JPH06301151A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To select a dye having a good absorption spectrum characteristic, obtain diffusion resistance, excellent eluting property, and decoloring property, and give no adverse effect to photographic characteristics such as photographic fog and desensitization by containing at least one kind of the silver salt of specific compounds. CONSTITUTION:At least one kind of the silver salt of compounds expressed in the formulas I, II, III is contained, where R1 indicates the alkyl group or alkenyl group, and R2, R3 indicate the hydrogen atom, alkyl group, allyl group, heterocyclic group, respectively, A indicates a group in the formula IV, etc., and A' indicates a group in the formula V, etc. In the formulas IV, V, R4 indicates the hydrogen atom or alkyl group, and X2 indicates the oxygen atom or sulfur atom. The silver salt of dyes expressed by the formulas I, II, III can be contained in a silver halide emulsion layer for use as a irradiation preventing dye or can be contained in a non-photosensitive hydrophilic colloidal layer for use as a filter dye or an antihalation dye.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a novel diffusion resistant dye, and more specifically, it contains a novel diffusion resistant dye having improved decolorization during processing. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Generally, in a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), a light absorption filter,
It is well known that a dye is contained in a constituent layer of a light-sensitive material in order to absorb light having a specific wavelength for the purpose of preventing halation, preventing irradiation or adjusting the sensitivity of a light-sensitive emulsion. It has been conventionally practiced to color the hydrophilic colloid layer with.

Of the constituent layers of the above-mentioned light-sensitive material, the filter layer is usually located above the light-sensitive emulsion layer or between the emulsion layer and another emulsion layer, and the incident light reaching the emulsion layer is preferably spectrally separated. It plays a role in changing the composition.
Further, an antihalation layer is provided between the light-sensitive emulsion layer and the support or on the back surface of the support for the purpose of improving the sharpness of the image, and is provided at the interface between the emulsion layer and the support or the spine of the support. The sharpness of the image is improved by absorbing harmful reflected light.

Further, the sharpness of an image is improved by coloring a photosensitive emulsion layer with a dye to absorb harmful reflected light and scattered light to silver halide grains and prevent irradiation. Has also been done.

The dye used for such purpose has, of course, good absorption spectrum characteristics depending on the purpose of use, and is, for example, completely decolorized during development processing and easily removed from the light-sensitive material during development processing. It is eluted and does not cause residual color contamination by dye after processing, and does not adversely affect fog or desensitization on the photosensitive emulsion, and diffuses from a colored layer to another layer. However, it must satisfy various conditions such as stability over time in a light-sensitive material or in an aqueous solution and no discoloration or fading.

[0006] To date, many studies have been conducted for the purpose of developing dyes satisfying the above-mentioned various conditions, for example, US Pat. Nos. 3,540,887, 3,544,325 and 3,560,21.
No. 4, JP-B No. 31-10578 and JP-A No. 51-3623, a benzylidene dye, and US Pat. No. 506,385 and JP-A-39-22069, an oxonol dye, US Pat.
No. 3,747 proposes a merocyanine dye, and US Pat. No. 1,845,404 proposes a styryl dye.

Some of these conventional dyes have a relatively small effect on the emulsion performance and have the ability to be bleached / eluted / bleached in the processing step, but from the viewpoint of diffusion resistance. It was not enough. That is, when a specific layer of a plurality of emulsion layers is selectively colored and used as a filter layer or an antihalation layer, not only the diffusion to other layers is remarkable, but the light absorption effect is lowered, and
There was a defect that it gives an undesired spectral effect to other layers.

Therefore, as a method of selectively dyeing a specific hydrophilic colloid layer, a method of fixing a dye with a mordant and a method of using a diffusion resistant dye have been proposed.

However, the method using a mordant has a poor coating property, is insufficient in suppressing the diffusion between layers, and has a poor elution property and decolorization property during processing, which requires a processing bath having a high pH, and speeds up the process. However, it has a drawback that it is inferior in processability.

A number of studies have been carried out on the method of using a diffusion resistant dye. Among them, US Pat.
049 and U.S. Pat. No. 3,471,293 describe silver salts of oxonol dyes having a thiobarbituric acid mother nucleus of a specific structure.

These known silver salt of dyes have the characteristics of having sufficient diffusion resistance and suppressing the diffusion between layers, but they have the drawback of being poor in decolorization and elution during processing.

