green-sensitive silver halide emulsion layer (GH-11 emulsion-I!...
・ Coating amount of silver 1.47 m2 Sensitizing dye ■■... 1.5 Xl0-' mol sensitizing dye ■■ per 1 mole of silver
... 1.0 Xl0-' mol magenta coupler (Tl) per 1 mol of silver... 0.020 mol per 1 mol of silver Colored magenta coupler (CM-1)... per 1 mol of silver O,002 mol DIR compound (D-3) ... 0.0010 mol per mol of silver 8th P1. Yellow Filter Layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer; low-speed blue-sensitive silver halide emulsion layer (!IL-1
) AgB with average particle size 0.48 μm and containing 8g 16 mol zero
Monodisperse emulsion consisting of r1 (emulsion! ■ Ri... Silver coating amount 0.9 g/m2 Sensitizing dye ■... 1.3 Xl0-' mol per 1 mol of silver Yellow coupler (Y-1) ・...0.29 per mole of silver
Mole 10th layer: Highly sensitive blue-sensitive emulsion layer (B) I-1) Monodisperse emulsion consisting of 8 girls with an average grain size of 0.8 μm and 15 moles of Agl (emulsion +V)... Silver coating amount 0. 5g/
m' Sensitizing dye V... 1. OXl0-'mol yellow coupler (Y-1)...

0.08 mol per mol of silver DIR compound (D-2) ... 0.0015 mol per mol of silver 11th F1. First protection 11 (Pro-1) Silver iodobromide (
＾gl 1 mol zero average particle diameter 0.07 μm) Silver coating amount 0.
5g/a' Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer; second protective layer (Pro-2) gelatin layer containing polymethyl methacrylate particles (diameter 1°5μ) and formalin scavenger ()Is-1) In addition to the above composition, each layer contains: Gelatin hardener (H-1
) and surfactants were added.

The compounds contained in each layer of sample No. 401 are as follows.

m-sensitivity color 1tl; anhydro-5,5゛-dichloro-9-
Ethyl-3,3°-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye I ■: Anhydro-9-ethyl-3,3°-di(3-sulfopropyl) -4,5,4° .

5"-Dibenzothiacarbocyanine hydroxide sensitizing dye!1!; Anhydro-5,5"-diphenyl-
9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye! v; Anhydro 9-ethyl-3,3"-di(3-sulfopropyl) 5,6.5°.

6°-dibenzoxacarbocyanine hydroxide sensitizing dye V: Anhydro 3,3°-di(3-sulfopropyl)-4,5-benzo-5°-methoxythiacyanine-I C-t H υH CM-1 Sample N except that the DIR coupler in layer 6 of sample No. 401 was changed as shown in Table 4 below.

Samples Nos. 402 to 405 were prepared in the same manner as No. 401. The structural formula of the newly used DIR coupler (D-4) is as follows.

Each sample No. 401 to No. 4 created in this way
05 was wedge exposed using white light, and then subjected to self-development.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds fixation 6 minutes 30 seconds washing with water 3 minutes 15 seconds stabilization
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color development? &] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfur Ql salt 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide
1.3 g nitrilotriacetic acid.
Trisodium (monohydrate) 2.5 g
Potassium hydroxide 1.0g Add water to make 11.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0mj2 water and make 1
λ and adjust the pH to 6.0 using aqueous ammonia.

[Fixing] Ammonium thiosulfate 17.5g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 11, and adjust to pH 6.0 using acetic acid.

[Stabilizer] Formalin (3°796 aqueous solution) 1.
5mJ2 Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7. Sm1L
Add water to make IJZ.

The relative sensitivity (S) and sharpness (MTF) of each sample obtained were measured using white light (W).

The results are shown in Table 4.

Note that the relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives the fog density +0.1, and the W sensitivity of No. 401 is 10
It is shown as a value of 0. The sharpness improvement effect is due to the M of the dye image.
T F (Modification Transfer
Function) was calculated and expressed as a relative value of MTF in lO tree/■ (Sample No. 401 is set as 100).

Table 4 As is clear from Table 4, the sample containing the compound of the present invention has a greater sharpness improvement effect than the sample containing the conventional DIR compound, even in multilayer samples.

