JPH0356462B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic light-sensitive material containing a novel photographic compound capable of releasing photographically useful development inhibitor residues in a timely manner. Photographic additives, especially those that act during processing, may exhibit other undesirable side effects if added as such. In order to improve this, by adding it in a protected form, so-called a precursor, it is possible to not only reduce the effects before processing, but also to obtain the effect of being released in response to the processing time. In some cases, additives may be used in a form that can be used in a natural or even imagewise manner. For example, Whitmore et al., US Pat. No. 3,148,062 and Barr et al., US Pat. Discloses that it will be released. 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 a direct release method may accelerate or delay the release time of the photographically useful groups mentioned above in relation to various reactions caused by other materials that occur within the silver halide photographic light-sensitive material. When adjustment is necessary, or because the desired effect is expected in a predetermined constituent layer or position within a silver halide photographic light-sensitive material, adjustment is necessary to move a photographically useful group by a predetermined distance. In such cases, 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. This is inconsistent with the purpose and effect expected of a useful group, and thus results in a loss of freedom in selecting a compound with respect to a given purpose. On the other hand, one technique to improve these is to provide a bonding group (timing group) between the protecting group or coupler and the photographically useful group, thereby maximizing the respective functions. Disclosed. Japanese Patent Publication No. 54-39727 and Japanese Patent Application No. 55-17644 describe linking groups which form quinone methide or naphthoquinone methide and release photographically useful groups. However, this compound has the disadvantage that it is unstable and partially decomposes during storage, releasing photographically useful groups, leading to undesirable effects. Further, JP-A-54-145135 and JP-A-55-53330 describe a bonding group that causes an intramolecular nucleophilic substitution reaction to release a photographically useful group. 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. However, when using the means and compounds described in the above-mentioned publication, since some compounds are included that also undergo a nucleophilic substitution reaction with hydroxide ions in the color developing solution, the effect is exerted only in the exposed areas. Despite this promise, it has the drawback that photographically useful groups are released even in unexposed areas. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide photographic light-sensitive material containing a compound that is significantly improved in decomposition by photographic processing solutions and that releases photographically useful development inhibitor residues indirectly and in a timely manner. It is about providing. The present inventors have achieved the above object by incorporating at least one compound represented by the following general formula (1) (hereinafter referred to as "compound according to the present invention") into a silver halide photographic light-sensitive material. I found out what can be achieved. General formula (1) In the formula, × represents an atomic group necessary to complete the benzene nucleus, and Y represents 5, which is a condensed ring of the benzene nucleus.
represents the atomic group necessary to complete a 6-membered or 6-membered heterocycle, A is a hydrogen atom or a group that can be separated under photographic processing conditions,

[Formula] is in ortho or para position with A -O-, R ₁ and R ₂
is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic residue; PUG is a photographically useful development inhibitor residue having at least one heteroatom in its molecular structure;

