JPS6118174B2 - - 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 in which the back layer of a support contains an inorganic compound that gives bromide ions when eluted into a developer. Silver halide photographic materials are subjected to running processing in large-scale laboratories in response to the recent demand for rapid processing. For example, the so-called lithium-type silver halide photographic light-sensitive materials used for photoengraving in the field of the printing industry, etc., are produced using a high-contrast developer called an infectious developer with a low concentration of free sulfite ions, which uses hydroquinone as a developing agent. A running process is carried out using a continuous automatic developing machine using Lith developer. However, the running process in this lithographic development process is generally carried out under optimum development conditions such as the optimum development temperature, time, and amount of replenishment per unit area of the silver halide photographic light-sensitive material to be developed to form a line image or halftone image. and set
Under these conditions, various types of silver halide photographic materials are continuously developed. Therefore, during this running process, components added to the silver halide photographic light-sensitive material that are eluted into the developer are sequentially eluted and accumulated in the developer, and the concentration of these eluted components in the developer is reduced. The size will change. Some of the components eluted into the developing solution affect the photographic properties of the silver halide photographic light-sensitive material to be developed, and become a cause of impairing the stability of the finished quality. This disadvantage arises because if silver halide photographic materials of the same type (same components) are continuously developed, the elution amount of the components that affect the photographic performance of the material is maintained constant, and the amount of the developer replenisher is reduced. This problem is solved because the accumulated amount in the developer is kept constant in relation to the overflow of the developer due to replenishment and the amount of developed photosensitive material carried out, but as mentioned above, silver halide of different types (different components) When photographic light-sensitive materials are continuously developed, it is common for the amounts of components added to the light-sensitive materials to vary. At present, it is undeniable that the elution amount is not constant and the concentration changes in magnitude. The above-mentioned development is performed when a direct X-ray photosensitive material and an indirect X-ray photosensitive material are simultaneously subjected to a running process in an X-ray photosensitive material, and when processing various gravure, facsimile, and micro photosensitive materials, or when processing various photosensitive materials for gravure, facsimile, and micro photosensitive materials. This is a phenomenon that occurs when two or more types of color photosensitive materials with different amounts of bromide ions eluted into the developer are continuously subjected to running processing, and from the viewpoint of stabilizing photographic properties. , development of a solution is desired. Therefore, the first object of the present invention is to create a photographic light-sensitive material in which the amount of bromide ions contained in the photographic constituent layer on the side of the support coated with the light-sensitive silver halide emulsion layer and eluted into the developer is varied. It is an object of the present invention to provide a silver halide photographic material configured such that the amount of bromide ions accumulated in a developer during development is maintained substantially constant even when subjected to running processing. The above object of the present invention and other objects described below are to provide two or more types of silver halide photographic light-sensitive materials that are subjected to running processing together in the same developer solution and have different amounts of bromide ions eluted into the developer solution. At least one of the silver halide photographic sensitizers has a light-sensitive silver halide emulsion layer on only one side of the support, and contains an inorganic compound on the other side that dissolves into a developer and gives bromide ions. This is achieved by a silver halide photographic material having layers. The type of inorganic compound that generates bromide ions (hereinafter referred to as a component of the present invention) contained in the back layer of the support of the silver halide photographic light-sensitive material according to the present invention is determined by the type of the silver halide photographic light-sensitive material. Generally, the silver halide photographic light-sensitive material and the silver halide photographic light-sensitive material which may be subjected to continuous running processing with the silver halide photographic light-sensitive material and which do not contain the components of the present invention, Alternatively, even if it contains the same type of component as the component of the present invention, it is determined in relation to a photosensitive material containing a different amount. The components of the present invention contained in the back layer of the support of the silver halide photographic light-sensitive material of the present invention are not limited to the same types of components as those contained in the surface layer of the support of the light-sensitive material. However, the determination of the components of the present invention to be contained in the back layer of this support is as follows:
