JPS58209736A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material contg. a compd. releasing a photographically useful group indirectly at a timing, by adding at least one of the compds. represented by a specified formula. CONSTITUTION:In the formula shown, A is H or a group releasable under photographic processing conditions. PUG is a photographically useful group having at least one hetero atom in the molecular structure, and a development inhibitor is most preferable. PUG is combined by the medium of a timing group with a component capable of coupling, and since it is indirectly released, its action and effect can be controlled with respect to time and distance, and hence, excellent synergistic effect can be expected.

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.

Regarding photographic additives, especially those that act during processing (
However, if all additives are added, they may exhibit other undesirable effects. To improve it, we use a protected form, the so-called precursor:'
:ll not only reduces the effects before processing, but also helps! ! It is also possible to obtain effects by releasing additives in response to processing time, and in some cases, additives are used in a form that allows them to act imagewise.

For example, U.S. Pat.
No. 148ρ62 and U.S. Pat. No. 3.22 to Barr et al.
No. 7,554 discloses that the reaction between a photographic coupler and an oxidized color developer releases a development inhibitor or dye from the coupling site of the photographic coupler.
There are 7.

Also, Ho1tz's US*lfF No. 3,705.8 (
No. 11 discloses a photographic coupler that releases a bleach inhibitor from the coupling site after reaction of the coupler with an oxidized color developer.

Method 2 and the compounds used as disclosed above as prior art are all based on methods in which photographically useful groups are directly released from these compounds.

However, this more direct release method is important in relation to the reactions caused by other materials that occur within silver halide photosensitive materials. In cases where it is necessary to accelerate or delay the IMI at the time of release, or in order to expect the effect in a predetermined constituent layer or position in a non-rogenated photographic material,
When adjustment is required to move a photographically useful group by a predetermined distance, the adjustment is very difficult.

Therefore, in order to improve this according to the prior art, it is necessary to select components that release photographically useful groups, and also to attach photographically useful groups to such components. In addition to considering the method, it is also important to carefully consider the selection of the photographically useful group itself, so it is important to consider it from a wide range of viewpoints. This is contrary to the purpose and effect expected of a photographically useful material.
This results in a loss of freedom in selecting compounds for a given purpose. On the other hand, one technique to improve these is to provide a linking group (coupling/imming group) between a binding group or coupler and a photographically useful group, thereby maximizing the functions of each. means are disclosed.

Special Publication No. 54-'39727 and Patent Application No. 176-1982
No. 44 describes linking groups which form quinone methides or naphthochimeretides, releasing 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.

Also, JP-A-54-145135 and JP-A-55-5333
No. 0 describes a bonding group that causes an intramolecular nucleophilic substitution reaction to release a photographically useful group.

According to the layout of the above publication, after reacting with the chemical compound 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, and the final target product is obtained. In order to release a certain photographically useful group and thereby control many parameters such as temporal or distance adjustment of the effect of the photographically useful group,
Allows adjustment over a wide range.

However, when using the means and compounds described in the above-mentioned publication, since some compounds are included that undergo a nucleophilic substitution reaction with hydroxide ions in the color developing solution, effects should not be expected only in the exposed areas. However, it has the disadvantage that photographically useful groups are released even in the unexposed region.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material containing a compound which is significantly improved in decomposition by a photographic processing solution and which releases photographically useful groups indirectly and in a timely manner. It is in.

The present inventors have developed a compound represented by the following general formula (1) -(
Hereinafter, it will be referred to as "the compound according to the present invention". It has been discovered that the above object can be achieved by incorporating at least a portion of ) into a halogenated photographic material.

General formula (υ 2 In the formula, × represents the atomic group necessary to complete the benzene residue, and Y represents the atomic group necessary to complete the 5- or 6-membered heterocycle formed by the above benzene residue. , A is a hydrogen atom or a group that can be separated under photographic processing conditions, 1 2 , R1 and R2 are a hydrogen atom, /S rogen atom, an alkyl group, an aryl group or a bicyclic ring residue, PUG is bonded to -C- with at least one heteroatom in the molecular structure.

