JPH063770A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material containing a water-soluble dye which gives less contamination after a treatment by incorporating a specified compd. CONSTITUTION:At least one kind of compd. expressed by formula is incorporated into the silver halide photographic sensitive material. In formula, R<1> and R<2> denote heterorings, phenyl groups having two or more sulfo groups, and L1-L5 denote methyn groups. An oxonol dye expressed by this formula may be incorporated into the silver halide photographic emulsion and used as an irradiation preventing dye, or may be incorporated into a nonphotosensitive hydrophilic colloid layer and used as a filter dye or hallation preventing dye. Also, according to the utilization purpose, two or more dyes may be combined or other dyes may be combined for use. In order to incorporate these dyes into the silver halide photographic sensitive emulsion layer or other hydrophilic colloid layers, a general method can be adopted.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION In a silver halide photographic light-sensitive material, a dye is incorporated into the silver halide photographic light-sensitive material for the purpose of absorbing light of a specific wavelength for the purpose of preventing filters, halation, prevention of irradiation or adjusting sensitivity. Are well known and have colored hydrophilic colloid layers with these dyes.

The filter layer is usually located above the photosensitive emulsion layer or between the emulsion layers and plays a role of making incident light reaching the emulsion layer into light having a preferable spectral composition. For the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back surface of the support to prevent harmful effects on the interface between the emulsion layer and the support or on the back surface of the support. It is often practiced to absorb reflected light to prevent halation, or to color the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains to prevent irradiation. There is.

The dyes used for such purposes have good absorption spectrum characteristics depending on the purpose of use, are completely decolorized during photographic development processing, or are used in silver halide photographic light-sensitive materials. Easily eluted and no residual color contamination by dyes after development, no adverse effects such as fog or desensitization on photographic emulsion, and stability over time in solution or silver halide photographic light-sensitive material It must satisfy various conditions such as excellent quality and no discoloration.

To date, many efforts have been made and numerous dyes have been proposed in order to find dyes which satisfy the above conditions. For example, U.S. Pat.
Oxonol dyes described in Japanese Patent No. 127, Japanese Patent Publication No. 39-22069, Japanese Patent Publication No. 55-10059, etc. are known.

Among them, as an oxonol dye, one having an ester type at the 3-position is known as a good dye, and is disclosed in JP-A-48-85130, JP-A-48-62826,
It is described in JP-A-62-275246, JP-A-64-26850, JP-A-2-131233, JP-A-3-209466 and the like.

Although these dyes certainly satisfy the above-mentioned performance to some extent, problems such as residual color contamination have come up again in recent years with the rapid processing seen in color paper and the like.
As mentioned above, the dye has some necessary properties, among which, the dye is erased during the photographic processing and / or is easily eluted from the photographic light-sensitive material into the processing solution, resulting in residual color contamination. The absence is an especially important property for rapid processing. Originally, it is ideal that all dyes will be decolored within the processing time, but pyrazolone oxonol dyes are types that decolorize by nucleophilic attack, so if the decolorization reaction speed is too fast, water will be stored during storage. There is a disadvantage that some dyes are decolorized by the nucleophilic attack of the molecule.

Therefore, even if only the decoloring property is improved, a sufficiently satisfactory light-sensitive material cannot be obtained, and the elution property of the dye into the processing solution is an important factor for the residual color contamination. This time, we reviewed the ester type dyes at the 3rd position from the above viewpoint, and when the dyes at the 3rd position are methyl ester and the 1st position has two or more heterocycles or sulfo groups, the residual color contamination is peculiar. It turns out that there are few. This is unexpected. The above-mentioned publications and the like do not describe any examples of the compounds of the present invention, and the fact that no data is described in the Examples indicates that the results are surprising.

[0009]

OBJECTS OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material containing a water-soluble dye which causes little stain after processing.

[0010]

The above objects of the present invention are represented by the following general formula [I]:
This is achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by

[0011]

[Chemical 2] [In the formula, R ¹ and R ² represent a heterocycle and a phenyl group having two or more sulfo groups, and L _{1 to} L ₅ represent a methine group. The present invention will be described in more detail below.

