JPS6149655B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material for black and white photography that exhibits good photographic properties with respect to lithium-type developers and non-lithium-type developers. Silver halide photographic materials are used in a wide range of fields because of their ease of adjusting sensitivity, gradation, etc. Particularly in the field of lithography, it is necessary to have a fairly high contrast due to the necessity of its use, and the special technology for this purpose is to use silver halide photographic materials that contain a relatively large amount of silver chloride. This is processed with a developer containing a dihydroxybenzene compound as a developing agent and having a relatively low sulfite concentration (hereinafter referred to as a lithium developer) to create an image consisting of halftone dots and lines with extremely high contrast. The method of forming was commonly used. Furthermore, when the silver halide emulsion layer of the above-mentioned silver halide photographic light-sensitive material contains a compound having a polyalkylene oxide chain in its molecule, for example, as described in Japanese Patent Publication No. 42-25201 and Japanese Patent Application Laid-Open No. 52-108130, The image becomes even more sharp and the image quality improves. In addition, as a photosensitive material for graphic arts,
Good physical properties such as dimensional stability, film formation, and automatic processor processing characteristics are also required, and for this reason, the gelatin content is designed to be as small as possible. However, the image quality improvement effect of the above-mentioned polyalkylene oxide compounds is greatly influenced by the amount of gelatin, and if the amount of gelatin is small, the effect becomes considerably small, so a considerably large amount is required to compensate for this effect. Sometimes silver halide 1
The amount may be as high as several grams per mole. On the other hand, as a processing solution, although it is difficult to obtain the same high contrast as a lithium-type developer, due to its stability, it contains a relatively large amount of sulfite and the developing agent is not limited to dihydroxybenzene-based compounds. The combination is more common, and the Lith-type developer is rather special. When processed with a liquid, good photographic properties cannot be obtained because fog increases and contrast decreases significantly. Therefore, one of the objects of the present invention is to develop a lithium-type developer,
It is an object of the present invention to provide a silver halide photographic light-sensitive material which can obtain good photographic performance even when processed with a non-Lith type developer. Another object of the present invention is to provide a silver halide photographic material having excellent image contrast without affecting sensitivity or fog by using a novel combination of components. Other objects will become apparent from the description of the present specification and examples. According to the present invention, the object of the present invention is to provide a silver halide photographic material having at least one photographic constituent layer containing silver halide containing at least 50 mol% of silver chloride, in which the photographic constituent layer contains: It has been revealed that this can be achieved by using a silver halide photographic light-sensitive material for graphic arts containing fine paraffin having a particle size of 5 μm or less and at least one compound having an alkylene oxide chain in the molecule. That is, the present invention is characterized in that a polyalkylene oxide compound is contained together with liquid or solid paraffin in the photographic constituent layer of a silver halide photographic light-sensitive material for squirrels. A silver halide photographic material with excellent characteristics and high contrast could be obtained. The present invention will be explained in more detail below. In the present invention, the compound having a polyalkylene oxide chain in the molecule used in combination with paraffin can preferably be represented by the following general formulas (1) to (3). General formula (1) General formula (2) R ₅ O (CH ₂ CH ₂ O) m ₃ (CH ₂ CH ₂ CH ₂ CH ₂ O) p ₃
(R ₂ O) n ₂ (CH ₂ CH ₂ CH ₂ CH ₂ O) p ₄ (CH ₂ CH ₂ O)
m ₄ R ₆ General formula (3) R ₇ O (R ₂ O) n ₃ (CH ₂ CH ₂ O) m ₅ R ₈ In the above formula, R ₁ , R ₃ , R ₅ , R ₆ , R ₇ and R ₈ is
Represents a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group or acyl group, and R ₂ is

[Formula] or represents − CH ₂ CH ₂ CH ₂ CH ₂ −, and R ₄ and R ₉
is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
It represents a cycloalkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryloxy group. n ₁ , n ₂ and n ₃ are integers from 0 to 5, p ₁ + p ₂ and p ₃ + p ₄ are 0
~50 integers, and m ₁ + m ₂ , m ₃ + m ₄ and m ₅
is an integer between 10 and 80. Typical specific examples of compounds represented by each of the above general formulas are listed below, but the present invention is not limited thereto.