It is connected to [expression]. Specifically, the group represented by A that can be separated under photographic processing conditions is an acyl group that can be hydrolyzed with an alkali, a sulfonyl group, or a group that is bonded at a position that can be coupled with an oxidized form of a color developing agent. a group that can be eliminated by a redox reaction, especially a group that can be eliminated by being oxidized by an oxidized color developing agent, or a group that can be eliminated by being reduced by a reducing agent such as hydroquinone. etc. Specifically, the 5-membered or 6-membered heterocycle represented by Y, which is a fused benzene ring, is a saturated or unsaturated 5-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. and represents a 6-membered ring, etc.
Along with the benzene ring formed by A nucleus, an indole nucleus, an oxindole nucleus, a benzofuran nucleus, a benzothiophene nucleus, a benzoxathiazole nucleus, etc. are formed. These include alkyl groups, aryl groups, alkoxy groups, amino groups, acid amide groups, sulfonamide groups, carboxy groups, alkoxycarbonyl groups, carbamoyl groups, cyano groups, nitro groups, sulfo groups, sulfamoyl groups, sulfonyl groups, and carbonyloxy groups. , a formyl group, or a halogen atom. Examples of coupling components that can react with the oxidized form of a color developing agent include color couplers commonly used in color photographic materials. For example, yellow couplers are
2298443, 2407210, 2875057, 3048194, 3265506, 3447928 and {Farb
−Kuppler−eine Literaturubersicht・Agfa
Mitteilung (Band)} pages 112-126 (1961)
A benzoylacetanilide type yellow coupler or a pivaloylacetanilide type yellow coupler described in et al. can be used.
Also, regarding the magenta coupler, U.S. Patent No.
No. 2369489, No. 2343703, No. 2311082, No. 2600788, No. 2908573, No. 3062653,
No. 3152896, No. 3519429 and the above {Agfa Mittelung (Band)} {Agfa
Mitteilung (Band)} pages 126-156 (1961)
Various magenta couplers can be used, such as pyrazolone magenta couplers or indazolone magenta couplers described in, et al. 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 Mittelung (Band)} {Agfa
Mitteilung (Band)} pages 156-175 (1961)
The naphthol-based or phenolic couplers described in . In addition to these couplers, West German patent publication no.
A black dye-forming coupler can be used as described in No. 2644915. 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 according to the present invention. Same No. 3928041, Same No. 3958993
No. 3961959 and British Patent No. 861138. The photographically useful group may be any group that can be made available in an image-like pattern within the silver halide photographic light-sensitive material. Representative examples of these photographically useful development inhibitor residues include U.S. Pat.
Mercaptotetrazole, selenotetrazole, mercaptopenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzo described in UK Patent No. 3384657, UK Patent No. 3615506, UK Patent No. 3617291, UK Patent No. 3733201, and UK Patent No. 1450479. Examples include oxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole, benzodiazole or iodide. Among the compounds represented by the general formula (1), those represented by the following general formula (2) are particularly preferred in the present invention. General formula (2) In the formula, A, R ₁ , R ₂ , Y and PUG each have the same meaning as defined in the general formula (1) above,
m and n represent 1 or 2 (however, m≠n)