For this reason, it is the actual situation that a dye satisfying the above-mentioned various conditions has not yet appeared, and its appearance is desired.

[0013]

Therefore, the first aspect of the present invention
The object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye having good absorption spectrum characteristics and diffusion resistance in a light-sensitive silver halide emulsion layer or a non-light-sensitive colloid layer. is there. A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which is excellent in elution and decolorization during a photographic processing step and which is accelerated in photographic processing suitability. A third object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye that does not stain the alkaline developing solution by being decolorized by the alkaline solution treatment and decolorized by the fixing solution treatment.
A fourth object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which does not adversely affect photographic characteristics such as fog and desensitization to a light-sensitive silver halide emulsion.

[0014]

The above objects of the present invention are achieved by the following silver halide photographic light-sensitive material.

Halogenation characterized by containing at least one silver salt of the compound represented by the general formula [I] "Chemical formula 1" or [II] "Chemical formula 1" or [III] "Chemical formula 1". Silver photographic light-sensitive material.

The present invention will be described in detail below.

First, the compounds represented by the general formulas [I] to [III] will be described.

In the general formulas [I] to [III], R _{1 to} R
_The alkyl group represented by ₁₃ , for example, a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group,
Examples thereof include a tert-butyl group, a cyclopentyl group, a cyclohexyl group. These alkyl groups further include a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom),
Alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group, 4-sulfophenoxy group, 2,4-disulfophenoxy group), aryl group (eg, phenyl group, 4-sulfophenyl group) , 2,5-disulfophenyl group), an alkoxycarbonyl group (for example,
It may be substituted with a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group) or the like.

Examples of the aryl group represented by R _{2 to} R ₁₃ and W include a phenyl group and a naphthyl group. These groups are alkyl groups represented by R _{1 to} R ₁₃ ,
And a substituent similar to the substituent shown as the substituent of the alkyl group.

Examples of the heterocyclic group represented by R _{2 to} R ₁₃ and W include a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a virazinyl group, a pyrimidinyl group, a pyridazinyl group and a purinyl group. Group, selenazolyl group, sulforanyl group, piperidinyl group, birazolyl group, tetrazolyl group and the like. These groups can be substituted with the alkyl groups represented by R _{1 to} R ₁₃ and the same groups as the substituents shown as the substituents of the alkyl group.

Examples of the alkenyl group represented by R _{1 to} R ₁₃ include a vinyl group and an allyl group. These groups can be substituted with the alkyl groups represented by R _{1 to} R ₁₃ and the same groups as the substituents shown as the substituents of the alkyl group.

In the general formula [I], the hetero ring formed by Q is, for example, JP-A-61-282832, 23.
~ Heterocycles described on page 26 and

[0023]

[Chemical 3]

The hetero ring represented by can be mentioned.

[In the formula, R ₁₄ has the same meaning as R ₄ in the general formula [A ₁ ] and R ₁₅ has the same meaning as R ₂ in the general formula [III]. l ₁ is an integer of 0 to 3. The compound represented by the general formula [I] or [II] or [III] of the present invention is characterized by containing at least one acid group in the molecule, and examples of the acid group include a sulfo group and a carboxyl group. Groups and the like.

Typical specific examples of the compounds represented by the general formulas [I] to [III] are shown below, but the present invention is not limited thereto.

[0027]

[Chemical 4]

[0028]

[Chemical 5]

[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

Regarding the method for producing a silver salt from these dyes and the method for adding it to a light-sensitive material, the above-mentioned British Patent 1,
The methods described in 077,049 and US Pat. No. 3,471,293 can be referred to.

In the light-sensitive material of the present invention, the silver salt of the dye represented by the above general formula [I] to general formula [III] is contained in the silver halide emulsion layer and used as an anti-irradiation dye. It can also be incorporated into the non-photosensitive hydrophilic colloid layer and used as a filter dye or an antihalation dye. Also,
Two or more kinds of silver salts of the dye of the present invention may be used in combination depending on the purpose of use, and as long as the effects of the present invention are not impaired.
It may be used in combination with other dyes.

In the present invention, the coating amount of the silver salt of the dye in the filter layer or the antihalation layer is from 0.05 to
Preferably 2.0 g / m ^2, in particular 0.1~l.0g / m ² is preferred.
The amount with the layer of gelatin, preferably 0.3 to 2.0 g / m ^2, in particular 0.5 to 1.0 g / m ² is preferred.

