JPH0318174B2 - - 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 with controllable timing. Various methods are known for imagewise release of photographically useful groups by utilizing compounds used for photographic purposes. For example, Whitmere
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 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. . Therefore, there are undesirable problems in that a coupler component having low coupling performance must be used in some cases, or that it decomposes during storage and deteriorates the silver halide photographic light-sensitive 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 silver halide photographic material containing 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 capable of coupling with an oxidized color developing agent, and is bonded to an oxygen atom at a position capable of coupling with the oxidized product, and R ₁ , R ₂ and R ₃ are each a hydrogen atom, represents an alkyl group or an aryl group, R ₄ is a hydrogen atom, an alkyl group, an aryl group, a sulfonyl group,
It represents a carbamoyl group, an alkoxycarbonyl group or a carboxy group, and PUG represents a photographically useful development inhibitor group. The alkyl group in the above general formula is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an iso-propyl group, a t-butyl group,
n-octyl group, n-octadecyl group, etc., and the alkyl group has a substituent such as an alkoxy group, hydroxy group, carboxy group, alkoxycarbonyl group, cyano group, amino group, or aryloxy group. Good too. The aryl group refers to a phenyl group or a naphthyl group, and the aryl group mentioned above includes a hydroxy group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, an acylamino group, a cyano group, a nitro group, a halogen atom, and an amino group. , a sulfo group, a sulfonamido group, a carbamoyl group, or a sulfamoyl group. A sulfonyl group is represented by _-SO2 - _R5 , and _R5
represents an alkyl group or an aryl group. What is carbamoyl group?

[Formula], R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, or an aryl group. What is an alkoxycarbonyl group?

[Formula] where R ₈ represents an alkyl group or an aryl group. The alkyl group and aryl group of R ₅ to _{R 8} are the same as those described above. The coupling component represented by Coup in the compound according to the present invention (hereinafter referred to as "coupling component according to the present invention") is a color-forming coupler commonly used in color photographic materials. For example, regarding yellow couplers, US Patent Nos. 2298443, 2407210, 2875057,
No. 3048194, No. 3265506, No. 3447928 and {Falpkupler Einellitera Traubersicht AGFA Mitstelung (Band)}
“Farbkupplereine Literaturubersieht”Agfa
Mitteilung (Band)} pages 112-126 (1961)
A benzoylacetanilide type yellow coupler or a bivaloylacetanilide type yellow coupler described in et al. can be used. Regarding magenta couplers, US Patent No. 2369489, US Patent No. 2343703, US Patent No. 2311082,
Same No. 2600788, Same No. 2908573, Same No. 3062653,
No. 3152896, No. 3519429 and the above-mentioned {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-mentioned Agfa Mittelung (band) {Agfa
Mitteilung (Band)} pages 156-175 (1961)
The naphthol or phenolic couplers described in . 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 No. 3928041, No. 3958993, No. 3961959, British Patent No. 861138, etc. Photographically useful development inhibitor-based PUGs include:
It may be any development inhibitor group that is made available in an image-like pattern within the silver halide photographic material. Representative examples of these photographically useful development inhibitor groups include U.S. Pat.
No. 3615506, No. 3617291, No. 3617291, No. 3615506, No. 3617291, No.
Mercaptotetrazole group, selenotetrazole group, mercaptobenzothiazole group, selenobenzothiazole group, mercaptobenzoxazole group, selenobenzoxazole group, mercaptobenzimidazole group, selenobenzimidazole described in No. 3733201 and British Patent No. 1450479, etc. group, benzotriazole group, benzodiazole group, and 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. Examples of synthesis of compounds according to the present invention will be described below. Synthesis example (synthesis of exemplified compound (1)) Tetrahedron Letters Tetrahedron
17 g of β-chlorocinnamaldehyde obtained with reference to Letters, (1968) 1317 and 1,4-dihydroxy-N-(2-n-tetradecyloxyphenyl).
24 g of -2-naphthamide was stirred in 200 ml of DMF under a nitrogen stream, and an aqueous solution of 2.5 g of NaOH was gradually added dropwise. After reacting at 80°C for 5 hours, the mixture was poured into ice containing hydrochloric acid and the crystals were filtered off. After washing with ethanol and drying, β-{4-hydroxy-3-(2-n-tetradecyloxyphenyl)carbamoyl-1-naphthoxy}-β-phenyl-cinnamaldehyde ()
27.2g of was obtained. 20 g of () was dissolved in 100 ml of DMF, 1 g of NaBH ₄ was added while stirring at room temperature, and after 1 hour the reaction solution was poured into ice water containing hydrochloric acid. Extract with ethyl acetate, dry over anhydrous magnesium sulfate, and concentrate under reduced pressure to obtain an oily β-
{4-hydroxy-3-(2-n-tetradecyloxyphenyl)carbamoyl-1-naphthoxy}
-18.7 g of β-phenyl-cinnamic alcohol ()
I got it. 15 g of () was dissolved in benzene, 5 ml of acetyl chloride was added, and the mixture was stirred at room temperature for 3 hours. It was concentrated under reduced pressure and dissolved in 100 ml of acetone. 1-phenyl-5-mercaptotetrazole
5 g of Na salt was added, and the mixture was stirred at room temperature for 2 hours. After concentration under reduced pressure, the target band was separated by silica gel column chromatography using benzene/ethyl acetate as a developing solvent. 8.3 g of Exemplified Compound (1) was obtained. Confirmed by mass spectrum NMR at mp123-125.5°C. 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 as required. 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 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 any one or more of these constituent 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 oxidized 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, curing agents, plasticizers and surfactants. Regarding silver halide emulsions and additives, please refer to "Research Disclosure" for example.
Further details are given in 1971/12/9232. 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 Hydroxyamine 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 sample to which the compound of the present invention was added had a more pronounced gamma adjustment effect than the comparative sample to which the DIR coupler (A) was directly connected to the inhibitor. It turns out that it is possible to change it. The above five types of samples were stored at 60 degrees 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 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 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-1,2,4triazolidin-4-yl)-2'-chloro-5'-
Blue-sensitive silver iodobromide emulsion layer containing 1.80 g/m ² of (α-dodecyloxycarbonyl-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 multilayer 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. Then, 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-β-hydroxyethylaniline sulfate 3.55g Potassium sulfite 2.0g Anhydrous potassium carbonate 30.0g Potassium bromide 1.25g Potassium iodide 0.0006g pH adjusted to 1 by adding water 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] As is clear from Table 3, the γB/γW values of samples (8) and (9) to which the compound of the present invention was added are larger than those of samples (6) and (7). , meaning 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, it is clearly shown that when using the compounds according to the present invention, a greater interlayer effect (interimage effect) can be obtained than when using conventional DIR couplers. 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 capable of coupling with an oxidized color developing agent, and is bonded to an oxygen atom at a position capable of coupling with the oxidized product, and R ₁ , R ₂ and R ₃ are each a hydrogen atom. ,
It represents an alkyl group or an aryl group, R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group or a carboxy group, and PUG represents a photographically useful development inhibitor group.