JPH0440701B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to silver halide photographic materials containing novel photographic compounds capable of releasing photographically useful groups at controllable timing. Various methods are known for imagewise release of photographically useful groups by utilizing compounds used for photographic purposes. For example, Whitmore
U.S. Pat. No. 3,148,062 to Barr et al. and U.S. Pat. No. 3,227,554 to Barr et al. disclose the release of a development inhibitor or dye from the coupling site of a photographic coupler by reaction of the photographic coupler with an oxidized color developer. is disclosed. Holtz, US Pat. No. 3,705,801, also discloses photographic couplers that release bleach inhibitors from the coupling site after reaction of the coupler with oxidized color developer. The methods disclosed above as prior art and the compounds used all belong to the system in which photographically useful groups are directly released from these compounds. However, such direct release methods require that the release time of the photographically useful groups described above be accelerated, delayed, or adjusted in relation to various reactions with other materials that occur within the photographic element. or because you want to expect the effect at a certain constituent layer or position within the photographic element.
In cases where adjustment is required to move a photographically useful group by a predetermined distance, such adjustment is extremely difficult. Therefore, in order to improve this using the prior art, it is necessary to select components that release photographically useful groups, and also to find a means for attaching photographically useful groups to such components. It is important to consider this from a wide range of perspectives, such as the selection of photographically useful groups themselves. It is inconsistent with the purpose and effect expected of a useful group,
This results in a loss of freedom in selecting compounds for a given purpose. On the other hand, JP-A-54-1415135 describes a means for indirectly releasing photographically useful groups. According to the description in the above publication, after reacting with the oxidized color developing agent and cleavage as the first step, an intramolecular nucleophilic substitution reaction is performed to perform the second step of cleavage.
In order to release the final target, a photographically useful group, and thereby control many parameters such as temporal and distance adjustment of the action and effect of the photographically useful group, it is possible to This allows for adjustments across the board. The photographic coupler specifically described in the above-mentioned publication has the disadvantage that the degree of freedom in selecting the coupler component and the nucleophilic group is restricted because it is essential that the nucleophilic group is directly bonded to the coupler component. . Therefore, it may be necessary to use a coupler component with low coupling performance, or the alkali stability of the photographic coupler may be undesirable. The object of the invention is to provide a solution to the above-mentioned drawbacks. The object of the present invention was achieved by containing at least one compound represented by the following general formulas (1) to (7). In the general formula (1), A is a component that can react with the oxidized form of the color developing agent and is bonded to N at a position that can react with the oxidized form, PUG is a photographically useful group, and Y represents an oxygen atom or a sulfur atom, and is located at the 2nd or 4th position relative to the N bonded to A.
M represents a condensed benzene ring, n is 0 or 1, and Z becomes a nucleophilic group after A is cleaved by reacting with an oxidized developing agent. Through an intramolecular nucleophilic substitution reaction with Y, 3
~ _CH2 -CO-* capable of forming a 7-membered ring represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (2), R ₁ and R ₂ are each a hydrogen atom, or a carbon chain in which R ₁ and R ₂ are condensed with two adjacent carbon atoms of a pyridone ring or a thiopyridone ring to jointly form a benzene ring. represents A, PUG,
Y is A, PUG, Y each represented by general formula (1)