Procedural amendment (1 cited September 11, 1986, Commissioner of the Patent Office Black 1) Mr. Yu Akira 1, Display of the case Patent application No. 17'0762 of 1988 2, Name of the invention Relationship with the case Name of the patent applicant (127) Roku Konishi Photo Industry Co., Ltd. Representative Keio Ide 4 Address of agent 11-1 Ichiban-cho, Chiyoda-ku, Tokyo 102; 5 Date of amendment order Voluntary action 7 Contents of amendment 1) Page 4 of the specification In line 17, "in this case" is corrected to "the above."

2) "..." on page 9, lines 13 to 14 of the specification
...... General formula [■ Represented by L. ” is written as “...-Type 119-L Yu”
− is represented. ” is corrected.

3) In the 2nd and 3rd lines of page 10 of the specification, replace the position where it says ``...after white, Int leaves the factory,'' with ``.・Int is (
), after leaving the organization.

4) “represents G2 in lines 4 to 7 of page 14 of the specification
deletes hydrogen atoms, halogen atoms, alkyl groups (e.g. methyl groups, ethyl groups, 2-(phenoxycarbonyl)ethyl groups, etc.).

5) "..." on page 14, lines 11 to 12 of the specification
・・・・・・・・・-CO2CH2CH2CΣ group, etc.”
The position marked as “・・・・・・-CO2CH2
CHz CN group, etc.”.

6) In the second line of page 16 of the specification, "already explained" is corrected to "same as G1 shown in general formula [1a-1]".

7) "One product" on page 19, line 10 of the specification is corrected to "product."

8) "Body" on page 21, line 17 of the specification is corrected to "product."

9) Correct "e" in line 4 of page 25 of the specification to "toku".

10) “Photographic effect” on page 26, lines 12-13 of the specification
``Photographic action of a photographically useful group that produces from A1'' is inserted between ``than'' and ``than''.

11) "Buy and sell" on page 26, line 14 of the specification is corrected to "expression."

12) 'R1-Xl-X2-RI J' on page 27, line 15 of the specification
Correct to 2-R2J.

13) Insert "r" between "continued" and "after completion of the reaction" on page 44, line 15 of the specification.

14) Correct "r kao" to "ko" on page 47, line 6 of the specification.

15) "Riki" on page 48, line 14 of the specification is corrected to "Kagin".

16) Correct "nnn" to "n" on page 49, line 3 of the specification.

17) Page 51 of the specification, lines 18 to 19:
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・
・ ・ ・ ・ ・ ・ Correct the position where it says "Coup..." to reoupJ.

18) Delete "No." on page 56, line 9 of the specification.

19) On page 58, line 1 of the specification, “Unexamined Japanese Patent Publication No. 52-2391
1" is corrected to "Unexamined Japanese Patent Publication No. 52-23911."

20) "Pyrazolino-Cl, raimidazole series" on the last line of page 81 of the specification is changed to "pyrazolino<>raimidazole series"
Correct to.

21) "Dekie," on page 64, lines 14 to 15 of the specification.
``Delete the ``ru'' in ``.

22) "Ethylene" on page 72, line 14 of the specification is corrected to "ethylene."

23) In the third line of page 73 of the specification, ``for example'' should be corrected to ``for example''.

24) Insert r(W-3) between rD I RJ and "compared to" in the second line from the bottom of page 80 of the specification.

25) Enter rMTFJ in the blank space above “30 wood/mm J” on the top right corner of Table 2 on page 81 of the specification.

26) Structural formula in the center of page 83 of the specification correct.

27) "Color" on page 19, line 10 of the specification is corrected to "color 亙".

28) Structural formula of D-1 at the bottom of page 93 of the specification correct.

29) The construction formula in D-2 at the top of page 94 of the specification is corrected.

30) In the 5th line from the bottom of page 99 of the specification, replace “nawo” with “
Corrected to "Note."

31) In Table 4 on page 100 of the specification, sample No. 4
The addition amount of D-3 in the column next to 02 is ro, 3J (0,
Fill in the blank space below 1).

that's all

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least one of the photographic constituent layers contains a photographically useful group precursor and the photographic material is added during photographic processing. 1. A silver halide photographic light-sensitive material comprising a compound that releases a reactive group (or a reactive reagent) that reacts with a sexually useful group precursor to produce a photographically useful group.