JP2632397B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a dye, and more particularly to a halogenated silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light absorbing dye. It relates to a silver photographic light-sensitive material.

[Background of the Invention]

Silver halide photographic material (hereinafter referred to as photosensitive material)
It is well known that a dye is contained in a photographic material for the purpose of absorbing light of a specific wavelength for the purpose of absorbing light of a specific wavelength for the purpose of filtering, preventing halation, preventing irradiation or adjusting the sensitivity of a photographic emulsion. It is common to color a hydrophilic colloid layer.

The filter layer is usually located above the photosensitive emulsion layer or between the emulsion layer and the emulsion layer, and serves to convert incident light reaching the emulsion layer into light having a preferable spectral composition. Further, for the purpose of improving the sharpness of the photographic image, an antihalation layer is provided between the emulsion layer and the support or on the back surface of the support,
Absorbs harmful reflected light at the interface between the emulsion layer and the support, at the back of the support, etc. to prevent halation, or colors the emulsion layer to harmful reflected or scattered light from silver halide grains. It is often practiced to absorb radiation to prevent irradiation.

Dyes used for such purposes have good absorption spectrum characteristics according to the purpose of use, are completely decolorized during photographic development, are easily eluted from the photographic material, and remain after dyeing. No color contamination, no adverse effects such as fog and desensitization on the photographic emulsion, no diffusion from the dyed layer to other layers,
It must have excellent stability over time in a solution or a photographic material and satisfy various conditions such as not discoloring.

To date, a number of efforts have been made and a number of dyes have been proposed with the aim of finding dyes satisfying the above conditions. For example, UK Patent 506,385, U.S. Patent 3,2
47,127, JP-B-39-2269, oxonol dyes described in JP-B-43-13168, styryl dyes represented by U.S. Patent No. 1,845,404, merocyanine dyes represented by U.S. Patent No. 2,493,747, U.S. Patent No. 2,843,486 Typical examples include cyanine dyes. However, in reality, there are very few good dyes that satisfy all of the above conditions and can be used in photographic materials.Especially, dyes that absorb in the red to infrared regions, and satisfy the above conditions. Few satisfactory dyes were known.

On the other hand, in recent years, recording materials sensitized to infrared wavelengths, such as antihalation and antiirradiation dyes that absorb in the infrared region of the spectrum for photographic photosensitive materials as recording materials for recording the output of near-infrared lasers. Development is requested.

[Object of the invention]

Accordingly, an object of the present invention is to have good absorption spectrum characteristics even in the red to infrared regions, decolorize during photographic development processing, and elute from photographic materials to minimize residual color contamination after processing. An object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which is inert to an emulsion.

[Configuration of the invention]

The object of the present invention has been attained by a silver halide photographic material having a hydrophilic colloid layer containing at least one dye represented by the following general formula [I].

General formula [I] In the formula, X and Y are each a cyano group, a carbamoyl group,
Represents a carboxyl group or a carboxylic ester group, R ₁ and R ₂ each represent a substitutable group, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R ₃ and R ₄ may form a ring. m is an integer of 0 to 6, n
Represents an integer of 0 to 4.

 Hereinafter, the present invention will be described more specifically.

Among the groups represented by X and Y, examples of the carbamoyl group include groups such as carbamoyl, N-hydroxyethylcarbamoyl, and N-monophorinocarbonyl.
Examples of the carboxylate group include groups such as ethoxycarbonyl and hydroxyethoxycarbonyl.

Substitutable groups represented by R ₁ and R ₂ include, for example, a parogen atom and alkyl, aryl, heterocycle, aralkyl, alkoxy, aryloxy, hydroxy, acyloxy, carboxy, alkoxycarbonyl, aryloxycarbonyl, mercapto, alkylthio , Arylthio, alkylsulfonyl, arylsulfonyl, acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl, sulfo or a salt thereof, cyano, nitro, isocyanate, ureide and the like. When m and n are each 2 or more, a plurality of R ₁ and R ₂ may be the same or different.

Examples of the alkyl group represented by R ₃ and R ₄ include groups such as methyl, ethyl, propyl, cyclohexyl, benzyl, and phenethyl; examples of the aryl group include groups such as phenyl and naphthyl; and examples of the heterocyclic group For example, groups such as pyridyl, tetrahydrofuryl, and sulfolanyl can be mentioned.