The ratio of the amount of the silver salt of the dye contained in the filter layer or the antihalation layer of the present invention to the amount of gelatin (the amount of the silver salt of the dye / the amount of gelatin) is 0.1 or more, preferably 0.1 to 2.0. , Particularly preferably 0.2 to 1.0.

As the support in the light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester film such as polyethylene terephthalate, polyolefin film such as polyethylene, polystyrene film, polyamide film, polycarbonate film, baryta paper, polyolefin coated paper, etc. , Polypropylene synthetic paper, glass plate, metal, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

As the hydrophilic colloid in the light-sensitive material of the present invention, gelatin, derivative gelatin such as phthalated gelatin and benzensulfonylated gelatin, water-soluble natural polymer such as agar, casein or alginic acid, polyvinyl alcohol and polyvinylpyrrolidone. And synthetic resins such as carboxymethyl cellulose and the like, and these can be used alone or in combination.

The silver halide emulsion in the light-sensitive material of the present invention may be a conventional silver halide emulsion such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. Any that are used are included.

The silver halide emulsion used in the light-sensitive material of the present invention can be manufactured by various methods including the methods usually used, for example, the method described in JP-B-46-7772.
Alternatively, a method as described in US Pat.
That is, an emulsion of silver salt particles having a solubility higher than that of silver bromide and comprising at least a part of silver salt is formed, and then at least a part of the particles is converted into a silver bromide salt or a silver iodobromide salt. It can be prepared by any manufacturing method such as the so-called conversion emulsion manufacturing method. This silver halide emulsion comprises a chemical sensitizer, for example, a sulfur sensitizer such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate and cystine, an active or inactive selenium sensitizer,
Gold compounds such as potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzothiazole methyl chloride etc., palladium compounds such as ammonium chloroparadate, sodium chloroparadite etc., like potassium chloroplatinate Noble metal sensitizers such as various platinum compounds, ruthenium compounds and the like, or a combination of such sensitizers can be used for sensitization. Further, this emulsion can be reduction-sensitized with a reducing agent in addition to chemical sensitization, and triazoles, imidazoles, azaindenes, benzothiazolium compounds, zinc compounds,
It can be stabilized with a cadmium compound, a mercaptan or a mixture thereof, and a thioether type, quaternary ammonium salt type or polyalkylene oxide type sensitizing compound can be contained.

The silver halide emulsion used in the light-sensitive material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. As the sensitizing dyes, various dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, streptocyanin dyes can be used. Can be used alone or in combination of two or more.

In the light-sensitive material of the present invention, a dihydroxyalkane such as glycerin and 1,5-pentanediol, an ester of ethylenebisglycolic acid, bisethoxydiethyleneglycol succinate, and an emulsifying agent are used in the emulsion layer and other hydrophilic colloid layers. A wetting agent such as a water-dispersible particulate polymer compound obtained by polymerization, a plasticizer, a film physical property-improving agent, etc. can be contained, and an aldehyde compound, N, N'-dimethylol urea or other N-methylol Compounds, mucohalogen acids, divinyl sulfonic acids, active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine, dioxane derivatives, divinyl ketones, isocyanates, hardeners such as levodiimides, saponins, Polyalkylene glycol, polyalkylene glycol ether, alkyl sulfonate Alkylbenzene sulfonate surfactant and alkyl naphthalene sulfonates, and further, optical brighteners, antistatic agents, anti-stain agents, ultraviolet absorbers, may contain photographic additives such as a stabilizer.

In the light-sensitive material of the present invention, a color coupler may be incorporated in the silver halide emulsion layer. The coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for masking or a coupler releasing a development inhibitor.

As the yellow-forming coupler, an acylacetamide-based open-chain ketomethylene-based compound, as the magenta-forming coupler, a pyrazolone-based compound, a pyrazolotriazole-based compound, a pyrazolotetrazole-based compound, and as the cyan-forming coupler, a phenol-based or naphthol-based compound The compounds are usually used with advantage.

Further, the light-sensitive material of the present invention can have any layer structure which can be obtained by a usual light-sensitive material.