represents the same group as -CH, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with N, which becomes a nucleophilic group after A reacts with the oxidized form of the developing agent and cleaves. ₂ −CO−＊ represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (3), A, PUG, and Y represent the same groups as A, PUG, and Y shown in the general formula (1), respectively, and Z is a group obtained after A is cleaved by reacting with the oxidized form of the developing agent. -CH ₂ -CO-*, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with N, which has become a nuclear group. represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (4), A, PUG, and Y represent the same groups as A, PUG, and Y shown in the general formula (1), respectively, and Z is a group obtained after A is cleaved by reacting with the oxidized form of the developing agent. -CH ₂ -CO-*, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with N, which has become a nuclear group. represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (5), A, PUG, and Y represent the same groups as A, PUG, and Y shown in the general formula (1), respectively, and Z is a group obtained after A is cleaved by reacting with the oxidized form of the developing agent. -CH ₂ -CO-*, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with O of the NO group, which serves as a nuclear group. represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In general formulas (6) and (7), A and PUG represent the same groups as A and PUG shown in general formula (1), respectively,
Z is -CH ₂ -CO, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with O of the CO group, which becomes a nucleophilic group after A is cleaved by reacting with the oxidized product of the developing agent. −＊ represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) X represents a halogen atom, and m represents an integer of 0 to 2. In general formula (1), the 6-membered aromatic nitrogen heterocycle formed by N and M may be substituted, and the substituent is preferably a halogen atom or NO ₂ . The group linking A and PUG in the general formula of the present invention is a group capable of releasing a photographically useful group at a controllable timing, and is hereinafter referred to as a timing or Time group. In the present invention, by separating the coupler and the nucleophilic group in the timing group and converting the nucleophilic group into a precursor, the compounds of the present invention are significantly improved in decomposition by photographic processing solutions, and moreover, the timing group provides a photographically useful compound. It has now become possible to significantly change the time it takes to release the group. Additionally, it has become possible to further emphasize the multilayer effect (interimage effect). Furthermore, the compounds of the present invention, in which the nucleophilic group is separated during the first step of cleavage that reacts with the oxidized product of the color developing agent, have a wider range of selection, and can provide compounds that perform the reaction more quickly. It has become possible to achieve the original purpose for which it was established. Furthermore, if we describe the present invention from the perspective of basic behavior, if component A can react with the oxidized product of the color developing agent and release the (Time)-PUG group, then what kind of reaction will occur? It may be a component. Such components include, for example, conventional couplers which react with oxidized forms of color developing agents to form colored substances, and those which react with oxidized forms of color developing agents to form colorless substances. Examples include compounds that Component A does not need to be stabilized (ballasted), or
It may be stabilized with oil-soluble groups or aliphatic groups. The -(Time)・PUG group is bonded at the position where it reacts with the oxidized form of the color developing agent of component A, and therefore, after the compound represented by the above general formula reacts with the oxidized form of the color developing agent. , its (Time)
-PUG groups will be released. On the other hand, some of the released (Time)-PUG groups cause electron delocalization in the conjugated system. As a result, for example, =Y in general formula (1) becomes a nucleophilic group, and can undergo an intramolecular nucleophilic substitution reaction with Z, which is an electrophilic group, ultimately releasing PUG. Y and Z are related to such steric positions. The term "intramolecular nucleophilic substitution reaction"
It is well known in the chemical field and has been published in Japanese Patent Application Publication No. 1983-
As stated in Publication No. 145135, a nucleophilic group of a compound reacts directly or indirectly with an electrophilic group at another position of the compound, resulting in substitution of the group bonded to the electrophilic group. can be defined as a reaction that takes place. In general, these compounds have a nucleophilic group and an electrophilic group sterically located in accessible positions, and are formed into a cyclic organic compound, preferably a 3- to 7-membered cyclic organic compound, by an intramolecular nucleophilic substitution reaction. The arrangement is such that a compound, more preferably a 5- to 6-membered cyclic organic compound, or a transitional organic compound can be formed. As used in the text, a nucleophilic group is a group of atoms in which one of its constituent atoms is electron-rich, and an electrophilic group is a group in which one of its constituent atoms is electron-poor. Indicates that it is a group of atoms. For example, when the compound represented by general formula (1) reacts with an oxidized color developing agent, A and the timing group are first cleaved, and PUG is thought to be released through the following reaction. In the cleaved timing group, electrons move through the bond system in M, and a certain equilibrium state is achieved as a so-called tautomer. In the case of (1), Y becomes a nucleophilic group and undergoes an intramolecular nucleophilic substitution reaction with the sterically adjacent electrophilic group Z to release PUG. However, the equilibrium moves to the right side, and eventually all PUGs