[Formula] is in the ortho position with respect to A-O- when m=1 and n=2, and is in the ortho or para position when m=2 and n=1. Specific examples of compounds according to the present invention are listed below, but the invention is not limited thereto. Next, a synthesis example of the compound according to the present invention will be described. Synthesis Example 1 Synthesis of Exemplified Compound 1 5-Chloromethyl-8-hydroxyquinoline hydrochloride was published in The Journal of Organic Chemistry
25, 4080 (1961). 23 g of this 5-chloromethyl-8-hydroxyquinoline hydrochloride was dissolved in 20 ml of acetone and 10 ml of water.
0.79 g of pyridine was added. To this, 1-phenyl-5-mercaptotetrazole sodium salt 2.0
g and stirred for 1 hour. 100% water to reaction solution
ml and 100 ml of ethyl acetate were added, the ethyl acetate layer was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a white solid. This was recrystallized from ethyl acetate to obtain 1.0 g of Exemplified Compound 1. Mass spectrum M/e=175 (M ⁺ ) Synthesis example 2 Synthesis of exemplified compound 4 Synthesis of () 0.66 g of potassium hydroxide was dissolved in 20 ml of methanol, 1.75 g of 5-hydroxymethyl-8-hydroxyquinoline was added thereto, stirred for 30 minutes, and then concentrated under reduced pressure. Add to this 6.06g of () and DMF30
ml and stirred for 3 hours. _H2O200 to the reaction solution
ml and 200 ml of ethyl acetate were added, and the ethyl acetate layer was separated. The ethyl acetate layer was first washed with dilute hydrochloric acid, then with a sodium hydrogen carbonate solution, then with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. From this crude product, the target product was separated and purified by silica gel column chromatography using benzene-acetone as a developing solvent. A pale yellow caramel-like substance was obtained. It was confirmed by NMR and mass spectra that it was (). Synthesis of () Dissolve 2.5g of () in 50ml of chloroform,
After adding 0.7 g of phosphorus pentachloride and reacting for 2 hours,
The chloroform layer was extracted by adding 100 ml of H ₂ O. The chloroform layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a pale yellow caramel-like substance. It was confirmed by NMR and mass spectra that it was (). Synthesis of Exemplified Compound 4 2.5 g of () and 0.7 g of 1-phenyl-5-mercaptotetrazole sodium salt were heated under reflux for 1 hour in 50 ml of acetonitrile, and then concentrated under reduced pressure. The extract was extracted with ethyl acetate, washed with 5% sodium carbonate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Compound 4 was separated from this crude product by silica gel chromatography using benzene-acetone as a developing solvent, and recrystallized with a benzene-hexane mixed solvent. Exemplified compound 4 by NMR and mass spectra
It was confirmed that Other exemplified compounds can also be synthesized in the same manner. A silver halide photographic material containing the compound according to 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. Furthermore, U.S. Patent No. 3674490, U.S. Patent No. 3822129, U.S. Patent No. 3834907,
Same No. 3841873, Same No. 3847619, Same No. 3862842,
Image amplification processing using oxidizing agents such as transition metal complexes (e.g. cobalt hexamine) or peroxides (e.g. hydrogen peroxide) as described in No. 3902985 and No. 3923511 can also be performed. . A silver halide photographic light-sensitive material containing the compound according to the present invention may have a single silver halide emulsion layer on a support, or may be composed of 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 silver halide photographic light-sensitive material of the present invention can also be used for black-and-white photography consisting of a single layer using a black dye image type coupler on a support. The compound according to the present invention may be contained in the light-sensitive silver halide emulsion layer of these silver halide photographic materials, or may be contained in a layer adjacent thereto. Further, it can be contained in any one or more of these constituent layers at the same time. When the compound according to the present invention is contained in a silver halide photographic light-sensitive material, the amount added is silver halide 1
It is about 0.01 to 3 moles per mole. There are various methods for incorporating the compound according to the present invention into a silver halide photographic light-sensitive material, and typical examples thereof are as follows. (a) The compound according to 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 according to 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 according to the present invention, the above-mentioned solvents may be mixed and used, and a dispersion aid may also be used. If the timing group to which the photographically useful group is bonded or if the photographically useful group is diffusive, one or more scavenger layers may be added to the appropriate layers of the silver halide photographic light-sensitive material. By intervening at a specific position, the layer or unit layer affected by the above-mentioned photographically useful group can be controlled. Further, the silver halide used in the silver halide photographic light-sensitive material of the present invention is prepared by a conventional method, and includes silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chlorobromide, and silver chloride. It may be of any composition such as silver oxide. These silver halide emulsions can be prepared by conventional methods and further chemically sensitized. Therefore, silver halide emulsions may be monodispersed or polydispersed, and may vary in grain size, grain shape, negative emulsion, positive emulsion, internal latent image type,
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, hardeners, plasticizers, and surfactants. Regarding silver halide emulsions and additives,
For example “Research Disclosure” December 1971 9232
is detailed in more detail. The compound according to the present invention can be added to a silver halide photographic light-sensitive material for various purposes and arrangements according to the action and properties of the photographically useful group, and if necessary, various couplers or other various types can be added. May be mixed with additives. And when the photographically useful group released from the compounds according to the invention is a development inhibitor, for example US Pat. No. 3,227,554
It can be used with the silver halide photographic materials described in each of No. 3,620,747 and No. 3,703,375. As described in detail above, in the compound according to the present invention, the photographically useful group is bonded to the coupling component via the timing group, so that the release of the photographically useful group is indirectly caused. By using this, the action and effect of silver halide photographic materials 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 U.S. Pat. No. 3,632,345
Compared to the interlayer effect (interimage effect) obtained by the development inhibitor-releasing compound (DIR compound) described in No. 3958993, the interlayer effect obtained by the compound according to the present invention is superior. You can expect good results. Example 1 As a magenta coupler, 1-(2,4,6-
trichlorophenyl)-3-[3-(2,4-di-
15 g of t-amylphenoxyacetamido)benzamide]-5-pyrazolone 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. Thereafter, this dispersion was mixed with a green-sensitive silver iodobromide agent (containing 3.0 mol% silver iodide) 1
After dispersion, it was applied to a triacetate base and dried. This is designated as sample (1) (control sample). In addition to the above control sample (1), the following 2
Species DIR couplers and compounds according to the present invention were added to the emulsion according to the amounts listed in Table 1 below, and samples (2), (3), (4), and (5) were prepared in the same manner. ,
(101), (102), (103), (104), (105), (106
) and (107) were created. The above-mentioned 12 types of samples were subjected to wedge exposure, color development was performed at 38° C. for 3 minutes using a color developer having the composition shown below, bleached and fixed, and then washed 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 potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water and adjust to 1 using potassium hydroxide to pH
Adjust to 10.0. The results obtained are shown in Table 1 below.