【table】

[Table] Next, regarding the solid paraffin used in the present invention, the solid paraffin has a solid particle size of 5 μm or less, preferably 1 μm or less. That is, solid paraffin with a particle size of 5μ or more can achieve some of the effects of the present invention, but
As the particle size becomes larger, the stability of the paraffin dispersion or paraffin coating solution over time deteriorates, and the transparency of the resulting coating film deteriorates. The liquid or solid paraffin of the present invention is contained in the photographic constituent layer as a dispersion liquid, but in order to prepare a dispersion liquid of solid paraffin having the above particle size, the solid paraffin is dissolved in a low boiling point solvent to form a solution, and gelatin It is produced by dispersing it in water containing protective colloids and surfactants such as, for example, using a homogenizer. The low boiling point solvent used above is
Even if it remains in the dispersion, it does not impede the effects of the present invention, but it is preferable to remove it by heating or reducing pressure after dispersion is completed. In the present invention, the amount of paraffin added to the photographic constituent layer has an effect depending on the amount added, but in reality, adding a large amount may deteriorate the physical strength of the coating film. Usually 5% by weight or more based on the hydrophilic binder in the paraffin-containing layer
100% by weight, particularly preferably 10% to 50% by weight. On the other hand, a polyalkylene oxide compound represented by the above general formula, particularly a polyoxyethylene compound, exhibits a development accelerating effect in a non-lithium type developer, but on the contrary exhibits a development suppressing effect in a lithium type developer. This peculiar behavior is well known in the art. This lithium development inhibitory effect gives good photographic performance when processed with a lithium type developer, but as mentioned above, when processed with a non-lithium type developer, due to its unfavorable development accelerating effect. ,
This results in increased fog or decreased contrast, making it difficult to obtain good photographic performance. Generally, fog suppressants are added as a countermeasure, but these reduce fog, and most of them also reduce sensitivity and contrast, and also suppress lithographic development, so polyalkylene oxide-based compounds are used. It becomes necessary to reduce the amount of the film, and as a result, the photographic performance in lithographic development also deteriorates. According to the present invention, the amount of the polyalkylene oxide compound added to the photographic constituent layer is:
The amount is in the range of 0.01 g to 2.0 g per mole of silver halide, preferably 0.03 g to 1.0 g. As the solvent for addition, water or an organic solvent miscible with water, such as ethanol, methanol, acetone, etc., is used. There is no particular restriction on the timing of adding the liquid or solid paraffin and polyalkylene oxide compound used in the present invention to the photographic constituent layer, but for example, they may be added after the silver halide grain formation step or after the second ripening step. It is preferable to add and contain the following photographic constituent layers:
Although an emulsion layer containing silver halide is most preferred, the effects of the present invention can also be obtained by containing silver halide in other adjacent layers, auxiliary layers, intermediate layers, etc. on the same side of the support. According to the present invention, the paraffin and the polyalkylene oxide compound may both be contained in a single layer, but it is also possible to separately add and contain the paraffin and the polyalkylene oxide compound to the constituent layer. It is. The effects of the present invention can only be achieved by using liquid or solid paraffin in combination with polyalkylene oxide compounds that have the drawbacks mentioned above. It was a surprising discovery that the contrast was improved for both lithium-type and non-lithium-type processing solutions, and the photographic performance was significantly improved. In the composition of the silver halide used in the light-sensitive emulsion in the present invention, a high development speed is required in order to cause explosive development such as lithographic development, so silver chloride is used in contrast to silver halide. Silver chlorobromide or silver chloroiodobromide is required to contain 50 mol % or more, and more preferably silver chlorobromide or silver chloroiodobromide containing 40 mol % or less of silver bromide and 5 mol % or less of silver iodide. These silver halides are also described in "The Theory of the Photographic Process" by James James, 4th edition, Macmillan Publishing (1977) 88-104.
Neutral method, acidic method, ammonia method, forward mixing method, back mixing method, single jet method, double jet method, controlled double jet method, convergence method, core-shell method, etc. described in the literature such as p. It can be manufactured by the following method. Furthermore, there are no particular limitations on the grain size, grain size distribution, crystal habit, form (normal crystal, twin crystal, etc.) of the silver halide grains used, but silver halide grains with relatively uniform grain sizes of 1 μm or less are preferred. Further, these silver halide grains or silver halide emulsions may contain an iridium salt and/or a rhodium salt in order to improve the closed light exposure characteristics and the like. These silver halides generally include sulfur sensitizers, such as sodium thiosulfate, thiourea, etc.; noble metal sensitizers, such as gold sensitizers, specifically chloroaurates, gold trichloride, etc., palladium sensitizers, specifically Examples include palladium chloride, palladate chloride, platinum compounds, iridium compounds, etc.; selenium sensitizers, such as selenite, selenourea; reduction sensitizers, such as stannous chloride, polyamines such as diethylenetriamine, It can be chemically sensitized by using chemical sensitizers such as sulfite and silver nitrate alone or in combination, and it can be optically sensitized by using optical sensitizers such as cyanine dyes and merocyanine dyes alone or in combination. It can be sensitized to a desired wavelength range. Electron capture compounds such as metal dopants or desensitizing dyes can also be used in the present invention,
