JPS58209737A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material superior in coupling performance and contg. a compd. good in storage stability, by adding at least one compd. represented by a specified formula. CONSTITUTION:In the formula shown, Coup is a coupling component capable of coupling with the oxidation product of a color developing agent and combined with a pyrazolotriazole ring at that coupling position; R1, R2 are each H, alkyl, or aryl; R3, R4 are each alkyl or aryl; PUG is a photographically useful group, and whatever group is made usable by an imagewise pattern may be used, and the most preferable form is a development restrainer. The component represented by Coup may be a color forming coupler generally used for color photographic sensitive material.

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 groups in a timely manner.

Various means are known for imagewise release of photographically useful groups from compounds intended for photographic use. For example, Whitmere et al., U.S. Pat. No. 3,148,062 and 13arr et al., U.S. Pat. No. 3,227,554, disclose the release of development inhibitors or dyes from the coupling site of a photographic coupler by reaction of the photographic coupler with an oxidized color developer. Also, U.S. Pat. No. 3,705,801 to Hotz discloses a photographic strength dollar that releases a bleach inhibitor (H) from the coupling site after reaction of the coupler with an oxidized color developer. .

The methods disclosed above as prior art and the compounds used all belong to the system of directly releasing photographically useful groups from these compounds. However, such direct The method of release may be necessary to accelerate, retard, or adjust the release time of the photographically useful groups described above in relation to various reactions with other materials occurring within the photographic element, or It is very difficult to make adjustments when it is necessary to move a photographically useful group by a predetermined distance in a predetermined constituent layer or position within the photoreceptor, in order to expect the desired effect.

Therefore, in order to improve this using the prior art, it is necessary to select a component that liberates a photographically useful group, and also to find a means for attaching a photographically useful group to such a component. In addition to this, we must also carefully consider the selection of the photographically useful group itself.
Although consideration from a wide range of viewpoints is essential, such adjustments, however, are inconsistent with the purpose and effect expected of the ingredients or photographically useful bases described above, and are therefore less effective for a given purpose. This results in a loss of freedom in selecting compounds.

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 form of the color developing agent and cleavage as the first step, an intramolecular nucleophilic substitution reaction is performed to perform the second step of cleavage. This allows for the release of photographically useful groups, thereby controlling many parameters such as temporal adjustment of the effects of photographically useful groups, distance, all, etc.
In order to achieve this, X* is made possible over a wide range.

The photographic strength dollar specifically described in the above 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 cases where it is necessary to use a coupler component with low coupling performance, or there are undesirable problems in that the coupler component decomposes during storage and deteriorates the silver halide photographic light-sensitive material.

In order to improve these drawbacks, Japanese Patent Application Laid-Open No. 56-1149
Although an improvement was proposed in No. 46, the above-mentioned drawbacks have not yet been completely solved.

An object of the present invention is to further improve the above-mentioned drawbacks and to provide a silver halide X-sensitive material containing a compound having excellent coupling performance and good storage stability.

As a result of extensive 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. It has been found that the above object can be achieved by incorporating it into a photographic material.

In the formula, Coup represents a coupling component capable of coupling with the oxidized color developing agent, and is bonded to the pyrazolotriazole nucleus at a position capable of coupling with the oxidized color developing agent, and R1 and R2 are each a hydrogen atom. , represents an alkyl group or an aryl group, and R1 and R4 each represent an alkyl group or an aryl group. PUG represents a photographically useful group.

The alkyl group in the general formula preferably has 1 carbon atom.
~20, such as methyl group, ethyl group, 1ao-
propyl group, ter-butyl group, n-octyl group or n
-octadecyl group, etc., and the alkyl group described above may have a substituent such as an alkoxy group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a sia/group, an amino group, or an aryloxy group.

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 carboxyne group, an alkoxycarbonyl group, an acyl group, an acylamino group, a cyano group, a nitro group, a halogen atom, and an amide group. , a sulfone group, a sulfo group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group.

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") includes color-forming couplers that are generally used in color photographic materials.