These groups may have a substituent, and examples of the substituent include a halogen atom and each group such as hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, alkylsulfonyl, sulfonamide, cyano, sulfo, acylamino, carbamoyl, and sulfamoyl. Can be mentioned. Further, R ₃ and R ₄ may combine to form a ring (for example, a morpholine ring).

At least one of R ₁ , R ₂ , R ₃ and R ₄ is itself a water-soluble group such as a sulfo group or a carboxyl group, or a group having a sulfo group or a carboxyl group as a substituent Is preferred.

Specific examples of the dye represented by the general formula [I] (hereinafter, referred to as the dye of the present invention) used in the present invention are shown below, but the present invention is not limited thereto.

Next, a method for synthesizing the compound of the present invention will be described.

The compound of the present invention can be easily obtained in the following step.

Regarding this synthesis method, for example, Chemistry Letters, 1987, No. 9, pages 1761 to 1762 can be referred to.

Alternatively, in the reaction, instead of the N, N-dialkyl-P-phenylenediamine compound, 4-nitroso-N,
It can also be obtained by reacting N-dialkylarylamine.

In the light-sensitive material of the present invention, the dye represented by the general formula I can be used as an anti-irradiation dye by being contained in a silver halide emulsion. It can be used as a filter dye or an antihalation dye by being contained therein. Further, two or more dyes may be used in combination depending on the purpose of use, or may be used in combination with another dye. The dye of the present invention in a silver halide emulsion layer or
In order to make it contained in other hydrophilic colloid layers, it can be easily carried out by a usual method. Generally, a dye or an organic / inorganic alkali salt of a dye is dissolved in water to prepare an aqueous solution of a dye having an appropriate concentration, and the resulting solution is added to a coating solution and coated by a known method to contain the dye in a photosensitive material. Can be. The content of these dyes varies depending on the purpose of use, but is generally 1 to ² per square meter of photographic material.
It is applied so as to be ~ 800 mg before use.

Examples of the photosensitive material to which the present invention is applied include color photographic photosensitive materials in addition to black-and-white photographic photosensitive materials.
Examples of the former include a photosensitive material for printing. At this time, two or more silver halide emulsion layers can be provided. The coated silver amount is preferably in the range of 1 to 8 g / m ² .

Silver halide used in the present invention, for example, silver chloride,
Any of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, and silver chloroiodide may be used.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedron may be used, or may have irregular crystal forms such as spheres, crystal defects such as twin planes, or composite forms thereof. May be.

The grain size of the silver halide may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method. For example, Research Disclosure (RD), Vol. 176, No. 17643 (December, 1978), pp. 22-23, and N.
o. 18716 (November 1978), p.648.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.

In the case of chemical sensitization, usual sulfur sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine; and noble metal sensitizers such as potassium chloroaurate, auras thiosulfate and potassium chloroparadate. Agents: reduction sensitizers such as tin chloride, phenylhydrazine and reductone;

The silver halide emulsion used in the present invention is optionally spectrally sensitized by a known spectral sensitizing dye. As the spectral sensitizing dye to be used, those described in Research Disclosure (supra) No. 17643, Section IV can be used.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a reduction in sensitivity and generation of fog during the production process, storage or processing of the photographic material. These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole, and many other heterocyclic compounds. Very many compounds such as mercury compounds, mercapto compounds and metal salts have been known for a long time.

As the binder or protective colloid used for the photosensitive material, gelatin is advantageously used, but a hydrophilic synthetic polymer or the like can also be used. As gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin, and the like can also be used.

In the photosensitive material of the present invention, in addition to the above, a desensitizer,
Whitening agents, couplers, hardeners, coating aids, plasticizers, slippers, matting agents, high-boiling organic solvents, stabilizers, development accelerators,
An antistatic agent, an antistain agent and the like can be used. As these additives, those described in Research Disclosure (supra) No. 17643, Sections I to XVI can be used.

For the photographic processing of the light-sensitive material of the present invention, any of known methods can be used, and a known processing solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied.

