JPH10339926A - Silver halide photographic sensitive material - Google Patents

Abstract

(57) Abstract: In a silver halide photographic material, a silver halide photographic material having improved dry fog is provided. The present invention relates to a silver halide photographic material having at least a photosensitive silver halide emulsion layer on a support, characterized in that the silver halide emulsion layer contains a wax. Silver photographic photosensitive material.

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 having improved fog.

[0002]

2. Description of the Related Art Photographic materials are generally prepared from a support such as cellulose triacetate, polyethylene terephthalate, paper or paper coated on both sides with a polyolefin, or on both sides directly or through an undercoat layer. The silver halide photographic emulsion layer and, if necessary, various layers such as an intermediate layer, a protective layer, a filter layer, an antistatic layer and an antihalation layer are coated in various combinations.

Among these layers, silver halide photographic emulsion layers contain silver halide crystals having various grain sizes and shapes, sensitizing dyes and various other additives depending on the purpose. With the increase in sensitivity of materials, problems in the production of photographic materials have been increasingly highlighted. As one of them, coating and drying at higher speeds are constantly being considered by manufacturers to improve production efficiency.However, in order to produce at higher speed in limited equipment, drying is An increase in speed is required. However, when the layer containing the silver halide emulsion is rapidly dried, the binder rapidly undergoes volume shrinkage due to drying, causing stress concentration due to the volume shrinkage in the silver halide crystal, which causes so-called stress fogging. Many occurred. Such fogging phenomenon of silver halide crystals due to stress concentration or residual stress has been widely improved as a cause of dry fogging.

Patents relating to drying conditions that do not cause dry fogging are described in, for example, Japanese Patent Application Laid-Open Nos.
Examples of the antifoggant include polyhydric alcohols described in JP-A-6-273889 and JP-A-2-24739, and JP-A-1-159635. Examples thereof include a method of using dextran in combination and a method of adding polyhydroxybenzenes as disclosed in JP-A-2-281251. It is also known that polymer latex is effective for drying fog.

Although the above-described method may be effective under limited conditions, it is widely applied to the production of photographic materials under high-speed and high-temperature conditions as the object of the present invention. Could not.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which does not cause dry fog even when the silver halide photographic light-sensitive material is manufactured under high-speed and high-temperature drying conditions. It is.

[0007]

To find a solution that does not cause dry fogging even when a silver halide photographic light-sensitive material is manufactured under a high-speed and high-temperature drying condition is to contain a wax in a silver halide emulsion layer. To achieve this.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The wax referred to herein is a low-temperature compound having a long-chain hydrocarbon group and solid at room temperature, and is a compound other than a hydrophobic hydrocarbon compound such as paraffin wax or carnauba wax or a long-chain hydrocarbon group. And a long-chain aliphatic carboxylic acid having a hydrophilic group. Preferred examples of the wax include compounds as described in Examples, but the present invention is not limited thereto. The above-mentioned wax is preferably added to the silver halide emulsion in a state of being dispersed in water.To disperse the wax, emulsification is carried out using a surfactant commonly used for photography as a dispersant. Dispersible, for example, saponin (steroid type), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars,
Carboxyl groups, such as alkyl carboxylate, alkyl sulfates, alkyl phosphates,
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate groups, and phosphate groups, amino acids,
From amphoteric surfactants such as aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphate esters, cationic surfactants such as fatty acids or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium hydrochlorides such as pyridinium and imidazolium Use what is appropriately selected,
Using an appropriate disperser such as an ultrasonic homogenizer or a valve homogenizer, create an O / W emulsion,
This dispersion is then added to a silver halide emulsion to form a coating solution.

The average particle size (volume average particle size) of the wax prepared by the above method is not particularly limited, but the smaller the particle size, the more significantly the dry fogging is effected.
Further, in the case where transparency is required as a photosensitive material, if the particle size of waxes exceeds several microns, the transparency is impaired, which may cause a problem. Alternatively, if waxes are agglomerated or present in the emulsion layer with a particle size exceeding several microns, light scattering occurs during exposure,
In some cases, this is not preferable because the resolution of an image line or the like is reduced. Therefore, the preferred particle size of the wax is preferably in the range not exceeding 1 micron. More preferably, it is 0.5 micron or less. Especially 0.05-0.
It can be used most preferably when there is at most 1% or less of components within a range of 4 microns and a particle size distribution of 1 micron or more in particle size distribution. Even when a wax having such a particle size range is introduced into the emulsion layer, the film is homogeneous, excellent in transparency or gloss, and can be used extremely preferably without adversely affecting light scattering during exposure. Conventionally, in the emulsification and dispersion of wax, only an emulsion having a particle diameter of about several microns has been obtained, but in recent years, the development of emulsification and dispersion technology has made it possible to reduce the particle size. For example, Chukyo Yushi Co., Ltd. has supplied wax emulsions of about 0.1 to 1 micron. The inventor has also found that the use of a finely divided wax emulsion significantly improves dry fog.