2. Specifically, the groups that can be separated under photographic processing conditions, as shown in A above, include acyl groups that can be hydrolyzed with alkali, sulfonyl groups, and groups that can be coupled by coupling with oxidized products of color-developing crude drugs. The portion of the coupler that is bonded at the nucleation position, the group that can be separated by oxidation-reduction reaction, especially the group that is released by being oxidized by the color developing main chestnut oxidant, or the group that is reduced by a reducing agent such as hydroquinone. Indicates a group that can be separated by

Specifically, the 5- or 6-membered heterocycle represented by Y, which is a fused benzene ring, is a saturated or unsaturated 5- or 6-membered heterocycle containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.
It represents a membered ring, a six-membered ring, etc., and together with the benzene ring formed by x, examples include quinoline nucleus, inquinoline nucleus, phthalazine nucleus, quinoxaline nucleus, quinazoline nucleus, dinoline cedar, benzotetrazine nucleus, coumarin nucleus, coumaranone cherry tree, benziodine nucleus. Long thiazine nucleus, active water phthalic acid nucleus, phthalimide nucleus,
Indole nucleus, oxindole cherry, benzofuran nucleus,
Forms a benzothiophene nucleus or a benzoxathiazole nucleus. These include alkyl groups, aryl groups, alkoxy groups, amino groups, acid amide groups, sulfonamide groups, carboxy groups, alkoxylponyl groups, carbamoylnitro groups, sulfo groups, sulfamoyl groups, sulfonyl groups, carbonyloxy groups, formyl groups, or )・May have a substituent such as a rogen atom.

Examples of coupling components that can react with the oxidant of the color development condensate include color couplers that are commonly used in color photographic materials.

For example, yellow couplers are disclosed in U.S. Patent No. 2,298.
No. 443, No. 4407,210, No. 2,87
5,057, same No.3.

No. 048, 194, No. 3,265.506, No. 3
, No. 447, 928 and (Falpukpraaineri de la Toul/Kuji,/Toagfaminoterungu (Buff)
tl','l l・(Farb-Kupler
- eine Literaturubersich
t+AgfaMitteilung (Band II
) ] pages 112 to 126 (1961), benzoylacetanilide type yellow couplers or pivaloylacetanilide type yellow couplers can be used.

Regarding magenta couplers, U.S. Patent Nos. 2 and 3
No. 69,489, No. 2,343,703, No. 2,
No. 311,082, No. 2,600,788, No. 2
, 908, No. 573, No. 3ρ6a653, No. 3
No. 52,896, No. 3,519,429 and the above (Agfamittelung (Band II)) (
hg-fa Mitteilung (Band II)
) 126-156 Negative (1961), various magenta couplers such as pyrazolone magenta couplers and bindazolone magenta couplers can be used.

Furthermore, in the case of cyan couplers, U.S. Pat.
No. 7,531, No. 2,423,730J, “No. 2,
No. 474,293, No. 2,774162, No. 2,
No. 895,826, No. 3ρ02,836, No. 3,
No. 034,892, No. 3.041,236 and the above (Agfa Mittelung (band n)) [Agfa-
Mitteilung (Bind n)) 156 ~
The naphthol or phenolic couplers described on page 175 (1961) can be used.

In addition to these couplers, West German Patent Publication G 1644,9
The black dye-forming coupler described in No. 15 can also be used.

On the other hand, compounds that react with oxidized color-developing crude drugs, such as cyclic carbonyl compounds, but do not form color-forming dyes can also be used as compounds according to the present invention.
U.S. Pat. No. 3,632,345 for these compounds.
No. 3,928,041, No. 3,958,99
No. 3, No. 3,961,959 and British Patent No. 8
61°138.

The photographically useful group may be any group that can be used in a conventional pattern in a silver halide photographic light-sensitive material.

Specific examples of photographically useful groups include development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, developing agents, fixing agents, silver halide solvents, and silver-complexing agents. , hardeners, tanning agents, toning agents, capri agents, antifoggants, chemical or optical sensitizers, desensitizers, photographic dyes or their precursors, sword pullers (e.g., competitive couplers, color forming couplers, Development inhibitors - releasable force pullers, i.e. f) IR-
couplers, etc.).

Of these four truly useful groups, the most preferred are development inhibitors, representative examples of which are U.S. Pat.
, 227,554, 3,384,657, 3゜615.506, 3.617291, 3,733.201 and British Patent No. 1,450,4.
Merca described in No. 79, poutetodizole, selnotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole,
Selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole, benzodiazole or iodide.

Among the compounds represented by the general formula (1), those represented by the following general formula Q) are particularly preferred in the present invention.