For example, yellow couplers are described in U.S. Pat. No. 2,298.
No. 443, No. 2.407, 210, No. 2.8
No. 75.057, No. 3,048,194, No. 3
No. 265.506, No. 3,447,928 and Fasis “Kuzuraai” Literatoulva ~ Jitsuhito Agfa Mitztelung (Band II) (Fa
rpku-pplure:Lne Literatu
rubersi@ht Agfa Mitteilun
It is possible to use benzoylacetanilide type yellow couplers or pivaloylacetanilide type yellow couplers, which are described in eg (Band■)) pp. 112-126 (1961). In addition, Magenta Cabra~ is US Patent No. 2,369,489, US Pat.
, 343,703, 2,311,082, 2,600,788, 2.90L 573, 3,062,653, 3,152.896,
No. 3,519,429 and the above-mentioned Agfa Mitteilung (Band [I)
ung (Band II)) pp. 126-156 (
Various magenta colorants can be used, such as pyrazolone magenta couplers and indacylon magenta couplers, as described in 1961).

Furthermore, in the case of cyan couplers, U.S. Pat.
No. 7.531, No. 2,423,730, No. 2.4
No. 74,293, No. 2.77i, No. 162, No. 2.
No. 895,826, No. 3,002,836, No. 3
．． No. 034,892, No. 3,041,236 and the above-mentioned Agfa Mitztelung (Tendo II) Agfa
Mitteilung (Band II)) 1
56-175 (1961))
- In addition to these couplers, phenolic or phenolic thread couplers may be used, such as German Patent Application No. 2,644
The black dye-forming coupler described in No. 914 can also be used. On the other hand, compounds that react with oxidized color developing agents such as cyclic carbonyl compounds or do not form color dyes can also be used in the cup according to the present invention. These coupling components are described in U.S. Pat.
, No. 632,345, No. 3,928,041, No. 3,958,993, No. 3,961,959, and British Patent No. 861°138.

The photographically useful group PUG may be any group that can be made available in an image-like pattern within the silver halide photographic light-sensitive material.

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. membrane agent,
Tanning agents, toning agents, fogging agents, antifoggants, chemical or optical sensitizers, desensitizers, photographic dyes or their precursors, couplers (e.g. competitive couplers, color forming couplers or development inhibitors - release power blurrs) (i.e., DIR-coupler, etc.). Furthermore, C; y u p is not necessarily a color-forming coupler, but may also be a so-called colorless coupler, and PT7G can also be freely selected depending on the individual purpose f. Among these photographically useful groups, the most preferred is a development inhibitor. A typical example is U.S. Patent No. 3.
, 227,554, 3,384,657, 3,615,506, 3,617,291, 3,733,201 and British Patent No. 1.450.
Mercaptotetrazole group, selenotetrazole group, mercaptobenzothiazole group, selenobenzothiazole group, mercaptobenzoxazole group, selenobenzoxazole group, mercaptobenzimidazole group, mole/benzimidazole group, benzotriazole group, which are described in No. 479 etc. groups, benzodiazole groups, and iodine atoms1, and these compounds also include PU()
Because it can be released at the right time, the photographic effect is outstanding.

Specific examples of the compounds according to the present invention are shown below.

The present invention is not limited to these compounds.

Exemplary compound Examples of synthesis of compounds according to the present invention will be described below.

Synthesis Example (Synthesis of Exemplary Compound (1)) 3-phenyl-6-methyl-pyrazolotriacy #20
9 was dissolved in 250 m of 5% NaOH solution, stirred at room temperature, and 35% formalin solution 20- was added.

After 1 hour, the mixture was neutralized with acetic acid and the crystals were filtered off. Washing with methanol gave iB of 3-phenyl-6-methyl-7-hydroxymethyl-virazolotriazole (1).

α-chloro-α-pivaloyl-2-chloro-5-Cr-
(2,4-di-t-amyl 7eth/xy]butyramide)
Acetanilide 30.9 and (1) 12.9 were dissolved in acetonitrile 3001jK, 6 g of triethylamine was added, and the mixture was stirred at 50°C for 8 hours. The reaction solution was reduced under reduced pressure [itl, -,
The syrupy substance obtained by extraction with ethyl acetate and concentration was precipitated with methanol to give α-pivaloyl-α-(3-phenyl-6-methyl-7-hydroxymethyl 1-pyrazolotriazolyl)- 27.4.9 of 2-chloro-5-(r-(2,4-di-t-amylphenoxy)phythylamido]aceto7nylide (II) was obtained.

16 g of (II) was dissolved in benzene, and while stirring at room temperature, 4.2 p of phosphorus pentachloride was added, and after 2 hours, cold water was added.