[0048]

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

Example 1 0.1 mol of the dyes listed in Table 1 and 10.1 g of triethylamine (0.1
(1 mol) was dissolved in 1000 ml of water, and 200 ml of a 1 mol / liter silver nitrate aqueous solution was added dropwise with stirring. The resulting precipitate was collected by filtration, washed with water and dried to obtain the desired silver salt of the dye.

In 700 ml of a 3% aqueous gelatin solution, 0.05 mol of the silver salt of the above dye and the surfactant Triton X-200 (Rohm
& Haas) 6.7% solution (30 ml), glass beads (diameter 1 mm) 2 kg, and a medium stirring mill (Aquamizer QA-5, manufactured by Hosokawa Micron Co., Ltd.) for 8 hours for dyeing silver salt. A dispersion liquid of was obtained.

100 g of each of the above dispersions was added with 0.1 g of bisvinylsulfonylmethyl ether [H
-1] and a coating aid [Su-1] are added, and then coated on a cellulose triacetate film support on which a gelatin layer has been subbed so that the silver salt coating amount of each dye is 0.001 mol / m ^2. And dried to obtain samples 1-1 to 1-10.

Further, a fine particle dispersion liquid of Dye D-2 was prepared by the method described in Example 1 of JP-A-3-23441,
The hardener [H-1] and coating aid [Su-1] were added in the same manner as in Samples 1-1 to 1-10 described above, and the dye coverage was 0.001 mol /
Sample 1 was prepared by coating on a cellulose triacetate film support with a gelatin layer subbed to give m ² and drying.
I got -11.

Further, Example 1 of JP-A-63-291051
To dye D-3 and an aqueous gelatin solution containing about 40 times the amount of the polymer dispersion mordant as the dye D-3 on the cellulose triacetate film support with the gelatin layer subbed. Of 0.001 mol / m ² was applied and dried to obtain Sample 1-12.

The structures of the dyes D-1 to D-3 (comparative), the coating aid [Su-1] and the polymer dispersion mordant used in the above samples are shown below.

[0055]

[Chemical 12]

[0056]

[Chemical 13]

Samples 1-1 to 1-12 were treated with the following fixing solution A, alkaline solution B and water at 20 ° C. for 15 seconds, washed with water and dried, and then measured with a spectrophotometer. The decolorization rate at the maximum absorption wavelength for the untreated sample was obtained by the equation.

The results are also shown in Table 1.

Decolorization rate (%) = [1- (concentration of treated sample / concentration of untreated sample)] × 100 [fixing solution A] sodium thiosulfate 240 g anhydrous sodium sulfite 15 g glacial acetic acid 15 g aluminum potassium sulfate 15 g water Add to 1000 ml [Alkali solution B] 37.5 g of potassium carbonate Add water to make 1000 ml, and adjust to pH 0.2 using IN H ₂ SO ₄ .

[0060]

[Table 1]

It can be seen from Table 1 that the silver salt of the dye of the present invention has a higher decolorization rate after treatment and less residual color than the silver salt of the comparative dye. Further, it is characterized in that it does not decolorize when treated with an alkaline solution and decolorizes when treated with a fixing solution, so that it is less contaminated with a developing solution than a known comparative dye. Further, it has a feature that the decolorizing effect by the treatment of the fixing solution is remarkable as compared with the known comparative dyes. It was also found that the silver salt of the dye of the present invention has good diffusion resistance equivalent to the silver salt of the comparative dye and the comparative diffusion-resistant dye.

Example 2 (Preparation of Sample 2-1) A 10% aqueous gelatin solution was applied onto a cellulose triacetate film support which had been undercoated with a gelatin layer to form a first layer. At the same time, a light-sensitive silver halide emulsion layer having the following composition and a surface protective layer were multilayer-coated thereon to prepare Sample 2-1.

<Photosensitive Silver Halide Emulsion Layer Composition> Silver halide emulsion (monodisperse and uniform composition emulsion having an average grain size of 0.48 μm and containing 2 mol% of iodine) 3.2 g / m ² gelatin 1.6 g / silver 1g additives sensitizing dye 4.8 × lO ^-4 mol / silver l mol

[0064]

[Chemical 14]

Coating aid dodecylbenzene sulfonic acid sodium salt [Su-1] 0.1 mg / m ² <Surface protection layer composition> Gelatin 0.6 g / m ² Coating aid N-oleoyl-N-methyl taurate sodium salt [ Su-2] 0.2 g / m ² hardening agent Bisvinylsulfonylmethyl ether [H-1] 0.05 g / 1 g gelatin (Preparation of samples 2-2 to 2-12) 10% of the first layer in sample 2-1 A multilayer photographic element (Samples 2-2 to 2-2) was prepared in the same manner as Sample 2-1, except that the aqueous gelatin solution was replaced with an aqueous dispersion gelatin solution containing dyes shown in Table 2 prepared according to the examples.
2-12) was prepared. The amount of dye applied was set to 0.001 mol / m ² .