The reaction seems to end with the release of It is estimated that the compounds represented by general formulas (2) to (7) also release PUG according to a similar reaction formula. The most required conditions for these compounds are appropriate reaction rates for first and second step cleavage, and stability under storage conditions and alkaline processing solution conditions; This is due to the strength of the bond with the timing group and the bond between the timing group and PUG. In the present invention, these bonding formats can be freely selected, and the most suitable compound can be selected. As mentioned above, examples of compounds that can react with the oxidized form of the color developing agent according to the present invention include color couplers that are commonly used in color photographic materials. For example, regarding yellow couplers, US Patent No. 2298443, US Patent No. 2407210, US Patent No. 2875057,
No. 3408194, No. 3265506, No. 3447928 and “Farbkuppler-eine Lite-
raturubersicht”Agfa Mitteilung (Band) 112
A benzoylacetanilide-type yellow coupler or a pivaloylacetanilide-type yellow coupler described in 1961, p. 126, etc. can be used. Regarding magenta couplers, US Patent Nos. 2369489 and 2343703
No. 2311082, No. 2600788, No. 2600788, No. 2311082, No. 2600788, No.
No. 2908573, No. 3062653, No. 3152896, No. 3519429 and the above-mentioned Agfa Mitteilung.
Various magenta couplers can be used, such as pyrazolone magenta couplers and indazolone magenta couplers, which are described in J.D. (Band) pp. 126-156 (1961). Furthermore, in the case of cyan couplers, U.S. Pat.
No. 2367531, No. 2423730, No. 2474293, No. 2772162, No. 2895826, No. 3002836,
No. 3034892, No. 3041236 and the above
Agfa Mitteilung (Band) pp. 156-175 (1961
The naphthol-based or phenolic couplers described in 2006) can be used. In addition to these couplers, West German patent publication no.
The black dye-forming couplers described in No. 2,644,914 can also be used. On the other hand, compounds that react with oxidized color developing agents such as cyclic carbonyl compounds but do not form coloring dyes can also be used as compounds of the present invention, and these compounds are described in U.S. Pat. No. 3928041, No. 3958993,
It is described in British Patent No. 3961959 and the specification of British Patent No. 861138. The photographically useful group PUG can be any group that is made available in an image-like pattern within a photographic element. Specific examples of photographically useful groups include development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, developers, fixers, silver halide solvents, silver-complexing agents, hardeners, etc. Filming agents, tanning agents, toning agents, fogging agents, antifogging agents, chemical or optical sensitizers,
Desensitizers, photographic dyes or their precursors,
Couplers (e.g., competitive couplers, color forming couplers, development inhibitor-releasing couplers, i.e. DIR)
- couplers, etc.). The most preferred of these photographically useful groups are development inhibitors, and typical examples include U.S. Pat.
Mercaptotetrazole group, selenotetrazole group, mercaptobenzothiazole group, selenobenzothiazole group, mercaptobenzoxazole group, seleno group, which are described in No. 3615506, No. 3617291, No. 3733201 and British Patent No. 1450479, etc. Examples include a benzoxazole group, a mercaptobenzimidazole group, a selenobenzimidazole group, a benzotriazole group, a benzodiazole group, and an iodine atom. Specific examples of the compounds of the present invention are shown below. The present invention is not limited only to these compounds. In addition, A is not necessarily a colored coupler, but may also be a so-called colorless coupler, and PUG
It is also characterized by the fact that it can be freely selected according to individual purposes. In addition, the compound of the present invention is not only advantageous for use because it is not affected by hydroxyl ions in the developer during the cleavage reaction.
Since PUG can be released at the right time, the photographic effect is outstanding. (Exemplary compound) Next, a synthesis example of the compound of the present invention will be described. (Synthesis example 1) Synthesis of exemplified compound (1) Using pyridine-3-aldehyde as a raw material, “J.
