JPS6410061B2 - - 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 development inhibitors or dyes released from the coupling site of a photographic coupler by reaction of the photographic coupler with an oxidized color developer. This 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 must be accelerated, delayed, or adjusted in relation to the various reactions with other materials that occur within the photographic element. In some cases, or because you want to expect that effect at a given constituent layer or position within a 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. 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, JP-A-54-145135 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, a wide range of Allows for adjustments over time. 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. . For this reason, there are undesirable problems in that it is sometimes necessary to use a coupler component with low coupling performance, and that it decomposes during storage, causing deterioration of the photosensitive material. In order to improve these shortcomings, Japanese Patent Application Laid-Open No. 56-114946
Although improvements have been proposed in this issue, the above drawbacks have not yet been completely resolved. An object of the present invention is to further improve the above-mentioned drawbacks and to provide a compound that has excellent coupling performance and good storage stability. As a result of intensive research into controlling the action time of photographically useful substances, the present inventors have determined that at least one of the compounds represented by the following general formula (hereinafter referred to as "compounds according to the present invention") is a silver halide compound. By incorporating it into the photographic material,
It has been found that the above object can be achieved. general formula [In the formula, Coup is a coupling component that can couple with the oxidized color developing agent, and R ₁ and
R ₂ is a hydrogen atom, an alkyl group or an aryl group, Z is a component that can form a 6-membered heterocycle (including those forming a condensed ring), and Coup is an oxidized color developing agent. is bonded to the heterocycle via an oxygen atom at a position that can be substituted with. PuG has a heterocyclic ring bonded to the oxygen atom.
It is a photographically useful group that can be released after leaving the Coup. ] The alkyl group in the above general formula is an alkyl group having 1 to 1 carbon atoms.
For example, methyl group, ethyl group, iso-
Indicates a propyl group, ter-butyl group, n-octyl group or n-octadecyl group,
It may be substituted with an alkoxy group, a hydroxy group, a carboxy group, a cyano group, an amino group, an aryloxy group, or the like. Aryl group refers to phenyl group or naphthyl group, hydroxy group, alkoxy group, carboxy group, alkoxycarbonyl group, acyl group, acylamino group, cyano group, nitro group, halogen atom, amino group, sulfone group, sulfo group, It may be substituted with a sulfonamide group, a carbamoyl group, a sulfamoyl group, or the like. For example, the 6-membered heterocycle constituted by Z is,
Pyridine, quinoline, pyrimidine, pyridazine,
Examples include pyrazine, cinnoline, quinoxaline, naphthyridine, phthalazine, and their N-oxides. They also include those substituted with an alkyl group, a halogen atom, an aryl group, an alkoxy group, a carboxy group, a nitro group, a cyano group, an amino group, or the like. Furthermore, in the 6-membered heterocycle, via an oxygen atom,
to the carbon atom at the 2nd or 4th position relative to the carbon atom bonded to Coup.