This is because, as described above, it is generally determined in relation to different types of photosensitive materials that may be subjected to the same running process. In other words, regardless of whether the components of the present invention are contained in the support surface layer of the photosensitive material according to the present invention, the components of the present invention are contained in the support back layer of the photosensitive material according to the present invention. It can be made to contain. Typical specific examples of the components of the present invention to be contained in the back layer of the support of the silver halide photographic light-sensitive material according to the present invention are as follows. That is, typically potassium bromide, sodium bromide, ammonium bromide, etc. are used. The components of the present invention are the above-mentioned inorganic compounds from the viewpoint of solubility in a developer, photographic properties, etc. In the present invention, the amount of the component of the present invention to be added to the back layer of the support depends on the type of developer used in the development process, and the amount of other components that may be continuously subjected to running processing with this developer. Although it varies depending on the type of silver halide photographic light-sensitive material, in general, the components of the present invention are contained in constituent layers of other photographic light-sensitive materials that may be subjected to continuous running processing as described above. etc. are eluted into the developer or react with developer components to generate bromide ions, which are eluted and accumulated in the developer. When the material is subjected to running treatment, the components of the present invention described above similarly generate bromide ions,
The amount of the ions added is determined so that the concentration of the ions in the developer solution generated by accumulation remains the same. When the component of the present invention is also contained in the support surface layer, the concentration of ions eluted during development of the photosensitive material according to the present invention is as follows:
Of course, it is the sum of the eluted ion concentration and the eluted ion concentration of the component of the present invention contained in the back layer of the support of the present invention. Regarding the determination of the amount of the components of the present invention added, generally, the same components of the present invention are added to other silver halide photographic materials that may be subjected to running processing using the same developer. It can be calculated so that the total amount of the support surface layer and back layer is the same. When determining the amount added using this method, it is common to use the silver halide photographic light-sensitive material containing the largest amount of the components of the present invention as a standard; It is also possible to contain it in the back layer of the support of the light-sensitive material according to the present invention in such an amount as to be added. In short, in the present invention, when two or more types of silver halide photographic light-sensitive materials are subjected to running processing using the same developer, the concentration of bromide ions in the developer remains the same between the start and end of the run. The components of the present invention are contained in the back layer of the support of the photographic light-sensitive material according to the present invention so that there is no change in density or the amount of change is small. The components of the invention are added to the support back layer as described above. Conventionally, a gelatin layer, an anti-halation gelatin layer, or the like is generally provided on the back side of the support to prevent curling and halation. Accordingly, the components of the present invention may be added to these layers along with hardeners, matting agents, antihalation dyes, etc., or in one or more separate backside layers. The method for adding the components of the present invention can be the same as in the case of adding them to the constituent layers of conventional silver halide photographic materials. The silver halide photographic light-sensitive material according to the present invention has at least one light-sensitive silver halide emulsion layer as a surface layer of the support, and the component of the present invention is contained in the back layer of the support. In this step, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, and a protective layer are coated on a backed and subbed support as required. The photosensitive silver halide emulsion layer can include two or more layer structures sensitized to different wavelength ranges. The silver halide photographic light-sensitive material according to the present invention has a layer structure depending on other uses, but conventional techniques can be used as is for the structure of the surface layer of the support, and the structure of the back layer of the support is the structure of the present invention. It is a characteristic of The silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of various silver halides. In particular, when the light-sensitive material according to the present invention is of the so-called lithium type, silver chloride, silver chlorobromide, silver chlorobromide, silver halide, etc. Hydrophilic colloidal dispersions of silver halide containing silver chloride such as silver chloroiodide and silver chloroiodobromide, particularly preferably containing 50 mol % or more of silver chloride, are suitable. Hydrophilic protective colloids that are dispersants for silver halide include gelatin,