According to Am.Chem.Soc.Vol.76, 1286 (1954),
Compound (2) mp.115℃ was synthesized. 30g of compound (1),
14g of compound (2) and 5.5g of triethylamine
After boiling and stirring for 5 hours in 500 ml of acetonitrile, the acetonitrile was distilled off. After washing the residue with dilute hydrochloric acid, the solid material was squeezed with benzene and cyclohexane to obtain 28 g of white crystal compound (3). 25g of compound (3) in tetrahydrofuran:
Dissolve in 500 ml of a 1:1 methanol solution, and gradually drop 10 ml of an aqueous solution containing 15 g of sodium hydroxide therein. After stirring at 60°C for 1 hour, the mixture was poured into ice containing hydrochloric acid, and the precipitated gum was collected, dissolved in ethyl acetate, and washed with saturated sodium bicarbonate solution.
This ethyl acetate layer was dried over anhydrous magnesium sulfate, and while stirring at room temperature, 5 g of triethylamine was added.
40 ml of a benzene solution (moe/) of compound (5) is gradually added dropwise. After 1 hour, the reaction solution was washed with dilute hydrochloric acid and sodium carbonate solution, the solvent was distilled off, and the residue was subjected to silica gel chromatography using benzene-acetone as an eluent. This gives 12g
Compound (6) mp 98-100°C was obtained. This was confirmed by NMR and Mass. (Synthesis Example 2) Synthesis of exemplified compound (7) After boiling and stirring 30 g of compound (1) and 18 g of compound (2) in 500 ml of acetrinitrile for 5 hours, the acetrinitrile was distilled off. The residue was subjected to silica gel chromatography using benzene-acetone as an eluent. 18g of the obtained compound (3) was added to methanol.
200 ml, and 15 ml of an aqueous solution containing 10 g of sodium hydroxide was gradually added dropwise at room temperature. After stirring for 1 hour, the mixture was poured into diluted hydrochloric acid in ice water, extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, and dried over anhydrous sodium sulfate. compound into this solution
20 ml of a benzene solution (moe/) of (5) was gradually added dropwise while stirring at room temperature. After 1 hour, the reaction solution was washed with dilute hydrochloric acid and aqueous sodium carbonate solution, and then concentrated.
The residue was subjected to silica gel chromatography using benzene-acetone as an eluent. As a result, 8 g of caramel-like compound (6) was obtained. This was confirmed by NMR and Mass. Other exemplified compounds can also be synthesized in the same manner. A photographic light-sensitive material containing the compound of the present invention can be subjected to color development, bleaching, fixing, or processing according to the processing steps used for ordinary color reversal light-sensitive materials. Additionally, U.S. Patent No. 3,674,490;
Same No. 3822129, Same No. 3834907, Same No. 3841873,
Oxidizing agents such as transition metal complexes (e.g. cobalt hexamine) or peroxides (e.g. hydrogen peroxide) as described in 3847619, 3862842, 3902905 and 3923511. It is also possible to perform image amplification processing. The light-sensitive material containing the compound of the present invention may have a single silver halide emulsion layer on a support, or may have multiple silver halide emulsion layers. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The light-sensitive material of the present invention can also be used for black-and-white photography, which consists of a single layer using a black dye image-forming coupler on a support. The compound of the present invention may be contained in the photosensitive silver halide emulsion layer of these light-sensitive materials, or may be contained in a layer adjacent thereto. Further, it can be contained in any one of these constituent layers or unit layers, or in more than one layer at the same time. When the compound of the present invention is contained in a light-sensitive material, the amount added is 0.0005 to 0.1 per mole of silver halide.
