JPH04179948A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure perfect stability during storage and to enable rapid release of a photographically useful group even in a processing soln. of a low pH at the time of processing by incorporating a specified compd. CONSTITUTION:A compd. represented by formula I is incorporated into a silver halide photographic sensitive material with at least one silver halide emulsion layer. In the formula I, each of E1 and E2 is an electrophilic group, E1 is more electrophilic than E2, Y is a substituent which arranges E1 and E2 so that Z is released at the time of processing the sensitive material in the presence of a dinucleophilic seed, Z is a substituent releasable at the time of processing, PUG is a photographically useful group, each of (l), (p) and (q) is 0 or 1, (p) and (q) are not simultaneously 0, in the case of p=0, (PUG)p is H or a substitu ent, and in the case of q=0, (PUG)q is H or a substituent. Stability is ensured during storage and a photographically useful group can rapidly be released at the time of processing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to photographic materials, and more particularly to photographic materials containing blocked precursor compounds that release photographically useful groups during photographic processing.

[Background of the invention]

By incorporating a photographically useful group in a blocked form into a photographic material, various effects can be exerted.

When the photographically useful group is an irradiation-preventing dye, it is desirable that it flow out from the light-sensitive material during processing, so it is usually provided with a large diffusivity. Therefore, when added to a photosensitive material, it is difficult to contain it only in a specific layer, and a large decrease in sensitivity is unavoidable. In this way, by blocking a diffusible photographically useful group with a group having anti-diffusion ability, it is possible to immobilize it only in a specific layer.

If the photographic useful group is a development inhibitor or antifoggant, blocking it can suppress the effect on silver halide during storage, inhibit development without reducing sensitivity, and prevent fogging. It can be prevented.

When the photographically useful group is a component in the processing solution, the composition of the processing solution can be simplified by forming it into blocks and incorporating it into the light-sensitive material.

Precursor technology, which blocks photographically useful groups and incorporates them into light-sensitive materials and releases them during the photographic processing process, is expected to be extremely effective, but it is not stable during storage. It is necessary to release photographically useful groups quickly during processing, and it is not easy to satisfy both requirements.

In this way, by blocking useful photographic groups such as dyes, development inhibitors, development accelerators, developers, fogging agents, etc. with groups that have anti-diffusion ability, they can be fixed only in specific layers,
Precursor technology in which photographically useful groups are released during processing after being dispersed in oil is important, but known blocking groups have poor storage stability or a slow release rate, and conventional blocking groups with low processing pH The performance of photographic light-sensitive materials was far from being practical.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a precursor compound that is completely stable under storage conditions and that rapidly releases photographically useful groups even in a low pH processing solution during processing. Our goal is to provide the following.

[Structure of the invention]

The object of the present invention has been achieved by a silver halide photographic material containing a compound represented by the general formula CI].

General formula [I'1 In the formula, El and E2 are electrophilic groups, and El is more electrophilic than E2. Y is a substituent that arranges El and E2 so as to release Z during processing of the sensitive material in the presence of a dinucleophilic species. Z is a substituent that can be released upon processing. PUG is a photographically useful group. 1. p and q are 0
or an integer of 1. However, p and q never become 0 at the same time. When p is 0, (PUG) p represents a hydrogen atom or a substituent; when q is 0, (PUG) Q represents a hydrogen atom or a substituent.

General formula [I] will be further explained. El and E2 are electrophilic groups, such as carbonyl, imido, sulfonyl, thiocarbonyl, phosphonyl, etc., and carbonyl groups are preferred.

Y is preferably a methylene group which may have a substituent.

A more preferable compound of general formula (I) is the following general formula (
These are compounds represented by I)-1 and (1)-2.

General formula (1)-1 % formula % () General formula (1-2 In the formula, R represents a hydrogen atom or a substituent. A is a group forming a ring. puc, z, p and q are general It has the same meaning as the formula [E]. Preferred groups for R are an alkyl group and an aryl group, more preferably an alkyl group (methyl, ethyl, etc.).When q is 0, (PUG)Q is an alkyl group. Groups (methyl, ethyl, etc.) are preferred.A is preferably a ring-forming group such as cyclopentanone or cyclohexanone.