"z-1, (" General formula (2) In the formula, AXR,, R2, Y and PUG are respectively synonymous with those defined in the above general formula (1), m and n
represents 1 or 2, where m (n.) When 1 2, h l is in the ortho position, m = 2, n =
When it is 1, it is in the ortho or rose position.

Specific examples of compounds according to the present invention are listed below, but the invention is not limited thereto.

14- 13, OH ＝　＼ Below - Margin X・　7 N==N L Kudzu C,Im Next, a synthesis example of the compound according to the present invention will be described.

(Synthesis example-1) Synthesis of exemplified compound? lJ Compound 1 5-chloromethyl-8-hydroxyquinoline base acid field is:
The Journal of Organic Ch.
emistry 25, 4080 (1961) was synthesized from a rare fish.

2.32 of this 5-chloromethyl-8-hydroxyquinoline hydrochloride was dissolved in 20 parts of acetone and 10 parts of water, and 0.7'l of pyridine was added. To this, 5-mercaptotetranyl sodium salt 2. The mixture was stirred for 1 hour using a tumbler. 100ml of water and 100ml of ethyl acetate were added to the reaction solution, and 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 Exemplified Compound 1 with ID2 (Synthesis Example-2) Synthesis of Exemplified Compound 6 (1zC2) It was dissolved in methanol 2o1Rt, 1.75f of 5-hydroxymethyl-8-hydroxygynoline was added thereto, and after stirring for a few minutes, m
m and fC,. Add to this 6.06f of (1) and DI)/iF
30- was added and stirred for 3 hours. H2O2 to the reaction solution
00rnt and 200ml of ethyl acetate were used to separate one cycle of ethyl acetate. Ethyl acetate was first washed with dilute hydrochloric acid and then with a sodium carbonate solution, then washed with water, dried on anhydrous sodium sulfate, and then evaporated under reduced pressure. The desired product was separated and produced by silica gel column chromatography using benzene-acetone as a gold dilution medium.

A pale yellow caramel-like substance was obtained, and its presence was confirmed by NMR and mass spectrometry.

(To) Synthesis (II) 2.52 was dissolved in 50-chloroform, 0.71 of phosphorus pentachloride was added, and after reacting for 2 hours, H2
The chloroform layer was extracted by adding O100m. The chloroform layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a pale yellow caramel-like substance. N.M.
It was confirmed that it was (2) by R and mass spectra.

2.51 of Synthesis (2) of Exemplified Compound 6 and 1-phenyl-5-mercaftotetrazole sodium! 0.7V to acetonitrile 50-
After heating for 11 minutes, concentrate under reduced pressure - Extract with ethyl acetate, and carbonate the extract 5%). Concentrated. Compound 6 was separated from this citrate "i" f21 by solitary gel chromatography using benzene-acetone as a developing solvent, and recrystallized with a benzene-dry mixed solvent.

It was confirmed by NMR and mass spectra that the exemplified compounds were the same.

Other exemplified compounds can also be synthesized in the same manner.

The halogenated photographic material containing the compound according to the present invention can be processed according to the processing steps used for color development, bleaching, slow-grading, or ordinary color reversal light-sensitive materials.11. Additionally, U.S. Patent No. 3,674,490
No. 3,822,129, No. 3,834,90
No. 7, No. 3B41.873, No. 3,847,61
No. 9, No. 3,862.842, No. 3.902.9
85 and 3.923511 using oxidizing agents such as transition metal complexes (e.g. cobalt hexamine) or peroxides (e.g. hydrogen peroxide). We can also take care of the processing.

The compound according to the present invention can be used as a silver halide photographic material which has a single silver halide emulsion layer on a support or a multilayer halide emulsion layer. It may also consist of

Multilayer natural color photographic materials usually have at least one sensitive emulsion layer, one green-sensitive emulsion layer, one green-sensitive emulsion layer, one emulsion layer, and the order of these layers. Select arbitrarily as necessary. It is usual to use a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the evening-sensitive emulsion layer. You can also take

The silver halide photographic photosensitive material of the present invention can also be used for black-and-white photography consisting of a 1h-addition using a black dye-forming coupler on a support.

The compound wJ according to the present invention may be contained in a layer adjacent to the photosensitive silver halide emulsion layer of these silver halide photosensitive layers.

And, these compositions and wisdom are one or more! The small weight of the compound to be added to the halogenated compound in the original material is 0 per mole of silver halide. .01
~3 moles.

There are various methods for incorporating the uninvented compound into silver halide photographic materials, but what is the typical method? lI
If you fail, you will have to go back to the next step.