Moles are preferred. Particularly preferred is a range of 0.001 to 0.05 mol. There are various methods for incorporating the compound according to the present invention into a light-sensitive material, and typical examples thereof are as follows. (a) The compound of the present invention is dissolved in a high-boiling organic solvent that is difficult to dissolve in water, and this solution is emulsified and dispersed in an aqueous medium and added to an emulsion. (b) A solution of the compound of the present invention dissolved in a low boiling point solvent that is relatively insoluble in water is emulsified and dispersed in an aqueous medium and added to a photographic emulsion. The organic solvent used is removed during the photosensitive material manufacturing process. (c) When the compound of the present invention is dissolved in an organic solvent that is easily miscible with water and this solution is added to a photographic emulsion, the compound is dispersed in the form of fine colloidal particles. Depending on the solubility of the compound of the present invention, a mixture of the above solvents may be used, or a dispersion aid may be used. If the timing group to which the photographically useful group is attached or if the photographically useful group is diffusive, one or more scavenger layers may be interposed at appropriate positions in the constituent layers of the light-sensitive material. By doing so, it is possible to control the layer or unit layer that is affected by the above-mentioned photographically useful group. Further, the silver halides used in the photographic light-sensitive material according to the present invention are those prepared by conventional methods, such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide,
It may be of any composition such as silver chloroiodobromide. These silver halide emulsions were prepared by conventional methods,
Further chemical sensitization can be performed. Therefore, regardless of whether the silver halide emulsion is monodispersed or polydispersed, the size of the grains, the shape of the grains, and even the negative emulsion, positive emulsion, internal latent image type, etc.
Any surface latent image type is applicable to the present invention. In the above chemical sensitization, known chemical sensitizers can be used. Furthermore, these emulsions may contain commonly used additives such as photosensitive dyes, antifoggants, curing agents, plasticizers, and surfactants. Regarding silver halide emulsions and additives, see, for example, "Research Disclosure" December 1971.
9232, described in more detail. The compounds of the present invention have the effect of a photographically useful group,
They can be added to photosensitive materials for various purposes and in various locations depending on their properties, and may be mixed with various couplers or other various additives as necessary. When the photographically useful group released from the compound of the present invention is a development inhibitor, the photosensitive materials described in, for example, U.S. Pat. No. 3,227,554, U.S. Pat. can be used. As described in detail above, the compound of the present invention is
Since the photographically useful group is attached to the coupleable moiety via a timing group, so that release of the photographically useful group can take place indirectly,
By using this, the action and effect on the photosensitive material can be adjusted in terms of time and distance. Thus, the development inhibitor releasing couplers (DIR couplers) described in U.S. Pat. No. 3,227,554;
and development inhibitor-releasing compounds (DIR compounds) described in U.S. Patent Nos. 3,632,345 and 3,958,993.
Compared to the interlayer effect (interimage effect) obtained by the above methods, the interlayer effect obtained by the compound of the present invention can be expected to be more excellent. Example 1 As a magenta coupler, 1-(2,4,6-
trichlorophenyl)-3-[3-(2,4-di-
15 g of t-amylphenoxyacetamido)benzamide]-5-pyrazoline was dissolved in 30 ml of ethyl acetate and 15 ml of dibutyl phthalate, and this was mixed with 20 ml of a 10% aqueous solution of Alkanol B (manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution. The mixture was emulsified and dispersed using a colloid mill. After that, this dispersion was converted into a green finished silver iodobromide emulsion (containing 3.0 mol% silver iodide).
The dispersion was applied to a triacetate base and dried. This is designated as sample (1) (control sample). For the control sample (1) above, the following three types of
Control samples (2), (3), and (4) were prepared by adding each DIR coupler according to the amounts listed in Table 1 below. (DIR coupler) Further, to the above control sample (1), exemplified compounds (1), (2), (6), and (12) as compounds according to the present invention were added in accordance with the amounts listed in Table 1 below, respectively, Samples (5), (6), (18), and (19) of the present invention were prepared.