〔The invention's effect〕

According to the present invention, the silver halide photographic light-sensitive material has good image quality and has little residual color after development without losing sensitivity. Moreover, the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is colored with a water-soluble dye, has no adverse effect on the photographic properties of the photographic emulsion, has good stability upon storage, and is easily processed by photographic processing. It is extremely excellent in that it is decolorized.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 3.5 g of gelatin was added to and dissolved in 35 ml of distilled water.
5 ml of an aqueous solution containing 2.0 × 10 ^-4 mol of each of the exemplified dyes (1), (2) and (3) of the present invention was added, and 1.25 ml of a 10% aqueous saponin solution and 0.75 ml of a 1% formalin solution were further added. Then, water was added to make the total volume 50 ml. This dye solution was applied on an acetylcellulose film support and dried to obtain Samples 1, 2 and 3. Comparative Samples 4 and 5 were prepared in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention.

Each of these samples was immersed in a developer having the following composition at 25 ° C. for 1 minute, washed with water for 20 seconds, and then dried.

(Composition of developer) Methol 3.0 g Sodium sulfite (anhydrous) 45.0 g Hydroquinone 12.0 g Sodium carbonate (monohydrate) 80.0 g Potassium bromide 2.0 g Add water to make 1

The visible spectrum of each sample before and after immersion in the developer was measured, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below.

(E ₁ is the absorbance before the developer immersion, E ₂ is the absorbance after the developer immersion.) As is clear from Table 1, the dye of the present invention was found to exhibit excellent decolorization properties as compared with the comparative dye.

Example 2 A silver chloroiodobromide gelatin emulsion comprising 80 mol% of silver chloride, 19.5 mol% of silver bromide and 0.5 mol% of silver iodide and having an average grain size of 0.32 μm was prepared. 1 kg of this gelatin emulsion (48 silver
g, including gelatin 75g. ) Per 2,4-dichloro-6
-Hydroxy-1,3,5-triazine sodium salt (1%
After adding 35 ml of aqueous solution) and 50 ml of saponin (10% aqueous solution), the mixture was coated on a polyethylene terephthalate film support which had been subjected to a subbing treatment so as to contain 50 mg of silver per 100 cm ² and dried.

Further, a protective layer having the following composition containing Exemplified Dye (4) of the present invention was applied on the emulsion layer so that the dry film thickness was 2 μm. (Protective layer composition) Gelatin 40 g Water 850 ml Exemplary dye (4) of the present invention (2% aqueous solution) 100 ml 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (1 % Aqueous solution) 20 ml Saponin (10% aqueous solution) 30 ml Similarly, instead of the exemplary dye (4) of the present invention, the exemplary dyes (5) and (8) and the comparative dyes (A) and (B) used in Example 1. ) Were prepared as Samples 7, 8, 9, and 10, respectively.

Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using a developing solution and a fixing solution having the following compositions.
Development is performed at 20 ° C for 1.5 minutes, fixing is performed at 20 ° C for 2 minutes,
After washing with water at 20 ° C. for 5 minutes, it was dried.

(Developer composition) Hydroquinone 15 g Sodium bisulfite formaldehyde adduct 55 g Sodium sulfite anhydride 3 g Sodium carbonate (monohydrate) 80 g Boric acid 5 g Potassium bromide 2.5 g Disodium ethylenediaminetetraacetate 2 g Add water 1,000 ml (Fixing solution composition) Sodium thiosulfate 160g Anhydrous sodium sulfite 14g Glacial acetic acid 12ml Borax 12g Potash alum 5g 1,000ml with water Was examined. The results obtained are shown in Table 2 below.

In the sample using the comparative dye, coloring stain was observed in the sample. However, the dye of the present invention was excellent in outflow and decolorization properties, and did not have any coloring stain.

Example 3 A silver chlorobromide emulsion comprising 70 mol% of silver chloride and 30 mol% of silver bromide and having an average grain size of 0.3 μm was prepared. This emulsion 1
After adding 20 ml of formalin (1% aqueous solution) and 50 ml of saponin (10% aqueous solution) per kg (including 48 g of silver and 75 g of gelatin), the mixture is coated on a polyethylene terephthalate film support which has been subjected to a subbing treatment. Was coated with a protective layer having the following composition.

(Protective layer composition) Gelatin 40 g Water 960 ml Formalin (1% aqueous solution) 12 ml Saponin (10% aqueous solution) 30 ml Next, a gelatin layer containing a dye having the following composition is provided on the back surface of the support coated with the emulsion layer and the protective layer. 3μ dry film heat
m. (Composition of gelatin layer) (Gelatin layer composition) Gelatin 50g Water 835ml Exemplary dye (12) according to the present invention (2% aqueous solution) 100ml Formalin (1% aqueous solution) 15ml Saponin (10% aqueous solution) 50ml Samples 12 and 13 were prepared by using the exemplary dye (13) and the following dye (C) in place of the exemplary dye (12).