Z is a group that can be released during processing of the sensitive material in the presence of a dinucleophilic species, and is preferably a diffusion-resistant group.

In the present invention, 2 is selected from a group that does not have any photographic effect after being released during processing.

Examples of Z include alkoxy (hexyloxy, dodecyloxy, etc.), aryloxy (p-octylphenoxy, etc.), heterocyclic oxy (virazolyloxy, etc.),
Examples include groups such as acyloxy (octanoyloxy, benzoyloxy, etc.).

Dinucleophilic species used in the present invention include a variety of compounds such as hydroxylamine, hydrogen peroxide, monosubstituted hydroxylamine, hydrazine, and urea, with hydroxylamine being preferred.

Examples of PUG, which is a useful group for photography, include antifoggants, development inhibitors, color and black and white developing agents, auxiliary developers, development accelerators, fogging agents, contrast agents, dyes, bleach accelerators, bleach inhibitors, No. 10 Silver Genide Solvent, Silver Complex Forming Agent,
Fixing agents, curing agents, etc. can be mentioned. Specific examples of antifoggants and development inhibitors include benzotriazole compounds, benzimidazole compounds, mercaptoimidazole compounds, mercaptothiazole compounds, mercaptotetrazole compounds, mercaptothiadiazole compounds, mercaptotriazole compounds, mercaptooxadiazole compounds, and the like. Specific examples of the developing agent, auxiliary developer, and development accelerator include hydroquinone compounds, catechol compounds, aminophenol compounds, p-phiniciamine compounds, pyrazolidone compounds, and ascorhinic acid compounds. Specific examples of fogging agents and contrast enhancing agents include hydrazine compounds, hydrazide compounds, and tetrazolium salts.

Specific examples of dyes include azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizarin dyes, quinoline dyes, oxonol dyes, phthalocyanine dyes, melonanine dyes, and azomethine dyes. , styryl dye, etc. Specific examples of bleach accelerators include aminoethanethiol compounds, sulfoethanethiol compounds, aminoethanethiocarbamate compounds, and carboxyethanethiol compounds. /・Specific examples of silver halide solvents include thioether compounds, rhodanine compounds, no-warts, methylene bissulfone compounds, and the like. As a fixative, there is Tsutawart. Preferred PIGs include development inhibitors, color and black-and-white developing agents, auxiliary developers, fogging agents, contrast agents, dyes, bleaching accelerators, and the like. More preferred PUG is a dye.

Specific examples of the compound represented by the general formula CI) are shown below.

However, the present invention is not limited to the following compounds.

< v to Otsu
Big? ha ha co
“So
V;-!
! Q ha ha
Hat13 CH3 CH.

Next, a specific synthesis example of the compound represented by the general formula (1) will be shown.

Synthesis example (exemplified compound (1)) (A) CHs Compound (1) [B) It was synthesized by the method shown in the synthesis scheme above.

Compound [33.7 g of compound A and compound (B: 14.9 g and 2.1 g of synchhexylcarbodiimide with 50 g of dioxane
After adding m1 and stirring at room temperature for 3 hours, the reaction was further carried out at about 60° for 3 hours. After concentrating the reaction solution, the residue was purified by column chromatography to obtain 4.7 g of compound (1).

The amount of the compound of the present invention to be added to the photosensitive material and P
Although it varies depending on the type of UG, silver halide 1
10 −9 to 10 mol per mol, preferably 10
-5 to 1 mole.

The photosensitive material of the present invention can be applied to the following various types of photosensitive materials.

For example, it can be used for photosensitive materials such as color positive, color negative, color paper, reverse color, direct positive, color diffusion transfer, heat development, and monochrome, but especially for color photosensitive materials with multilayer structure. The application of is advantageous.