(a) The compound according to the present invention is bathed in a high-boiling point organic solvent, and the bath solution is emulsified and dispersed in an aqueous medium and cooled to form an emulsion.

←) The inventive compound gold bath dissolved in a low boiling point solvent that is relatively sparingly soluble in water is emulsified and dispersed in an aqueous medium and added to a photographic emulsion. The Ariiso solvent used is removed during the photosensitive material manufacturing process.

(c) When the uninvented compound is mixed with water and turns brown, when this solution is added to a photographic emulsion, the compound becomes fine colloidal particles and is dispersed.

1. Depending on the solubility of the liquid, the above baths and powders may be mixed and used, or the dispersion aid may be used in pieces.
If the photographically useful group is diffusible, then the photographically useful group is diffusible.
Singular again? By interposing a 9 fV scavenger layer at an appropriate position of the constituent layers of the halogenated photographic light-sensitive material, it is possible to control the layer or layer affected by the above-mentioned photographically useful groups. The silver halide used in the halogenated e-photographic light-sensitive material of the present invention is prepared by a conventional method, and includes chloride wax, silver bromide, dichlorobromide, silver iodobromide, and salt. It may be of any composition, such as iridescent. These silver halide emulsions can be prepared by conventional methods and further chemically sensitized.

Therefore, the silver halide buttock 1 can be used in the present invention regardless of whether it is monodisperse or polydisperse, grain size, grain shape, negative emulsion, positive emulsion, internal m-image type, or surface temperature image type. It is possible.

In the above chemical sensitization, known chemical sensitization 1♀1 can be used. Furthermore, these emulsions contain photosensitive dyes,
Commonly used additives such as antifoggants, curing agents, plasticizers, surface active agents, etc. may be included.

Regarding halogenated emulsions and additives, please refer to Section 11 "Re5earch Disclosure".
9232, December 1971, in further detail.

The compound according to the present invention can be added to p-silver saponide photographic light-sensitive materials for various purposes and arrangements according to the action and properties of photographically useful groups, and as necessary, various couplers or other compounds can be added. It may be mixed with various additives. The photographically useful group released from the compound according to the present invention can be used in silver halide photographic materials in which the photographically useful group is a development inhibitor.

As described in detail above, the compounds according to the invention are characterized in that one or more photographically useful groups are attached to the coupleable IN moiety via a timing group. Since the release of the group may occur indirectly, by using it, the action and effect of the silver halide photographic material can be adjusted in terms of time and distance. Thus, the development inhibitor releasing couplers (DIR couplers) described in U.S. Pat. No. 3,227,554 and the development inhibitor releasing couplers described in U.S. Pat. type compound (DIR compound)
Multilayer effect (interimage effect) obtained by etc.
1, a more excellent multilayer effect can be expected from the compound according to the present invention.

Example-1 As a magenta coupler, 1-(2,4,6-drichlorophenyl)-3-C3-(2,4-di-t-amylphenoxyacetamide)penzamide]-5-pyrazolone 15r was mixed with ethyl acetate. 30ml of dibutyl phthalate and 15ml of dibutyl phthalate, and 10ml of Alkanol B (manufactured by Devon) and 20ml of water bath solution. and 5tiselatin water soluble fL200rn1. and emulsified and dispersed using a colloid mill. After finishing, this dispersion was added to 1 kg of a green-sensitive iodizing agent (containing 3.0 moles of silver iodide), and after being dispersed, it was applied to a triacetate base and dried. This was designated as sample (1) (control sample) - 1 to the above control sample (1), and the following two DIR couplers and compounds according to the present invention were each listed in Table 1 below. Add it to the emulsion according to the amount added, and prepare sample (2) in the same way.
, created (3), (4) and (5).

(DIR coupler) 翰N=N (JP-A-54-145135 notation) A sample of the above description was exposed to light using a wedge, and color development was carried out at ℃ for 3 minutes using a color developing solution having the following composition, followed by bleaching. After fixing, washing was carried out with water.

(Color developer composition) 4-Amino-3-methylζN-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4,759 Anhydrous sodium sulfite 4.25 F Hydroxylamine sulfate 2.02 Carbonic anhydride Potassium 37.59 Sodium Bromide 1.37 Nitrilotriacetic acid trisodium salt (monohydrate) 2.59 Bufurium hydroxide 1.097! Add 1i to 1i and use potassium chloride to pH 1.
Adjust to O10○ The obtained lees bed is shown in Table 1 below.