In the general formula [I], the phenyl group having two or more sulfo groups represented by R ¹ and R ² is further an alkyl group (eg, methyl group, ethyl group, isopropyl group,
t-butyl group, pentyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, 1,1-dimethylethoxy group, n-hexyloxy group) , N-dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), aryl group (eg phenyl group, naphthyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group) ,
n-butoxycarbonyl group, 2-ethylhexylcarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group, naphthyloxycarbonyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), heterocyclic group (eg , 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group,
Piperazyl group, pyrimidyl group, pyrazolyl group, furyl group, etc.), alkynyl group (eg, propargyl group, etc.), amino group (eg, amino group, N, N-dimethylamino group,
Anilino group, etc.), hydroxy group, cyano group, sulfo group,
It may be substituted with a carboxyl group, a sulfonamide group (for example, a methylsulfonylamino group, an ethylsulfonylamino group, an n-butylsulfonylamino group, an n-octylsulfonylamino group, a phenylsulfonylamino group, etc.) and the like.

Examples of the heterocyclic group represented by R ¹ and R ² include a pyridyl group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group), thiazolyl group, oxazolyl group, imidazolyl group. , Furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group and the like. These groups are R
It can be substituted with a phenyl group represented by ¹ or R ² and a group similar to the group shown as the substituent of the phenyl group.

The methine group represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ may have a substituent, and the substituent includes a phenyl group represented by R ¹ and R ^2. The same group as the group shown as the substituent of the phenyl group can be mentioned.

The general formula [I] used in the present invention is as follows.
Specific examples of the compound represented by the formula (referred to as exemplified compounds in Examples) are shown, but the compound represented by the general formula [I] of the present invention is not limited to these dyes.

[0016]

[Chemical 3]

[0017]

[Chemical 4] The oxonol dye according to the present invention can be easily synthesized in the same manner as the method described in JP-A-48-85130 and JP-A-48-62826.

Hereinafter, specific synthesis examples of the present invention will be shown, but other dyes can be easily synthesized by the same method.

[0019]

[Chemical 5] 10 g of (1), 3.4 g of (2), 7.2 g of triethylamine and 50 ml of dimethylformamide were added to a 100 ml conical beaker, and the mixture was stirred at room temperature for 6 hours for reaction. 100 ml of ethanol,
The above reaction solution was added little by little to a uniform solution of 200 ml of methanol and 5 g of potassium acetate. The mixture was stirred at room temperature for 1 hour, filtered, and washed with ethanol to obtain the desired product (10 g, 87% yield). The structure was confirmed by NMR and mass spectrum.

In the photographic light-sensitive material of the present invention, the oxonol dye represented by the general formula [I] can be contained in a silver halide photographic light-sensitive emulsion to be used as an anti-irradiation dye, or it can be used as a non-irradiation dye. It can also be used as a filter dye or an antihalation dye by incorporating it in a photosensitive hydrophilic colloid layer. Further, two or more kinds of dyes may be used in combination depending on the purpose of use, or may be used in combination with other dyes. In order to incorporate the dye according to the present invention into the silver halide photographic light-sensitive emulsion layer or other hydrophilic colloid layer, a usual method can be adopted and can be easily carried out. Generally, a dye or an organic / inorganic alkali salt of a dye is dissolved in water,
A dye aqueous solution having an appropriate concentration can be added to the coating solution and coating can be carried out by a known method to incorporate the dye into the photographic light-sensitive material. These dyes differ depending on the purpose of use, but generally 1 to 800 m ² per 1 m ² area on the light-sensitive material.
It is used by coating so that it will be g.

As the support in the photographic 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 coating. There are paper, polypropylene synthetic paper, glass plate, metal, etc., and these supports are appropriately selected depending on the intended use of the photographic light-sensitive material.

Examples of the hydrophilic colloid in the photographic light-sensitive material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein and 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 photographic light-sensitive material of the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide,
It includes any of those usually used in silver halide photographic emulsions such as silver iodobromide and silver chloroiodobromide emulsions.