It can also be applied to direct positive photographic silver halide emulsions containing 50 mol% or more of silver chloride that have been given fog. As the silver halide vehicle having the above composition, gelatin, gelatin derivatives, synthetic hydrophilic polymers, etc. can be used. The silver halide photographic emulsion used in the present invention can contain various photographic additives. For example, antifoggants include azaindenes, specifically 4-hydroxy-6-methyl-1,
Any antifoggant known in the art can be used, including 3,3a,7-tetrazaindene, triazoles, thiazoles, and tetrazoles. Hardeners include aldehyde compounds, ketone compounds, halogen-substituted acids such as mucochloric acid,
Ethyleneimine compounds and the like can be used.
As the spreading agent, saponin, lauryl or oleyl monoether of polyethylene glycol, etc. are used. Although there are no particular limitations on the development accelerator, for example, compounds such as those described in JP-A No. 49-24427, quaternary ammonium salts, etc. can be used. As a physical property improver, a polymer latex made of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, etc. can be contained. The silver halide emulsion layer or other constituent layers of the light-sensitive material according to the present invention may include, for example, Japanese Patent Application No. 52-104940.
Antistatic agents such as those described in JP-A-51-56220 and JP-A-49-46733 can be added. Examples of the support used for coating the light-sensitive emulsion in the present invention include polyethylene terephthalate film, polycarbonate film, polystyrene film, cellulose acetate film, and the like. The present invention achieves the above-mentioned object through its technical configuration. In addition, the silver halide photographic light-sensitive material according to the present invention can be used in a form in which a silver image is formed by a development process, such as a cerium reducing solution, a cerium reducing solution, or a cerium reducing solution. ,
It has the effect that the force reduction width is wide and the force reduction operation is easy to perform when reducing force using a commonly used force reducing liquid such as EDTA iron salt reducing liquid. Here, a wide reduction width means that the reduction rate of the halftone dot size is greater than the reduction rate of the halftone dot density when reducing the force of a halftone image or the like. EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited to these embodiments. Example 1 In an aqueous binder containing gelatin, 69.8 mol% of silver chloride and 30% of silver bromide were prepared by double jet method.
After preparing a silver halide emulsion containing 0.2 mol% of silver iodide and chemically sensitizing it using a combination of noble metal sensitization using chloroauric acid and sulfur sensitization using sodium thiosulfate, the merocyanine shown below was prepared. A dye was added for optical sensitization, and a polymer latex consisting of 4-hydroxy-6-methyl-1,2,3a,7-tetrazaindene as a stabilizer, saponin as a spreading agent, and ethyl acrylate as a physical property improver was added. In addition, this was designated as Preparation Solution A. (merocyanine pigment) On the other hand, add 700 g of liquid paraffin to 300 g of ethyl acetate.
Dissolve in cc, mix 200g of gelatin, 260c.c. of Nitsusan Yushi Alkanol-XC10%, and 3.6cm of pure water.
After swelling, it was added to the solution kept at 60°C, and then dispersed at a pressure of 250 kg/cm ² using a pressurized homogenizer laboratory model manufactured by Manton-Gaulin Co., Ltd. in the United States to obtain a liquid paraffin dispersion with an average particle size of 0.13 μ. . Using the same method, the temperature was kept at 80℃ and the average particle size was 0.22.
A solid paraffin dispersion of μ was obtained. A portion of the adjustment solution A was divided into three parts: one in which nothing was added (Sample-1), one in which 500 mg of Exemplified Compound (1) was added to 1 mole of silver halide (Sample-2), and one in which Exemplified Compound (1) was added to 1 mole of silver halide (Sample-2). ) per 1 mole of silver halide
Added 1.0g of Exemplary Compound (1) per 1 mole of silver halide (sample-3), and added the above-mentioned liquid paraffin dispersion in an amount such that the paraffin was 25% by weight based on the hydrophilic binder. Mucochloric acid and glyoxal were added to each sample and coated on a polyethylene terephthalate support at a silver content of 35 mg per 100 cm ² to obtain a light-sensitive material. These samples were cut into small pieces and exposed to tungsten light for 2 seconds using a step wedge. This sample was subjected to Lith development at 27° C. using Sakura Automatic Processing Machine GQ-25S with Sakura Lis developer CDL-271 (both manufactured by Konishiroku Photo Industry Co., Ltd.). On the other hand, these samples were subjected to a non-lithographic development process at 38° C. using Sakura automatic processor QS-25 and CDM-621 (both manufactured by Konishiroku Photo Industry Co., Ltd.). The results of each treatment are shown in Table 1. The contrast during evaluation expressed the slope of the leg of the characteristic curve, which is considered to be particularly important as a photographic characteristic.