Table 1 As shown in Table 1, there is a clear excess in sensitivity, and there is almost no difference in sensitivity between the sample containing the compound of the present invention and the sample containing the DIR coupler (4) directly connected to the inhibitor. It can be seen that the effect is significant and that it is possible to change the effect.

Table 2 shows the rice produced by storing the samples of the above five types at 60° C. and 80 SRH for 2 days and then subjecting them to the same exposure and development process.

Part 2 Excerpt From Table 2 it is clear that the compounds according to the invention can be traced back.

Implementation 'A-2 A basic sample was prepared by carrying out a no-blood test using a vehicle pressure lower than that of the triacetate base.

(1) As a yellow coupler, 2-(2,2-dimethylpropionyl)-2-(1-pencyl-2-phenyl-3,5-dioquine-1,9,4-1lyasiridin-4-yl)-2 Red-sensitive silver iodobromide emulsion layer containing 1.8 + 1/m'' of '-nororo-5'-(α-dodenyloxycarbonyl-ethoxycarbonyl)acetanilide, 2.49/m of gelatin, and 69/m of halogenide. .

Cutting) Gelatin 0.59/n? , and a gelatin interlayer containing 0.17 m''i of 2,5-dioctylhydroquinone.

(3) As a cyan coupler, 1-hydroxy-N
-[4-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide 0.47? /lt? , gelatin 2.4 f/rPt'', and nitrogen halide 1.6 f/-.

(4) Protective layer of gelatin 0.8 f/m'.

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 multi-layer coated photosensitive material according to the usual amounts shown in Table 3.
Types of samples (6), (7), (s) and DIR
Coupler CC) DIR Coupler (I)) l Crystal.

Each sample was divided into two parts, one sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with red light.

Then, it was processed for 12 minutes at 38" C with a color developing solution having the following composition, bleached and fixed, and then washed with water C-.

(Color developer composition) 4-Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 3.55 5' Potassium sulfite 2.02 Anhydrous potassium carbonate 3Q, Or potassium bromide
1.25 F potassium iodide
Add 0.00069 water to make 1 t. The pH is 11.0.

For each sample, the sigamma value was determined from the characteristic curve of the yellow dye obtained by color development, and the values obtained by dividing the gamma (γR) due to red exposure by the gamma (γW) due to white exposure are shown in Table 3 below. show.

(〜・ Sample (6) shown in Table 53 above, as a control sample)
The fact that samples (8) and (9) to which the compound according to the present invention was added both have larger γR/γW values than samples (7) and (7) means that the amount of development inhibitor in the red-sensitive layer is This means that the sample according to the invention also has a higher 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 compounds were added to the sample (1) used in Example 1 according to the amounts shown in Table 4 to prepare samples (total) and alpha swords.

Comparative Compound (1) Compound described in Japanese Patent Publication No. 54-39727 These samples were exposed and processed according to Example 1. The results are shown in Table 4, and the results after forced storage are shown in Table 5.

Table 4 From Table 1 onward, the samples to which the compounds of the present invention were added as shown in Tables 4 and 5 were prepared by the agent of Japanese Patent Publication No. 54-39727.
Yoshimi Kuwahara Procedural Amendment 1982 9J4141 - (Patent + 4 length'1'1 Mr. Kazuo Wakasugi 7.gl Display of case 1982 Patent Application No. 93557 2 Title of invention "Silver halide photographic light-sensitive material 3" Amendment Relationship with the case of a person who does
Nobuhiko lives at 1-6 Sakura-cho, Hino-shi, Tokyo, Column 7 of "Detailed Description of the Invention" of the specification to be amended, Contents of the Amendment (11) The Detailed Description of the Invention is amended as follows.

2-

Claims (2)

[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, x represents an atomic group necessary to complete a benzene nucleus, and Y represents an atomic group necessary to complete a 5- or 6-membered heterocycle condensed with the benzene nucleus. , A is a hydrogen atom or under photographic processing conditions 〈-' -C-PUG is at the ortho or distal position to A-0-, R1 and R2 are nA atoms, halogen atoms, alkyl groups, respectively. , an aryl group or a heterocyclic residue, and PUG is a photographically useful substance having ÷at least one heteroatom in its molecular structure; There is. 2 (2) A patent claim characterized in that A is a cambling 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. A silver halide photographic material according to item (1).