[Formula] is preferably bonded. Coupling components according to the present invention include color-forming couplers that are commonly used in color photographic materials. For example, regarding yellow couplers, US Patent Nos. 2298443, 2407210, 2875057,
No. 3048194, No. 3265506, No. 3447928 and “Farbkupplereine Literaturubersicht”
Agfa Mitteilung (Band) pp. 112-126 (1961
It is possible to use benzoylacetanilide type yellow couplers or bivaloylacetanilide type yellow couplers described in 2003). Regarding magenta couplers, U.S. Patent No. 2369489, U.S. Patent No. 2343703, U.S. Patent No. 2311082
No. 2600788, No. 2908573, No. 3062653,
No. 3152896, No. 3519429 and the above
Agfa Mitteilung (Band) pp. 126-156 (1961
Various magenta couplers can be used, such as pyrazolone magenta couplers or indazolone magenta couplers described in 2003). 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 coupling components according to the present invention, and these coupling components are described in U.S. Pat. No. 3,632,345. , same no.
It is described in British Patent No. 3928041, British Patent No. 3958993, British Patent No. 3961959, British Patent No. 861138, and the specifications. 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 or development inhibitor-releasing couplers or DIR-
couplers, etc.). Further, Coup is not necessarily limited to a colored coupler, but may also be a so-called colorless coupler, and PuG can also be freely selected depending on the individual purpose. 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. Additionally, these compounds can release PuG in a timely manner, resulting in outstanding photographic effects. Specific examples of the compounds according to the present invention are shown below. The present invention is not limited to these compounds. These compounds can be synthesized by directly adding a photographically useful compound to a color-forming coupler, and typical synthesis examples thereof are listed below. Synthesis Example 1 (Synthesis of Exemplary Compound (1)) Synthesis was performed according to the following route. 12 g of compound (2), 3.5 g of 3-hydroxy-2-hydroxymethylpyridine hydrochloride, and 5 g of fine powder of anhydrous potassium carbonate were stirred in 2000 ml of alcohol at room temperature for 50 hours. After the reaction solution was concentrated under reduced pressure, it was dissolved in a trace amount of benzene, and the target product was separated and purified by silica gel column chromatography using benzene-ethyl acetate as a developing solvent. 8 g of caramel-like compound () was obtained. 5 g of compound () was dissolved in 20 ml of dry benzene, 1 ml of acetyl chloride was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was sufficiently concentrated under reduced pressure to obtain a candy-like compound (). This was dissolved in dry acetone, 2 g of sodium salt of 1-phenyl-5-mercaptotetrazole was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, extracted with ethyl acetate,
Wash thoroughly with aqueous sodium carbonate solution. The ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained candy-like substance was dissolved in a small amount of benzene, and the target product was separated and purified by silica gel column chromatography using benzene-ethyl acetate as a developing solvent. 4 g of Exemplified Compound (1) was obtained. mp95
Confirmed by ~95.5°C NMR and mass spectrometry. Other compounds can be synthesized in a similar manner. The silver halide photographic light-sensitive material of the present invention can be processed according to color development, bleaching, fixing, or processing steps used for ordinary color reversal light-sensitive materials. Furthermore, U.S. Patent No. 3,674,490;
3822129, 3834907, 3841873, 3847619, 3862842, 3902905 and 3923511, transition metal complexes (e.g. cobalt hexamine) or peroxides; An image amplification process using an oxidizing agent such as hydrogen peroxide can also be performed. The silver halide photographic material of the present invention may have a single silver halide emulsion layer on a support or may consist 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 according to need. 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-forming 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 one or more of these constituent layers or unit layers at the same time. Furthermore, when these compounds are contained in a silver halide photographic light-sensitive material, the amount added is silver halide 1
0.0005 to 0.1 mole per mole is 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 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 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 attached or 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. The layer or unit layer affected by the above-mentioned photographically useful group can be controlled by 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, or silver chlorobromide. 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. Known chemical sensitizers can be used in the above chemical sensitization. Furthermore, these emulsions may contain commonly used additives such as photosensitive dyes, antifoggants, hardeners, plasticizers and surfactants. Regarding silver halide emulsions and additives, please refer to "Research Disclosure" for example.
Further details are provided in December 1971, 9232. The compound according to the present invention can be added to light-sensitive materials for various purposes and arrangements according to the action and properties of the photographically useful group, and may be mixed with various couplers or other various additives as necessary. You may. When the photographically useful group released from the compound according to the present invention is a development inhibitor, for example, US Pat. No. 3,227,554;
It can be used with the photosensitive materials described in No. 3620747 and No. 3703375. 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, its action and effect on the photosensitive material can be adjusted in time and distance. Therefore, U.S. Pat.
Development inhibitor releasing couplers (DIR couplers) described in 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 the same No. 3958993, the interlayer effect obtained by the compound according to the present invention has a more excellent effect. You can expect it. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereby. 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. Afterwards, this dispersion was converted into a green-sensitive silver iodobromide emulsion (containing 3.0 mol% silver iodide).
After adding it to 1 kg and dispersing it, it was applied to a triacetate base and dried. This is designated as sample (1) (control sample). For the control sample (1) above, there were four types as shown in Table 1.
Samples (2), (3), (4), and (5) were prepared by adding DIR couplers in the amounts shown below. (Compound described in JP-A No. 56-114946) The above five 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 following composition.
After bleaching and fixing, it was washed with water. (Color developing agent composition) 4-amino-3-methyl-N-ethyl-N-
(β-hydroxylethyl)-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 to make 1, and use potassium hydroxide to
Adjust to PH10.0. The results obtained are shown in Table 1 below.

[Table] As is clear from Table 1, the gamma adjustment effect of the present invention is more remarkable than that of the comparative sample in which the DIR coupler (A) directly connected to the inhibitor is added, and it is also possible to change the effect. I understand. The above five 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] As is clear from Table 2, the silver halide photographic light-sensitive material of the present invention has excellent storage stability and is an excellent compound that does not cause deterioration of the light-sensitive material, compared to the compound described in JP-A-56-114946. It can be seen that it is. Example 2 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-(1-benzyl-2
-phenyl-3,5-dioxo-1,2,4-
triazolidin-4-yl)-2'-chloro-
Blue-sensitive silver iodobromide emulsion layer containing 1.80 g/m ² of 5'(α-dotecyloxycarbonyl-ethoxycarbonyl)acetanilide, 2.4 g/m ² of gelatin and 1.6 g/m ² of silver halide. (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 red-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. Among the constituent layers of the multi-layer coating photosensitive material, the following DIR couplers were added to the third layer containing cyan coupler according to the amounts shown in Table 3, and four types of samples (6), ( 7), (8) and (9) were 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 blue light. The film was then treated with a color developing solution having the composition shown below at 38°C for 2 minutes, bleached and fixed, and then washed with water. (Color developer composition) 4-Amino-3-methyl-N-(β-hydroxyethyl)aniline sulfate 3.55g Potassium sulfite 2.0g Anhydrous potassium carbonate 30.0g Potassium bromide 1.25g Potassium iodide 0.0006g Add water The pH of 1 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 (γB) due to blue exposure by the gamma (γW) due to white exposure are shown in Table 3 below. .

【table】

[Table] As is clear from Table 3, compared to samples (6) and (7), compounds (8) and (9) according to the present invention have γB/γW
A higher value 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 is the traditional DIR
This clearly shows that a larger interlayer effect (interimage effect) can be obtained than when using a coupler. Even if the above embodiments are applied to a so-called false color negative film in which the sensitive wavelength range of the emulsion layer and the absorption wavelength range of the dye formed from the coupler contained in that emulsion layer are not in a complementary color relationship, almost the same results will be obtained. I got it.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing at least one compound represented by the following general formula. general formula [In the formula, Coup is a coupling component that can couple with the oxidized color developing agent, and R ₁ and
R ₂ is a hydrogen atom, an alkyl group, or an aryl group, respectively, Z is a constituent that can form a 6-membered heterocycle (including those forming a condensed ring), and Coup is a component that can form a 6-membered heterocycle (including those forming a fused ring). is bonded to the heterocycle via an oxygen atom at a position that can be substituted with the heterocycle. PuG has a heterocyclic ring bonded to the oxygen atom.
It is a photographically useful group that can be released after leaving the Coup. ]