Synthetic resins such as polyvinyl alcohol or various colloidal substances such as gelatin derivatives are used alone or in combination. In addition, this silver halide emulsion can be chemically sensitized using gold sensitizers, sulfur sensitizers, etc., or optically sensitized using sensitizing dyes such as cyanine dyes and merocyanine dyes. can. Furthermore, various photographic additives can be added. For example, when the present invention is made into a so-called lithium-type silver halide photographic light-sensitive material, palladium,
High contrast agents such as platinum, rhodium, and cobalt, stabilizers or antifoggants such as triazole, tetrazole, and tetrazaindene compounds, halogen-substituted acids such as formaldehyde and mucopromic acid, hardening agents such as ethyleneimine compounds, saponin, and polyethylene. Spreading agents such as glycol lauryl or oleyl monoether, glycerin, esters of ethylene glycolic acid, polyvinylpyrrolidone,
Physical property improvers such as aqueous dispersions of synthetic resins (so-called luxes), halftone dot improvers such as alkylene oxide derivatives, lithium development accelerators such as imidazole and mercaptoimidazole compounds, and the like can be added. The support for the silver halide photographic light-sensitive material according to the present invention varies depending on the use of the light-sensitive material, but for example, when it is used for lithography or X-ray use, various supports such as polyethylene terephthalate are representative. Generally, polyester is used, but various supports such as polycarbonate, synthetic resins such as cellulose triacetate, or glass may be used depending on the purpose. For developing the silver halide photographic light-sensitive material according to the present invention, a developer suitable for the light-sensitive material is selected.
For example, in the case of a so-called lithium-type photosensitive material, a hydroquinone developer containing sulfite ions at a relatively low concentration is used. The composition of the Lith developer is mainly composed of a dihydroxybenzene-based developing agent such as hydroquinone, halogen-substituted hydroquinone, or alkyl-substituted hydroquinone, alone or in a mixture, and an adduct of an aldehyde-bisulfite alkali salt to this. Adducts of compounds having a carbonyl group (〓C=0) and soluble sulfites, such as adducts of cyclohexane or acetone with soluble sulfites, as well as their aliphatic primary or secondary
Preservatives for developing agents consisting of condensation products with class amines, alkaline agents such as alkali carbonates, alkali borates, and organic amines are mentioned. Furthermore, ascorpic acids, phenols, resordins, pyridazines, cysteines, primary, secondary or tertiary
air antioxidants such as class amines, hydrazines, hydroxyamines, and histidines, anti-capri agents such as 6-nitrobenzimidazole, 5-nitroindazole, and 1-phenyl-mercaptotetrazole, and glycols such as triethylene glycol. Organic solvents such as amines, alcohols, and halftone improvers such as polyalkylene oxides can also be used. In the present invention, the components of the present invention are contained in the back layer of the support of a silver halide photographic light-sensitive material.
It is possible to achieve the first object of the invention described above. The present invention is not only applied to achieve the first object of the present invention, but also may be applied to achieve other objects. For example, a silver halide photographic light-sensitive material is formed by coating at least one light-sensitive silver halide emulsion layer as a support surface layer, and during storage before development processing, the light-sensitive silver halide emulsion layer changes over time. known to cause capri, and
It is known that the occurrence of capri over time increases significantly when a photographic material is stored with its front side and back side overlapped, such as when the photographic material is stored wrapped in a cartridge or the like. . Therefore, as one of the other objects of the present invention,
To provide a silver halide photographic material capable of suppressing an increase in capri of a light-sensitive silver halide emulsion layer over time even when the photographic material is stored with its front side and back side stacked. (Hereinafter, this object will be referred to as the second object of the present invention.) This second object of the present invention is achieved by the same requirements as those of the present invention for achieving the first object. That is, a halogen-based material having a photosensitive silver halide emulsion layer on only one side of the support, and a layer containing an inorganic compound that dissolves in a developer and gives bromide ions on the other side. This can be achieved using silver oxide photographic materials. The content of the component of the present invention to achieve the second object of the present invention is not limited, and is equivalent to the content when the component of the present invention is contained in the surface layer of a conventional support. good. The present invention may be applied for the first purpose of the present invention, the second purpose of the present invention, or any other purpose. good. The present invention will now be illustrated by Examples, but the embodiments of the present invention are not limited thereto. Example 1 Direct X containing 1.5 mol% silver iodide was prepared by a conventional method.