[Table] The above eight types of samples were exposed to light using a wedge, and color development was performed at 38°C for 3 minutes using a color developer having the composition shown below, followed by bleaching and fixing, followed by washing with water. (Color developer composition) 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous calcium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to 1 and using potassium hydroxide
Adjust to PH10.0. The results obtained are shown in Table 2 below.

[Table] As is clear from Table 2, sample (5) according to the present invention
The concentration decrease due to development inhibitor release is smaller than that of the control sample (2), and the concentration decrease of the sample (6) according to the present invention is greater than that of the control sample (2). This demonstrates that the release time and rate of development inhibitor can be controlled simply by changing the timing group. Furthermore, by comparing the sensitivities of control samples (3) and (4) and samples (5) and (6) according to the present invention using the specific sensitivity of control sample (2) as a standard, control samples (3), ( In case 4), it can be seen that the development inhibitor was also released due to decomposition. Similarly, in samples (18) and (19) according to the present invention, the release time and release rate of the development inhibitor can be controlled simply by changing the timing group, and the release of the development inhibitor due to decomposition does not occur. It shows. Furthermore, similar results were obtained when Exemplified Compound (5) was used instead of Exemplified Compound (1). Example-2 In place of the magenta coupler in Example-1, 1-hydroxy-N-[4
-(2,4-di-t-amylphenoxy)butyl]
Using 10.6 g of -2-naphthamide, the following
DIR coupler and exemplary compound (8) according to the present invention,
Five types of samples were prepared in the same manner as in Example 1, except that (14) and (15) were added according to the table below. These five samples (7), (8), (9), (20), and (21) were exposed and developed in the same manner as in Example-1. (DIR coupler) The results obtained are shown in Table 3 below.

【table】

【table】

[Table] As is clear from Table 3, sample (9) according to the present invention
It was found that samples (20) and (20) had a greater decrease in concentration due to development inhibitor release than sample (8) using a conventional direct-coupled DIR coupler, and were therefore superior in effect.
Moreover, sample (21) according to the present invention similarly exhibits excellent effects. Example 3 Multilayer coating was performed on a triacetate base in the following order to create a basic sample. (1) As a yellow coupler, 2-(2,2-dimethylpropionyl)-2-(1-benzyl-2
-phenyl-3,5-dioxo-1,2,4-
triazolidin-4-yl)-2'-chloro-
5′-(α-dodecyloxycarbonyl-ethoxycarbonyl)acetanilide 1.80 g/m ² , gelatin 2.4 g/m ² and silver halide 1.6 g/m ²
A red-sensitive silver iodobromide emulsion layer containing. (2) Gelatin 0.5g/m ² and 2,5-di-t-
Gelatin interlayer containing 0.1 g/m ² of octylhydroquinone. (3) As a cyan coupler, 1-hydroxy-N
-[4-(2,4-di-t-amylphenoxy)
A green-sensitive silver iodobromide emulsion layer containing 0.47 g/m ² of butyl]-2-naphthamide, 2.4 g/m ² of gelatin, and 1.6 g/m ² of silver halide. (4) Protective layer consisting of gelatin 0.8g/ ^m2 . Among the constituent layers of the multilayer coating photosensitive material, the third layer containing the cyan coupler contains the following DIR couplers and DIR compounds as well as exemplified compounds (4) and (8) according to the present invention shown in Table 4 below. Four types of samples (10),
(11), (12), and (13) were created. (DIR couplers and DIR compounds)

[Table] Each sample was divided into two parts, and one sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with red light. Next, it was treated with a color developing solution having the following composition at 38°C for 2 minutes, bleached and fixed, and then washed with water. (Color developer composition) 4-amino-3-methyl-N-ethyl-N-β
-Hydroxyethylaniline sulfate 3.55g Potassium sulfite 2.0g Anhydrous potassium carbonate 30.0g Potassium bromide 1.25g Potassium iodide 0.0006g Add water to make 1. PH 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 values obtained by dividing the gamma (γR) due to red exposure by the gamma (γW) due to white exposure are shown in Table 5 below. .