The range in which the wax can be added to the emulsion layer depends on the coating amount of the emulsion layer itself, but is preferably in the range of 0.01 to 10 grams per square meter, and more preferably 0.1 to 10 grams per square meter. A range from 05 grams to 1 gram is preferred. When added below this range, the effect of adding the wax is unlikely to appear, and when added above this range, the transparency of the photosensitive layer decreases,
Problems such as deterioration of image quality due to light scattering may occur, which may be undesirable.

By introducing a wax into a silver halide emulsion layer, even when a photographic light-sensitive material is manufactured under conditions of high-speed and high-temperature drying, the wax reduces stress caused by shrinkage of the emulsion layer coating film, and the silver halide It has been found in the present invention that dry fogging can be effectively prevented in order to alleviate the influence of stress on the crystal. By the addition of such a wax to the emulsion layer, the production of a photographic light-sensitive material, which has been conventionally coated and dried at a drying temperature of at most about 40 to 50 ° C., causes dry fogging even under high-temperature drying conditions of, for example, about 50 to 80 ° C. One of the effects of the present invention is that it is possible to perform drying at a high speed without any problem, and that the contribution to the efficiency in the manufacturing process is extremely large.

The silver halide used in the photosensitive silver halide emulsion of the photographic light-sensitive material of the present invention is not particularly limited, but a surface latent image-type silver halide emulsion is preferred. Silver chlorobromide, silver chloroiodobromide, silver bromoiodide,
Silver bromide or the like can be used. When silver chloroiodobromide or silver bromoiodide is used, the content of silver iodide is preferably within a range of 5 mol% or less. Morphology of silver halide grains,
The crystal habit and size distribution are not particularly limited, but those having a particle diameter of 0.7 μm or less are preferred. Silver halide emulsions include a gold compound such as chloroaurate and gold trichloride, a sulfur compound which forms silver sulfide by reacting with a salt or a silver salt of a noble metal such as rhodium and iridium, a stannous salt, Sensitivity can be increased without reducing particles with a reducing substance such as an amine. Further, iron compounds such as salts of noble metals such as rhodium and iridium, and red blood salts can be present during physical ripening or nucleation of silver halide grains.

In the present invention, the term "surface latent image type halide emulsion" means an emulsion comprising silver halide grains having a surface sensitivity higher than the internal sensitivity. This emulsion is preferably US Pat. No. 4,224,401. It has a difference between the surface sensitivity and the internal sensitivity specified in the specification. The silver halide emulsion is desirably monodispersed, particularly in the above-mentioned U.S. Pat.
Emulsions having the monodispersity specified in JP-A-224,401 are preferred. The silver halide emulsion used in the present invention preferably contains a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, potassium rhodium (III) hexachloride, ammonium rhodium (III) hexachloride, etc.). . The addition amount of the rhodium salt is preferably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁴ mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.7 microns or less, particularly preferably in the range of 0.1 to 0.4 microns. The shape of silver halide grains is cubic,
It may be a regular one such as an octahedron or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow particle size distribution. The term "monodisperse emulsion" as used herein means an emulsion in which 90%, more preferably 95%, of the total number of grains falls within a grain size range of ± 40% of the average grain size. The form of reacting a soluble silver salt with a soluble halide salt for preparing a silver halide emulsion in the present invention may be any one of a single jet method, a double jet method, and a reverse mixing method formed in excess of silver ions. Although a means may be used, for the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form grains is particularly preferable. The silver halide emulsion prepared in this manner may or may not be chemically sensitized, and when chemically sensitized, ordinary silver sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, etc. Is used.

In the light-sensitive material of the present invention, a hydrazine compound may be contained in the silver halide emulsion layer.
Further, it may contain a new aqueous colloid layer adjacent to the surface latent image type silver halide emulsion layer. Such a layer is a layer having any function, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer, as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains. There may be. Since the content of the hydrazine compound in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound, and the development conditions, the appropriate content can vary over a wide range. A range of about 1.times.10.sup.- ⁶ to 1.times.10.sup.- ² mole per mole of silver in the latent image type silver halide emulsion is practically useful.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These sensitizing dyes
They may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that does not itself have spectral sensitization or a substance that does not substantially absorb visible light and that exhibits supersensitization.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, proteins such as casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate,
Various kinds of synthesis such as mono- or copolymers of sugar derivatives such as starch derivatives, polyvinyl alcohol, partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacramide, polyvinyl imidazole, etc. A hydrophilic polymer substance can be used. Examples of gelatin include lime-treated gelatin, acid-treated gelatin Bull. Soc. Sci. Ph
ot. Japan, No. 16, p. 30 (1966)
Enzyme-treated gelatin as described in (1) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

When a hydrazine compound is contained in the emulsion layer, a conventional safelight dye may be added to the emulsion layer or another hydrophilic colloid layer. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, thioketo compounds, azeindenes, etc. Many compounds, known as stabilizers, can be added. Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole).