The benzene layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. After dissolving in acetone, 4 g of 1-phenyl-5-mercagutotetrazole was added, reacted for 2 hours, and concentrated under reduced pressure. It was extracted with ethyl acetate and washed with sodium carbonate. After that, heat the ethyl vinegar layer.

The target product band was extracted from the candy-like residue by silica gel column chromatography using benzene/ethyl acetate as a developing solvent. 5.4 g of Exemplary Compound (1) with m and p of 74 to 81°C was obtained. Mass spectrum, NMR
Confirmed by.

Other compounds can also be synthesized in a similar manner.

The silver halide photographic light-sensitive material of the present invention can be processed according to the processing techniques 11MK used in color development bleaching, fixing, or ordinary color reversal materials. Same No. 3,822,12
No. 9, No. 3,834,907, No. 3,841,8
No. 73, No. 3,847,619, No. 3,862,
No. 842, No. 3,902,905 and No. 3,92
An image amplification process using an oxidizing agent such as a transition metal complex (e.g., cobalt hexamine) or a dissipated product (e.g., hydrogen peroxide) described in No. 3,511 can also be applied to the halokenes of the present invention. The silver oxide photographic material 'f+ has a single silver halide emulsion layer on a support (it may also consist of multiple silver halide emulsion layers).

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
The order of the stiff layers each having at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer can be selected as required.

Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming duller, and the blue-sensitive emulsion layer contains a yellow-forming duller, but different combinations may be used depending on the case. Further, the silver halide photographic hanging material format of the present invention has f.
It may also be used for single layer black and white photography with a black dye imaging cuffer.

The f-hybrid effect according to +/C of the present invention may be contained in the analyzeable silver halide emulsion layer of these silver halide photographic light-sensitive materials, or may be contained in the layer adjacent thereto (・0 and,
It can be contained in any one or more of these constituent layers at the same time.

Further, when these compounds are contained in a silver halide photographic light-sensitive material, the amount of il added is o, per mole of silver halide.
oos to 0.1 mol is preferred. Particularly preferably 0.
The range is from 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 filter compound according to the present invention is dissolved in a high boiling point 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 process of manufacturing the reflective material.

1. 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 becomes colloidal particles and is dispersed.

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 diffusible, one or more scavengers may be interposed at appropriate positions in the constituent layers of the monochrome-sensitive material. The layer or unit layer affected by the above photographically useful groups can be filtered by the method.

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 monobromide, silver iodobromide, or silver chloroiodide. These silver bromide emulsions can be prepared by conventional methods and further chemically sensitized.

Therefore, the silver halide emulsion can be applied to the present invention regardless of whether it is monodisperse or polydisperse, grain size, grain shape, negative emulsion, positive emulsion, internal a-grain type, or surface latent image type. be.

Known chemical sensitizers can be used in the above chemical sensitization. Furthermore, these emulsions may contain commonly used additives such as photosensitive dyes, anti-capri agents, curing agents, plasticizers and surfactants.

Regarding silver halide emulsions and additives.

For example, “Research Disclosure” 1971 1
Further details are given in February 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. Good too. and the present invention (where the photographically useful group released from such compounds is a development inhibitor, e.g. U.S. Pat. No. 3,227,554)
No. 3,620゜747 and No. 3,703,3
The compound according to the present invention can be used from the photosensitive material f described in No. 75. Since the release of the photographically useful group can take place indirectly, its use makes it easier to control its action and effect in the photographic material (in terms of time and distance). can be adjusted, so
Development inhibitor releasing couplers (DIR couplers) as described in U.S. Pat. No. 3,227.554 and development inhibitors as described in U.S. Pat. Compared to the interlayer effect (interimage effect) obtained by drug-releasing compounds (DIR compounds), the interlayer effect obtained by the compound according to the present invention can be expected to be more excellent.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The stiffness does not limit the embodiments of the present invention.

Example 1 As a masenta cuffler, 15 g of 1-(2,4,6--7-amylphenoxyacetamide)penzamide 5-pyrazolone was dissolved in 30-dK ethyl acetate and 15 dK diptylphthalate, and this was dissolved in Alkanol B (DuPont ) 10% aqueous solution 2〇- and 5% gelatin aqueous solution 2
00- and emulsified and dispersed using a colloid mill. Thereafter, this dispersion was added to a green-sensitive silver iodobromide emulsion (containing 3.0 mol % silver iodide) 1k17 and dispersed, and then applied to a triacetate base and dried. This is designated as sample (1) (control sample).