Each of the samples 2-1 to 2-1 produced in this way
2-12 was subjected to wedge exposure using white light, and then the following development processing was performed to compare effects on photographic characteristics.

Processing step (20 ° C.) Development 2 minutes Fixing 3 minutes Washing with water 3 minutes Drying The composition of the processing solution used in each processing step is as follows.

[Developer] Water 500 ml Hydroquinone 8 g Metol 2 g Anhydrous sodium sulfite 90 g Sodium carbonate monohydrate 52.5 g Potassium bromide 5 g Add water to make 1 liter [Fixer] Water 600 ml Ammonium thiosulfate 80 g Anhydrous sodium sulfite 5 g Heavy Sodium sulfite 5 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

The results obtained are shown in Table 2.

[0070]

[Table 2]

As shown in Table 2, the comparative dye D-1 slightly increased the fog density, and the effect on fog was observed.
Comparative dye D-3 has no effect on fog, but
The coatability is adversely affected. On the other hand, it can be seen that the silver salt of the dye of the present invention does not affect the coatability and has little influence on the silver halide in the adjacent layer. Further, the sharpness is improved as compared with Sample 2-1 and the dye has good characteristics.

[0072]

As the dye of the present invention, a dye having a good absorption spectrum characteristic can be selected according to the purpose, and it is excellent in elution property and decolorization property during the photographic processing step while being resistant to diffusion and fog. Since it does not adversely affect photographic characteristics such as desensitization and the like, silver halide photographic light-sensitive material which has no residual color contamination even in accelerated photographic processing and has no deterioration in photographic characteristics such as fog and desensitization. Can be provided.

Front Page Continuation (72) Akira Onishi, Akira Onishi, Konica Stock Market, Hino City, Tokyo, 1st Konica Stock Company (72) Inventor, Taketoshi Yamada, 1 Sakura City, Hino City, Tokyo Konica Stock Company, in-house

Claims (1)

[Claims] 1. The following general formula [I] or [II] or [III]
A silver halide photographic light-sensitive material containing at least one silver salt of the compound shown by. [Chemical 1] [In the general formulas [I] to [III], R ₁ represents an alkyl group or an alkenyl group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, respectively. A
Is a group represented by the following general formula [A ₁ ] to general formula [A ₄ ]
A ′ represents a group represented by the following general formulas [A ′ ₁ ] and [A ′ ₂ ]. [Chemical 2] [In general formula [A ₁ ] to general formula [A ₄ ] and general formulas [A ′ ₁ ] and [A ′ ₂ ], R ₄ , R ₅ , R ₇ and R ₉
Each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ₆ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a sulfo group, —COR ₁₀ , or —CON ( R ₁₀ ) (R ₁₁ ), −N (R ₁₀ ) (R ₁₁ ), −OR
₁₀ , -SOR ₁₀ , -SO ₂ R ₁₀ , -SO ₂ N (R ₁₀ ) (R ₁₁ ), -N (R ₁₀ ) C
OR ₁₁ , -N (R ₁₀ ) SO ₂ R ₁₁ , -N (R ₁₀ ) CON (R ₁₁ ) (R ₁₂ ), -SR
₁₀ represents -COOR ₁₀ . R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₈ has the same meaning as R ₂ and R ₃ . X ₁ represents an oxygen atom, a sulfur atom, a selenium atom, or = N-R ₁₃ .
R ₁₃ has the same meaning as R ₄ . X ₂ , X ₃ and X ₄ represent an oxygen atom and a sulfur atom, respectively. However, at least one of X ₃ and X ₄ represents a sulfur atom. L represents a methine group, and Q represents a nonmetallic atom group necessary for forming a heterocycle. W represents an aryl group or a heterocyclic group.
n ₁ represents an integer of ₁ to 3. However, the molecules represented by the general formulas [I] to [III] include at least one acid group in the molecule. ]