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds, and active halogen compounds (such as 2,4-dichloro-6) −
Such as hydroxy-s-triazine) can be used alone or in combination. In the photosensitive silver halide emulsion layer or a layer adjacent thereto, Research Disclosure (Research Disclosure) 17 is used for the purpose of increasing sensitivity, increasing contrast, or promoting development.
No. 465, Sections XX} BD. Particularly, it is preferable to add polyethylene glycol or a derivative thereof.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or hardly soluble synthetic polymer decomposition product in a photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid, α , Β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrenesulfonic acid and the like can be used as a monomer component.

[0020]

The present invention will be described more specifically with reference to the following examples, but the embodiments of the present invention are not limited thereto.

EXAMPLE In the formulation of the emulsion layer, the average particle size of iridium-containing particles adjusted by control double jet was 0.2.
A 5 micron monodispersed silver chlorobromide emulsion was prepared. After desalting, washing and re-dissolving by flow curation method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added to a concentration of 0.2 g / m ² to give a sensitizing dye. Anhydro-5,5-dichloro-9-ethyl-3,3 '
- di - (3-sulfopropyl) oxacarbocyanine hydroxide pyridinium was added to a 0.2 g / m ^2. In the emulsion thus obtained, each of the waxes (A) to (F) according to the present invention was added at a solid content of 0.5 g / m ^2.
And gelatin was further adjusted to 2.5 g / m ² . As a hardening agent, 2-hydroxy-
Sodium 4,6-dichloro-1,3,5-triazine was added at 1% of gelatin.

Emulsion (silver chlorobromide) 640 g gelatin 50 g amphitro-5,5-dichloro-9-ethyl-3,3'-di- (3-sulfofluoropropyl) oxacarboxycyanine human peroxytohidroxyniur 4 g wax (A ) To (F) 10 g 6-methyl-4-humanperoxy-1,3,3a, 7-tetrasaindene 4 g Finish with water to 1000 g.

Wax (A): Stearic acid (Cellosol 920, manufactured by Chukyo Yushi, volume average particle diameter 5 μm) Wax (B): Carna wax (Cellosol 524, manufactured by Chukyo Yushi, volume average particle diameter 0.2 μm) Wax (C): paraffin Wax (Hydrin-7, manufactured by Chukyo Yushi, volume average particle diameter 0.85 μm) Wax (D): Ethylene bis stearamide (Hymicron G-110, manufactured by Chukyo Yushi, 0.4 μm volume average particle diameter) Wax (E): Ethylene diesel Stearoamite II (Chukyo Yushi Hytulin B-961, volume average particle diameter 5.5 μm) Wax (F): Stearic acid amite II (Chukyo Yushi Hymicron G-270, volume average particle diameter 0.4 μm) Also, as a comparative sample, In the above formulation, a sample to which no wax was added (Comparative Sample 1) and a sample to which the same amount of polyethyl acrylate emulsion was added instead of wax. (Comparative Sample 2), a sample similarly containing the same amount of ethylene glycol (Comparative Sample 3), a sample similarly containing the same amount of trimethylolpropane (Comparative Sample 4), and a sample similarly containing the same amount of hydroquinone ( Comparative sample 5) was also prepared at the same time.

An emulsion coating solution having the above formulation was applied to an aqueous undercoat-treated polyethylene terephthalate film using a rod bar, and was set by applying a cool air thereto.
It dried in the air dryer set to 70 degreeC or 70 degreeC. The obtained photographic light-sensitive material sample was image-exposed using a xenon sensitometer, subjected to normal development processing, and then subjected to image density (Dm
ax) and the background density (Dmin) were determined by measuring the transmission density. The results are shown in Table 1.

[0025]

[Table 1]

As can be seen from the results in Table 1, the Dmin was not increased for the sample to which the wax was added even under the conditions of high temperature drying at 70 ° C., whereas the comparative sample 1 was significantly increased, and No sufficient effect was obtained with the anti-fogging agent known from U.S. Pat. Further, in the present invention, by using a wax emulsion having a particle size of 1.0 μm or less, and more preferably 0.5 μm or less, the effect is more remarkably exhibited. In this example, there was no effect on the photosensitive properties (sensitivity, tone, etc.) of the photosensitive material due to the presence or absence of the compound of the present invention, and the effect on the photosensitive properties was observed even after long-term storage. Did not.

[0027]

According to the present invention, a silver halide photographic light-sensitive material having significantly reduced dry fog is provided.

Claims (2)

[Claims] 1. A silver halide photographic material having at least a photosensitive silver halide emulsion layer on a support,
A silver halide photographic material comprising a wax in the silver halide emulsion layer. 2. The method according to claim 1, wherein the wax has a volume average particle diameter of 1.0.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is added in the form of a dispersion having a particle diameter of not more than micron.