【table】

[Table] As is clear from Table 1, the sample to which the compound according to the present invention was added was a DIR coupler directly connected to an inhibitor.
It can be seen that there is almost no difference in sensitivity compared to the samples containing (A) and (F), and the gamma adjustment effect is remarkable, and it is possible to change the results. It can also be seen that DIR coupler (E) is not a DIR coupler because the O atom and methine bond are in the para position. The above 12 types of samples were stored at 60° C. and 80% RH for 2 days and then subjected to the same exposure and development process. The results are shown in Table 2.

【table】

[Table] As is clear from Table 2, the compound according to the present invention has excellent storage stability compared to DIR coupler (B).
It can be seen that this is an excellent compound that does not contribute to the deterioration of photosensitive materials. Example 2 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 ^m2 . (2) Gelatin interlayer containing 0.5 g/m ² of gelatin and 0.1 g/m ² of 2,5-dioctylhydroquinone. (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 0.8 g/m ² of gelatin. The following DIR couplers and compounds according to the present invention were added to the third layer containing a cyan coupler among the constituent layers of the multilayer coated photosensitive material in accordance with the amounts shown in Table 3. Samples (6), (7), (8) and (9)
It was created. 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 through 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 3 below. .

[Table] As shown in Table 3 above, samples as control samples
Compared to (6) and (7), samples (8) and (9) to which the compound of the present invention was added both have larger γR/γN values, which means that the amount of development inhibitor in the red-sensitive layer is higher in the sample according to the invention than in the control sample, in other words, when using the compound according to the invention there is a greater interlayer effect ( This clearly shows that an interimage effect can be obtained. Example 3 The following compound was added to the sample (1) used in Example 1 as the fourth
Samples (10) and (11) were prepared by adding according to the amounts shown in the table. Comparative compound (1) Compound described in Japanese Patent Publication No. 54-39727 Table 4 shows the results of exposing and processing these samples according to Example 1, and Table 5 shows the results after forced storage.

【table】

[Table] As can be seen from Tables 4 and 5, the sample to which the compound according to the present invention was added released more inhibitory agents under the treatment conditions than the sample to which the compound described in Japanese Patent Publication No. 54-39727 was added. It is quick and has excellent storage stability.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing at least one compound represented by the following general formula (1). General formula (1) In the formula, × represents an atomic group necessary to complete the benzene nucleus, and Y represents 5, which is a condensed ring of the benzene nucleus.
represents the atomic group necessary to complete a 6-membered or 6-membered heterocycle, A is a hydrogen atom or a group that can be removed under photographic processing conditions, and [Formula] represents A -O- and the ortho or para position. located in R ₁ and
R ₂ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic residue, and PUG
is a photographically useful development inhibitor residue having at least one heteroatom in its molecular structure, which is bonded to the formula. 2. The compound according to claim 1, wherein A is a coupling component capable of coupling with an oxidized color developing agent, and is bonded to an oxygen atom at a position capable of coupling with an oxidized color developing agent. Silver halide photographic material.