The above control sample (1) K vs. j-4 types of DI as shown in Table 1
Samples (2), (3), (4) and (5) were prepared by adding R Kaglar in the amounts shown below.

DIR power dollar (4) (J Dl coupler 1B) (7! It was developed, bleached and fixed, and then washed with water.

(Color developing agent iIl composition) The results obtained are shown in Table 1 below.

Table 1 As is clear from Table 1, the sample to which the compound according to the present invention was added had almost no difference in sensitivity compared to the precipitated sample to which the DIR dyadr-container directly connected to the inhibitor was added, and the gamma adjustment effect was remarkable. It turns out that it is possible to change the effect.

The five types of samples mentioned above were stored at 60°C and 80% RI (for 2 days) and then subjected to a short exposure and development process. The results are shown in Table 2. 1 The compound according to the present invention is DI
Comparing R coupler fB) K, it can be seen that it is an excellent compound that has excellent storage stability and does not contribute to the deterioration of photosensitive materials.

Practical 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-triacyridin-4-yl)-2'-Chloro-5'-(α-dodecyloxycarbonyl-ethoxycarbonyl)acetanilide 1. so g/lri, gelatin λ4,! i' /
A blue-sensitive silver iodobromide emulsion layer containing yl and silver halide 1.61/m''.

(2) Luceratin interlayer containing 0.5 l/m'' of gelatin and 0.19/m'' of 2,5-di-t-meritylhydroquinone.

(3) As a cyan coupler, 1-hydroxy-N
-(4-(2,4-di-t-amylphenoxy)butyl]-2-su7tamide 0.47!j/go, gelatin 2-
49/ze, silver halide L 6 ,! (4) a protective layer consisting of gelatin 0.8 i/m".

Among the constituent layers of the multilayer coating sensory 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), ('
1′), (8) and (9) were created.

24- DIR Kadalar (DI I CH.

Each sample′? : The sample was divided into two parts, and one sample was subjected to wedge exposure using Ku white light, and the other sample was subjected to wedge exposure using blue light. Then, a color developing solution with the following composition was used for 38 minutes.
C. for 2 minutes, bleached and fixed, and then washed with water.

(Color developer composition) For each sample, determine the gamma value from the characteristic curve of the yellow dye obtained by color development, and divide the gamma (rB) due to blue exposure by the gamma (rW) due to white exposure using the following formula. It is shown in Table 3.

As is clear from Table 3, Samples (6) and ('I)
The fact that the γB/rW values of samples (8) and (9) to which the compound according to the present invention was added is larger than that of the samples (8) and (9) to which the compound according to the present invention was added means that the amount of development inhibitor in the red-sensitive layer is higher in the sample according to the present invention than in the sample (8) and (9). In other words, when the compound according to the present invention is used, the Kl/i is higher than that of the sample, and the conventional DIR
The above practical example clearly shows that a larger interlayer effect (interimage effect) can be obtained than when using a doubler. Almost the same results were obtained even when applied to a so-called false color negative film in which the absorption wavelength ranges of dyes are not complementary.

Agent Yoshi Kuwahara (Beautiful Procedural Amendment Show) n 57:1: 9n-jll, Patent 11 Chief 1+
Mr. Kazuo Wakasugi 1 filed a patent application with a sum of 11 μm and 57 in case J) 93558 2. Name of the invention Silver halide photographic light-sensitive material '3 Supplement 1 Address 1-26-25 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Konishiroku Photo Industry Co., Ltd. Ne1 Representative Director Nobuhiko Kawamoto 4 Agent Address 191 Address Tokyo 1 11 Noichi Gokurimachi 5 ;1lt
lh+173&)3i;] 17. Contents of amendment (1) The detailed description of the invention is amended as follows.

Claims (1)

[Scope of Claims] A silver halide photographic material containing at least one compound represented by the following general formula. In the formula, Coup represents a coupling component capable of coupling with the oxidized color developing agent, and is bonded to the pyrazolotriazole nucleus at a position capable of coupling with the oxidized color developing agent, and R1 and R7 each represent hydrogen. atom,
It represents an alkyl group or an aryl group, and R3 and R4 each represent an alkyl group or an aryl group. PTJG represents a photographically useful group.