The silver halide emulsion used in the present invention may be any silver halide used in conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, or silver chloride. can be used.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately.

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

Coupler is generally used in the emulsion layer of color light-sensitive materials. Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, Compounds that release photographically useful fragments such as antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, a formalin scavenger-1 ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, a development retardant, and a bleach enhancer can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of coating liquid) After dissolving 35 g of gelatin in 1.04 g of water, a coating aid (Su-1) and a hardening agent (H-1) were added to prepare a coating liquid.

(Dye Precursor Dispersion) 2.5×10-' moles of comparative compound (A) were added to 1.6 ml of high-boiling solvent (Oil-1). Ethyl acetate 5mQ
1 containing surfactant (Su-2).
It was added to 44 g of 0% gelatin aqueous solution to make an emulsified fraction.

The coating solution and the dye dispersion were mixed and dissolved to have the following composition, and a coating aid (Su-1) and a hardening agent (H-1) were added to prepare a coating solution for an emulsion layer.

(Preparation of Sample) Sample 101 was prepared by coating the above emulsion layer coating solution on a 100 μm polyethylene terephthalate film base subjected to latex undercoating described in JP-A-59-19941 and drying. The dye precursor (compound) loading was 3 X 10-' mol/m2.

(Processing) Each of these samples was processed with a developer having the following composition and a developer having the following composition except that only hydroxylamine sulfate was removed.

Development processing conditions Development processing 30 seconds 38℃ water washing
Dry for 30 seconds Dry for 2 minutes 60-80℃ [Color developer/pure water 800mj! Benzyl alcohol 15ml Triethanolamine 10.0g Hydroxyamine sulfate 2.0g Potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
4.5g potassium carbonate
32.0g1-hydroxyethylidene-
1,1-disulfonic acid (60% aqueous solution) 1.5ml
Whitex BB (50% aqueous solution) (optical brightener,
(Manufactured by Sumitomo Chemical Industries, Ltd.) Add pure water to make 11, and add 20% potassium hydroxide or 10
Adjust p to 0.1 with % dilute sulfuric acid.

(Evaluation) The presence or absence of residual color after treatment was evaluated as follows. The visible spectrum of each sample after treatment was measured, and the residual color rate was determined from the difference between the absorbance at the absorption maximum (E2) and the following E1 using the following formula.

(E I represents the absorbance at the absorption maximum of each sample before treatment.) The results are shown in Table 1.

Similarly, samples were prepared by replacing the compound used in Sample 101 with the compounds shown in Table 1, and each of these samples was added to Sample 1.
02 to 106.

(S u-1) (S u-2) (H-
1) Comparative Compound A Comparative Compound B As is clear from Table 1, the compounds of the present invention release dye only in the presence of hydroxylamine. This means that the drawback of conventional precursors, which release dye when attacked by hydroxyl ionone during storage prior to processing, has been overcome. Furthermore, although the comparative compound (B) does indeed suppress dye release in the system without hydroxylamine, the dye release in the presence of hydroxylamine is insufficient.

In comparison, the compounds of the present invention both show sufficient values, indicating that the objects of the present invention have been fully achieved.

Example 2 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side, each layer having the composition shown below was coated on the side of the polyethylene layer containing titanium oxide. A silver halide color photographic material was prepared. The coating solution was prepared as follows.

(First layer coating solution) Yellow coupler (Y l ) 26.7 g, dye image stabilizer (ST-1) lo, Og, dye image stabilizer (ST-2) 6.67 g, additive (HQ - 1)
0.67 g, and high boiling point organic solvent (DNP) 6.67
Add and dissolve 60 m of ethyl acetate (1) to g and dissolve this solution to 2
A yellow coupler dispersion was prepared by emulsifying and dispersing the mixture into 220 nv of a 10% aqueous gelatin solution containing 7v2 of 0% surfactant (SU-1) using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution. - (2nd layer coating solution) Gelatin aqueous solution with surfactant (SU-2), (SO-
3) and hardeners (H-1), (H-2), antifungal agents (F-
1) was added and mixed to prepare an M2 layer coating solution.