Silver iodobromide gelatin emulsion for lay (hereinafter referred to as emulsion [A])
That's what it means. ) and an ortho-sensitized silver iodobromide gelatin emulsion for indirect X-ray (hereinafter referred to as emulsion [B]) containing 2 mol % of silver iodide, and coated on a polyethylene terephthalate film support with the amount of silver coated. ,
For direct X-ray use, total 90mg/100cm ² on both sides of the support.
For indirect X-ray use, apply the coating to one side of the support at a concentration of 60mg/100cm ² , and dry to obtain a sample of silver halide photographic light-sensitive material for X-ray use [A]
And sample [B] was obtained. On the other hand, sample [C] was produced as a silver halide photographic light-sensitive material for indirect X-ray according to the present invention by the following method. That is, a gelatin layer containing 1.7 g/m ² of potassium bromide was coated on the back side of the support of sample [B] and dried. After exposing each of the obtained samples through a step wedge, they were developed for 30 seconds at 35°C in a roller-type film transport automatic developing machine using X-ray developer 15 with the following composition and a known acid hardening fixer for automatic developing machines. Then, it was fixed, washed with water, and dried.

[Table] On the other hand, sample [A] and [B] are 50% of the total area.
After sufficient exposure to completely blacken by development, using an X-ray developer having the above composition and automatically adding a known X-ray developer replenisher,
Development processing was performed using a fatigued developer obtained by continuously processing 1000 sheets of 10 x 12 inch size. However, the developer replenisher was replenished at 20 ml per sample. Further, samples [A] and [C] were exposed in the same manner as above, and then developed using a fatigued developer obtained by processing 1000 sheets of the same size.
The developer replenisher was used under the same conditions as the above samples [A] and [B]. Sensitivity and gamma were established for each sample obtained. The results are shown in Tables 1 and 2 below. Note that the sensitivity is expressed as a relative sensitivity, with the sensitivity when sample [A] was developed using a new developer as 100.

【table】

[Table] As is clear from Tables 1 and 2, when conventional sample [A] and sample [B] are treated with the same developer, the photographic properties change significantly, but the conventional photosensitive material samples It can be seen that stable photographic properties can be obtained even when sample [C] in which the present invention is applied to [B] and sample [A] are processed with the same developer. Example 2 Each sample [A], [B] and [C] of Example-1
We conducted a preservation test on That is, after obtaining each sample [A], [B], and [C], each sample was wrapped around the support so that the front side and the back side overlapped, and the sample was heated at 55°C and a relative humidity of 80%. Each was left under these conditions for 2 days. The sample preserved in this way was exposed and developed (using a new solution) in the same manner as in Example-1.
Relative sensitivity, fog and gamma were measured. The results are shown in Table 3 along with those without preservation treatment.

Table 3 shows that sample [C] according to the present invention suppresses the increase in fog over time compared to comparative samples [A] and [B].

Claims (1)

[Scope of Claims] 1. Having a photosensitive silver halide emulsion layer only on one side of the support, and having a layer containing an inorganic compound that dissolves in a developer and gives bromide ions on the other side. A silver halide photographic material characterized by: 2. In a method of developing two or more types of light-sensitive materials having different amounts of bromide ions eluted in a developer, at least one of the light-sensitive materials has a light-sensitive silver halide emulsion layer on only one side of the support. has
A continuous processing method characterized in that the silver halide photographic material has a layer on the other surface containing an inorganic compound that dissolves into a developer and gives bromide ions.