[Table] As is clear from Table 1 above, when only a polyalkylene oxide compound is added to the paraffin-free photosensitive emulsion according to the present invention and the amount added is increased, in lithium type development, Although it improves photographic properties, it degrades photographic properties upon non-lithographic development. On the other hand, when paraffin and a polyalkylene oxide compound are used in combination, photographic properties can be improved in both lithium-type development and non-lithography development, and excellent contrast can be obtained without increasing fog. Example 2 One portion of Exemplified Compound (9) was added to the remaining part of the adjustment solution A.
After adding 700mg to the molar silver halide, the samples were divided into three types: one without paraffin (sample-5), one with the same amount of liquid paraffin as sample-4 added (sample-6), and one with solid paraffin added in the same manner as sample-4. (Sample-7) was prepared, coated and dried in the same manner as in Example 1, and subjected to lithium-type and non-lithographic development treatments. The results are shown in Table 2.

[Table] According to Table 2 above, the paraffin according to the present invention was found to exhibit good improvement in photographic properties in both liquid paraffin and solid paraffin. Example 3 Exemplary compound (4) (400 mg per 1 mole of silver halide) was added to the remainder of the preparation solution A, and the same amount of liquid paraffin as in sample-4 was added to the sample without paraffin (sample-8). (sample-9), a sample with double the amount of liquid paraffin as sample-9 (sample-10), and a sample with 50 mg of 5-nitrobenzimidazole added per 1 mole of silver halide as a fog inhibitor (sample). -11), 5-nitrobenzimidazole added in twice the amount of sample-11 (sample-11)
12) was prepared and treated after coating and drying in the same manner as in Example 1. The results are shown in Table 3.

[Table] According to Table 3 above, when the fog suppressant 5-nitrobenzimidazole is added as a substitute for paraffin, although it has a suppressive effect on fog, it has an adverse effect on sensitivity or contrast. On the other hand, it has been found that the combined use of paraffin and polyalkylene oxide compounds according to the present invention suppresses fogging, has very little influence on sensitivity, and exhibits excellent contrast effects.

Claims (1)

[Claims] 1. In a silver halide photographic light-sensitive material having at least one photographic constituent layer containing silver halide containing at least 50 mol% of silver chloride, the photographic constituent layer contains fine paraffin with a particle size of 5 μm or less, and molecules. 1. A silver halide photographic light-sensitive material for graphic arts, which contains at least one kind of compound having an alkylene oxide chain.