2nd layer (protective layer) addition amount (g/m2)
Gelatin 2.0 1st layer (
Blue-sensitive layer) Gelatin 2.5 Blue-sensitive silver chlorobromide emulsion 0.26 Yellow coupler (Y-1) 0.69 Dye image stabilizer (
ST-1) 0.26 (ST-2)
0.17 Stain inhibitor (HQ-1) 0.02 Support polyethylene laminate paper However, the amount of silver halide emulsion is shown in terms of silver.

A blue-sensitive emulsion was prepared by a conventional method to prepare a silver chlorobromide emulsion with an average grain size of 0.70 μm and a silver bromide content of 90 mol%, and heated at 57°C using 1.5 mg of sodium thiosulfate and 1 mol of sodium thiosulfate.
Optimally sensitize with sensitizing dye CB5-1) 5 X 1
0-'mol 1 mol Agx and stabilizer,! l: 1. , TE (STAB-1) wo 5X 10-'mol 1 mol AgX
was added and adjusted. Further, each compound was added by dissolving it in a high boiling point solvent in the same manner as in Example 1. The amount added is 5×10 7 mol 1 mol AgX.

(DNP) dinonyl phthalate (SU-2) Comparative Compound D (Evaluation) After exposure using a conventional method, the yellow dye image obtained by the following processing was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Measurements were made.

Development processing conditions Color development 38°c 3 minutes 30 seconds Bleach fixing
33°c 1 minute 30 seconds washing process 25~3
Drying at 0°C for 3 minutes. Drying at 75-80'O for about 2 minutes. The results are shown in Table 2. The amount of compound added in Samples 202 to 206 in the table is the same as that of 5TAB-1 in Sample 202.

Processing solution composition (color developer) Benzyl alcohol 15mρ ethylene glycol I 5mQ Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate 30
．． 0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2-5g
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) -aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative 4) 1.0g Potassium hydroxide 2.0g Add water to total 1
112 and adjust the pH to 1o and 20.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate,
(70% solution) 100ml12 ammonium sulfite
(40% solution) Adjust the pH to 7.1 with 27.5 mQ potassium carbonate or glacial acetic acid, and add water to bring the total volume to lρ.

Table 2 As is clear from Table 2, it can be seen that the compounds of the present invention suppress fog without reducing sensitivity.

A blue-sensitive emulsion with an average grain size of 0.7 μm and a silver bromide content of 0.
A 5 mol% silver chlorobromide emulsion was prepared, and sodium thiosulfate 0.8 mg 1 mol 1 mol^Auric chloride 0.5 mg 1 mol 1
Optimally sensitize at 50°C using sensitizing dye B5-
1 4X10-'mol 1 mole 8gX, sensitizing dye B5-2
1 X 10-'mol 1 mol^gX and 5 as stabilizer
TAB-2 was prepared by adding 3 x 10-' moles of AgX to 4 moles of AgX. When these were coated and dried in the same manner as before and evaluated, the effects of the present invention were obtained.

Example 3 Samples that were the same as the silver halide emulsion used in Example 2, but with only the compounds changed as shown in Table 3, were prepared. It can be seen that gamma and sensitivity can be increased without increasing them.

Comparative compound E Comparative compound F

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer, characterized in that it contains a compound represented by the following general formula [I]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, E_1 and E_2 are electrophilic groups, and E_1 is more electrophilic than E_2. Y is E_1 and E_2 so that Z is released during processing of the sensitive material in the presence of di-nucleophiles.
is a substituent that places Z is a substituent that can be released upon processing. PUG is a photographically useful group. l, p, and q are integers of 0 or 1. However, p and q never become 0 at the same time. When p is 0, (PUG) p represents a hydrogen atom or a substituent; when q is 0, (PUG) q represents a hydrogen atom or a substituent. ]