The silver halide emulsion used in the photographic light-sensitive material of the present invention can be manufactured by various methods including commonly used methods, for example, the method described in JP-B-46-7772 or US Pat. No. 2,592,250. As described in the specification, i.e., forming an emulsion of silver salt grains consisting of at least a silver salt whose solubility is greater than that of silver bromide, and then at least a portion of this grain It can also be prepared by a so-called conversion emulsion production method such as conversion into a silver halide salt or a production method of a Lippmann emulsion comprising fine grain silver halide having an average grain size of 0.1 μm or less. This silver halide emulsion is a chemical sensitizer,
For example, sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate and cystine, active or inactive selenium sensitizers, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2 -Gold compounds such as aurothiabenzthiazole methyl chloride, palladium compounds such as ammonium chloroparatate, sodium chloroparatate, etc., platinum compounds such as potassium chloroplatinate, ruthenium compounds, rhodium compounds, iridium compounds etc. Sensitization can be carried out with such noble metal sensitizers or combinations of such sensitizers. Further, this emulsion can be reduction-sensitized with a reducing agent in addition to the above-mentioned chemical sensitization, and triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans or these Mixtures can be used and can also contain thioethers, quaternary ammonium salts or sensitizing compounds of polyalkylene oxides.

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

In the photographic light-sensitive material of the present invention, glycerin, glycerin, etc. are contained in the photographic emulsion layer and other hydrophilic colloid layers.
Dihydroxyalkanes such as 1,5-pentanediol,
Ester of ethylene bis glycols, bis-ethoxydiethylene glycol succinate, wetting agents such as water-dispersible fine particle polymer compound obtained by emulsion polymerization,
A plasticizer, a film physical property-improving agent, etc. may be contained, and an aldehyde compound, an N-methylol compound such as N, N'-dimethylolurea, mucohalogen acid, divinylsulfones, 2,4-dichloro-6- Active halogen compounds such as hydroxy-5-triazine, dioxane derivatives,
Hardeners such as divinyl ketones, isocyanates, carbodiimides, saponins, polyalkylene glycols,
Photo of surfactants such as polyalkylene glycol ethers, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, etc., as well as optical brighteners, antistatic agents, anti-stain agents, UV absorbers, stabilizers, etc. Additives can be included.

In the photographic light-sensitive material of the present invention, a color coupler may be contained in the photographic emulsion layer, and the coupler may be either 4 equivalents or 2 equivalents, and a colored coupler for masking and a development inhibitor may be used. It may be a releasing coupler. As a yellow-forming coupler, an open-chain ketomethylene-based compound such as an acylacetamide-based compound, a pyrazolone-based compound as a magenta-forming coupler, and a phenol- or naphthol-based compound as a cyan-forming coupler are usually advantageously used.

[0028]

The present invention will now be described with reference to examples and reference examples, but the present invention is not limited thereto.

The compounds used in the following Reference Examples and Examples are shown below.

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12] Reference Example 3.5 g of gelatin was added to 35 ml of distilled water and dissolved, and 2.0x10 of the dye according to the present invention or the comparative dye shown in Table 1 was dissolved therein.
^After adding 5 ml of an aqueous solution containing ^-4 mol, and further adding 1.25 ml of 10% saponin aqueous solution and 0.75 ml of 1% formalin aqueous solution,
Water was added to this to make the total volume 50 ml. This aqueous dye solution was applied onto an acetyl cellulose support and dried to prepare Samples 1-1 to 1-14, respectively, which were then treated with a model fatigue solution in which the following dyes were accumulated.

Each sample was stirred at 35 ° C. in an aqueous sodium hydroxide solution (pH 10.4) containing the same dye compound (10 / mol extinction coefficient) in a molar concentration as that used in preparing each sample, It was immersed for 20 seconds, washed with water for 15 seconds in a water bath containing a dye having a concentration of (1 / molar extinction coefficient), and dried.

For each of the above-mentioned samples, the visible spectrum was measured before and after immersion, and the elution rate was calculated from the absorbance at the maximum absorption wavelength by the following formula, and the results are shown in Table 1.

[0039]

[Equation 1]E ₁Is the absorbance before immersion in the aqueous sodium hydroxide solution, ₂
Represents the absorbance after immersion.

Each sample was immersed in a developing solution having the following composition at 35 ° C.
It was immersed for 30 seconds, washed with water for 15 seconds in a water tank containing a dye of (1 / molar extinction coefficient) molar concentration, and then dried.

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

[0042]

[Equation 2]E ₃Is the absorbance before immersion in the developing solution. _FourIs the absorption after immersion in the developer.
Represents luminous intensity. [Developer composition] Metol 3.0 g Sodium sulfite (anhydrous) 45.0 g Sodium carbonate (monohydrate) 80.0 g Potassium bromide 2.0 g Dye (molecular weight) x (10 / mol extinction coefficient) g Add 1 liter of water To do.