Developing treatment was performed in the same manner as in Example 2, and each sample 10
The sheets were superimposed one by one to evaluate coloring contamination. The results obtained are shown in Table 3 below.

As shown in the above table, in the sample using the comparative dye, coloring contamination was observed, but in the dye of the present invention, no coloring contamination was observed. It was also found that the dye of the present invention can provide a photosensitive material having an excellent antihalation effect without adversely affecting photographic emulsions such as fog and desensitization.

Example 4 On a support made of polyethylene-coated paper, the following layers were sequentially provided from the support side to prepare a color photographic material (Sample 14).

First layer: yellow coupler; α-pivalyl-α- (1-benzyl-2-phenyl-3,5-dioxotriazolidine-
4-yl) -2'-chloro-5 '-[γ- (2,4-di-
t-amylphenoxy) butyramide] acetanilide, a blue-sensitive silver halide emulsion layer containing a hardener (dichlorotriazine) and a surfactant (saponin) (a silver chlorobromide emulsion containing 90 mol% of silver bromide, Sensitized with a sensitizing dye) was provided so that the coated silver amount was 3.5 mg / 100 cm ² .

Second layer: a gelatin layer (intermediate layer) was provided.

Third layer: magenta coupler; 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacedamide) benzamide] -5-pyrazolone, hardener A green-sensitive silver halide emulsion layer containing (dichlorotriazine) and a surfactant (saponin) (a silver chlorobromide emulsion containing 80 mol% of silver bromide, sensitized with a sensitizing dye) Was provided so that the coated silver amount was 4.5 mg / 100 cm ² .

Fourth layer: a gelatin layer (intermediate layer) was provided.

Fifth layer: cyan coupler; 2,4-dichloro-3-methyl-
6- (2,4-di-t-amylphenoxyacetamide)
Red-sensitive silver halide emulsion layer containing phenol, hardener (dichlorotriazine) and surfactant (saponin) (a silver chlorobromide emulsion containing 75 mol% of silver bromide, sensitized with sensitizing dye) Was applied so that the coated silver amount was 2.0 mg / 100 cm ² .

Sixth layer: A gelatin layer (protective layer) was provided.

Further, a red-sensitive emulsion (fifth layer coating solution) was prepared by adding 200 ml of a 2% aqueous solution of the exemplary dye (11) of the present invention or the comparative dye (C) per 1 kg of the emulsion. Sample 15 and sample 16 were prepared.

After exposing these samples 14, 15 and 16, they were processed according to the following processing steps.

Processing time (31 ° C) Processing time 1. Color development 3 minutes 2. Bleaching and fixing 1 minute 3. Water washing 2 minutes 4. Stabilization 1 minute 5. Water washing 2 minutes The processing solution composition used in each processing step is as follows. It is as follows.

(Color developer composition)

4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.8 g anhydrous sodium sulfite 4.0 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 28.0 g potassium bromide 1.5 g Potassium hydroxide 1.0g Add water to make 1.

(Bleach-fix solution composition)

 Ferric ethylenediaminetetraacetate 65.0 g Disodium ethylenediaminetetraacetic acid 3.0 g Sodium sulfite anhydrous 9.5 g Ammonium thiosulfate 77.5 g Anhydrous sodium carbonate 4.0 g Add water to make 1.

(Fixer composition)

 Glacial acetic acid 9ml Sodium acetate 3g Add water to make 1.

 Table 4 shows the density of the unexposed portion of each sample after the treatment.

As is clear from Table 4, in the sample containing the dye of the present invention, coloring contamination due to the residual color of the dye as shown by the sample containing the comparative dye was not observed. When the sensitivities of the respective samples were compared, it was found that the dye of the present invention had very little adverse effect on the emulsion.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having a hydrophilic colloid layer containing at least one dye represented by the following general formula [I]. General formula [I] Wherein X and Y are each a cyano group, a carbamoyl group,
Represents a carboxyl group or a carboxylic ester group, R ₁ and R ₂ each represent a substitutable group, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R ₃ and R ₄ may form a ring. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. ]