[Table] As shown in Table 5 above, samples as control samples
Compared to (10) and (11), sample (12) according to the present invention,
The fact that the γR/γW values of (13) are both large means that the amount of development inhibitor in the red-sensitive layer is greater in the sample according to the present invention than in the control sample. It is clearly shown that when the compound of the invention is used, a greater interlayer effect (interimage effect) can be obtained than when using conventional DIR couplers and DIR compounds. Example 4 In Example-1, samples (14),
(15), (16), and (17) were created. These four types of samples were exposed and developed in the same manner as in Example-1.

【table】 The results obtained are shown in Table 7 below.

[Table] Detection of the sharpness improvement effect is performed using MTF (Modulation
Transfer Function), and the spatial frequency is 10
This was done by comparing the MTF size at lines/mm and 30 lines/mm. In addition, graininess (RMS) is the standard deviation of density value fluctuations that occur when scanning with a microdensitometer with a circular scanning aperture of 25μ.
This was done by comparing 1000x values. From Table 7, except for the control sample (14), the specific sensitivity and gamma values are almost the same. Sample (16) when used in combination with 1) had a significantly higher MTF value than when each was used alone.
It can be seen that the sharpness has been improved. Also, RMS
The value is also significantly smaller than that of the control sample (14). That is, it shows that the graininess is improved.

Claims (1)

[Claims] 1. Among the compounds represented by the following general formulas (1) to (7),
A silver halide photographic material containing at least one. In the general formula (1), A is a component that can react with the oxidized form of the color developing agent and is bonded to N at a position that can react with the oxidized form, PUG is a photographically useful group, and Y represents an oxygen atom or a sulfur atom, and is located at the 2nd or 4th position relative to the N bonded to A.
M represents a condensed benzene ring, n is 0 or 1, and Z becomes a nucleophilic group after A is cleaved by reacting with an oxidized developing agent. Through an intramolecular nucleophilic substitution reaction with Y, 3
~ _CH2 -CO-* capable of forming a 7-membered ring represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (2), R ₁ and R ₂ are each a hydrogen atom, or a carbon chain in which R ₁ and R ₂ are condensed with two adjacent carbon atoms of a pyridone ring or a thiopyridone ring to jointly form a benzene ring. represents A, PUG,
Y is A, PUG, Y each represented by general formula (1)
represents the same group as -CH, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with N, which becomes a nucleophilic group after A reacts with the oxidized form of the developing agent and cleaves. ₂ −CO−＊ represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (3), A, PUG, and Y represent the same groups as A, PUG, and Y shown in the general formula (1), respectively, and Z is a group obtained after A is cleaved by reacting with the oxidized form of the developing agent. -CH ₂ -CO-*, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with N, which has become a nuclear group. represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In the general formula (4), A, PUG, and Y represent the same groups as A, PUG, and Y shown in the general formula (1), respectively, and Z is a group obtained after A is cleaved by reacting with the oxidized form of the developing agent. -CH ₂ -CO-*, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with N, which has become a nuclear group. represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In general formula (5), A and PUG represent the same groups as A and PUG shown in general formula (1), respectively, and Z becomes a nucleophilic group after A is cleaved by reacting with the oxidized form of the developing agent. -CH ₂ -CO-*, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with O of the NO group represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) In general formulas (6) and (7), A and PUG represent the same groups as A and PUG shown in general formula (1), respectively,
Z is -CH ₂ -CO, which can form a 3- to 7-membered ring through an intramolecular nucleophilic substitution reaction with O of the CO group, which becomes a nucleophilic group after A is cleaved by reacting with the oxidized product of the developing agent. −＊ represents a bonding group having an electrophilic group represented by any one of the following. (However, R represents a lower alkyl group,
* represents the position where it binds to PUG. ) X represents a halogen atom, and m represents an integer of 0 to 2.