[0043]

[Table 1] Example 1 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, each layer of the constitutions shown in Tables 2 and 3 was added to a polyethylene layer containing titanium oxide. By coating on the side, multilayer silver halide color photographic light-sensitive material samples 2-1 to 2-12 were prepared. Each coating solution was prepared as follows. First layer coating liquid 26.7 g of yellow coupler (YC-8), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2)
To 6.67 g, stain inhibitor (HQ-1) 0.67 g and high boiling organic solvent (DNP) 6.67 g, ethyl acetate 60 ml was added and dissolved, and this solution was dissolved in 20% surfactant (SU-1) aqueous solution 7 m
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing l using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (Em-B) (containing 8.67 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(H-1) was added to the layer and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (SU-
2) was added to adjust the surface tension. (Preparation of blue-sensitive silver halide emulsion) In 1000 ml of 2% gelatin aqueous solution kept at 40 ° C, the following (solution A) and (B)
Solution) is added simultaneously over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (solution C) and (solution D) are added to pAg = 7.3, pH.
It was added simultaneously over 180 minutes while controlling to 5.5. At this time,
The pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water added 600 ml (Solution D) ) Silver nitrate 300g After adding water and adding 600ml, desalting was performed using 5% aqueous solution of Kao Atlas Demol N and 20% magnesium sulfate, and then mixed with gelatin aqueous solution to give an average particle size of 0.85 μm. A monodisperse cubic emulsion EMP-1 having a variation coefficient of particle size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was carried out at 50 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
The average particle size is 0.43μ in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
The average particle size is 0.50μ in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

Further, the following metal compounds were added to the above (C liquid).

K ₂ IrCl ₆ 3.8 × 10 ⁻⁸ mol / mol AgX K ₄ Fe (CN) ₆ 1.2 × 10 ⁻⁵ mol / mol AgX For the above EMP-3, the following compound was optimally used at 60 ° C. Sensitize and red-sensitive silver halide emulsion (Em-
R) was obtained.

Sodium thiosulfate l.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6x10 ^-4 mol / mol AgX Sensitizing Dye RS-l2 1x10 ^-4 mol / mol AgX

[0052]

[Table 2]

[0053]

[Table 3] The sample thus produced was exposed by a conventional method and then processed according to the following processing steps.

Treatment process Treatment temperature Time Color development 39.0 ± 0.3 ° C. 25 seconds Bleach fixing 35.0 ± 0.5 ° C. 25 seconds Stabilization 30 to 34 ° C. 60 seconds Dry 60 to 80 ° C. 60 seconds Color developer Pure water 800 ml Triethanolamine 10 g N , N-diethylhydroxylamine 5g potassium bromide 0.02g potassium chloride 2g potassium sulfite 0.3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-3,5-disulfonic acid disodium 1.0g N -Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 6.0g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Potassium carbonate 27g To 1 liter and adjust the pH to 10.10. Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 1 liter and add potassium carbonate or glacial acetic acid. Adjust pH to 5.7 with. Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Next, the following evaluation was performed on each of the obtained samples. <Whiteness> For each sample, use the Konica Color Printer / Processor CL-PP170QA (manufactured by Konica Corporation), and use the above-mentioned treatment liquid as the treatment liquid until the cumulative value of the replenishment amount exceeds the liquid amount at the start. Continuous replenishment processing was carried out, and the red light reflection density (D _R ) of the unexposed area was measured by 310TF of X Light Company.

The smaller D _R , the better the whiteness. D _R
The value of is acceptable if it is 0.02 or less,
When it exceeds 0.020, the whiteness is visually noticeable, and
If it exceeds 0.025, serious deterioration of photographic quality will occur.

[0057]

[Table 4] From the results in Table 4, it can be seen that the samples using the dye of the present invention have good whiteness even in rapid processing.

[0058]

INDUSTRIAL APPLICABILITY Since the present invention contains a water-soluble oxonol dye represented by the general formula [I] as a light-absorbing dye, the obtained silver halide photographic light-sensitive material has good spectral absorption characteristics. And has an excellent effect that it does not adversely affect the photographic light-sensitive material (inert to the emulsion), is easily decolorized and / or flows out in the photographic development process, and has little contamination after the process. Is.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula [I]. [Chemical 1] [In the formula, R ¹ and R ² represent a heterocycle and a phenyl group having two or more sulfo groups, and L _{1 to} L ₅ represent a methine group. ]