JPH0571934B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic material containing two or more types of dyes to prevent halation and irradiation, or to provide necessary safelight safety. (Prior art and its problems) When incident light passes through the photosensitive layer of a silver halide photosensitive material, the interface between the photosensitive layer and the support or the silver halide particles dispersed in the photosensitive layer causes the incident light to pass through the photosensitive layer. As a result, light reflection, light scattering, etc. occur, and the resulting image has extremely poor sharpness. Therefore, in order to prevent these phenomena, the hydrophilic colloid layer is colored with a dye to prevent irradiation, or by providing a so-called antihalation layer that colors the back surface of the support, reflected light, It is known that image sharpness can be improved by absorbing scattered light and the like. In recent years, it has also been known to improve safelight safety by using dyes in photosensitive materials that can be handled under visible light safelights (mainly safelights that emit light with a wavelength of 450 nm or more). The dyes used for these purposes must not only be used in appropriate combinations to obtain spectral absorption characteristics depending on the purpose of use, but also satisfy the following conditions. (1) Photochemically inert. (2) No harmful coloration remains on the photographic material after processing due to decolorization or dissolution removal during the photographic processing process. (3) The dye contained in the coating solution does not react or decompose during the manufacturing, preparation, and coating processes of photographic materials, and the spectral absorption characteristics do not change between the beginning and end of coating. (4) The dye contained in the coating layer does not react or decompose during storage of the photographic material, and the spectral absorption characteristics do not change. Many efforts have been made by those skilled in the art to find these conditions. For example, UK patent
oxonol dyes containing pyrazolone nuclei as described in No. 506385, British Patent No. 3247127;
There are other oxonol dyes such as those described in No. 3653905 and No. 2533472. However, although these dyes have good anti-scattering effects, they are rarely completely bleached;
A small amount of contamination may remain on the film after processing. Furthermore, dyes that are completely bleached are often unstable. In particular, the use of combinations of dyes to obtain spectral absorption characteristics tailored to the intended use increases instability, and dyes may react or Spectral absorption characteristics often change due to decomposition. Furthermore, this variation may also have an adverse effect on pigment loss. (Objective of the Invention) An object of the present invention is to provide a photographic material containing a dye that has good decolorization properties and exhibits little variation in spectral absorption characteristics during production and storage of the photographic material. (Structure of the Invention) The present inventors have discovered that by combining dyes of general formula (A) and dyes of general formula (B) and using them in the same layer,
It has been found that there is little variation in the spectral absorption characteristics of the coating solution as the solution ages. Furthermore, the present inventors further
By combining the dye of general formula (A) and the dye of general formula (B),
It has been found that, when used in the same layer, by containing the aldehyde compound in the same layer and/or in the adjacent layer, fluctuations in spectral absorption characteristics due to storage time of the coating film can be suppressed. That is, the present invention relates to a dye represented by the following general formula (A) and a dye represented by the following general formula (A).
A photographic material characterized by containing the dye represented by (B) in the same layer, and containing an aldehyde compound in the layer containing the dye represented by the following general formula (A) and/or in the adjacent layer. A photographic material characterized by containing: General formula (A)

[Formula, R ₁ and R ₃ are an alkyl group, a carboxyl group,
represents a group selected from an aryl group, an alkoxycarbonyl group and an aryloxycarbonyl group,
R ₂ and R ₄ represent a group selected from an alkyl group, an aryl group, a sulfonic acid group, an alkyl group substituted with a carboxyl group, an aryl group substituted with a sulfonic acid group or a carboxyl group. ) General formula (B)

[Chemical formula] (In the formula, R ₁ represents an alkyl group or an aralkyl group. R ₂ represents a hydrogen atom, an alkyl group, or an alkoxy group. _{R 3} represents a sulfoalkyl group or a sulfoallyl group. _{R 4} represents an alkyl group, aryl group,
Represents a carboxyl group or an alkoxycarbonyl group. ) The dyes of the general formulas (A) and (B) of the present invention may be contained in the emulsion layer or in a constituent layer containing a hydrophilic colloid inside or outside the emulsion layer.
When it is contained in the packing layer, no mordant is required and it is most advantageous. Specific examples of dyes represented by general formulas (A) and (B) used in the present invention are shown below. Note that the present invention is not limited to these chemicals.

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【table】

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[Table] The aldehyde compounds used in the present invention include those described in JP-A No. 50-56931. Specifically, formalin is used as a decomposition product of formalin, dimethylurea, trimethylolmelamine, etc. Compounds such as mucochloric acid, mucopromic acid, mucophenoxychloric acid, glyoxal, 2,3-dihydroxy-
Examples include 1,4-dioxane and glutaraldehyde. Specific examples of particularly preferred aldehyde compounds used in the present invention are shown below, but the invention is not limited to these compounds.

【table】

[Table] ｜
CHO
The amount of these compounds added is preferably from 0.1 mg to 1 g per m ² of coating area containing the dye, and particularly preferably from 1 mg to 100 mg. These aldehyde compounds have long been known as hardening agents, but in the present invention they are not necessarily required in amounts that exhibit a hardening effect. In the photographic material of the present invention, the dye can be introduced into the hydrophilic colloid layer by a conventional method. That is, an aqueous solution of the dye at an appropriate concentration is added to the silver halide emulsion liquid when coloring the emulsion layer, or to an aqueous solution of a hydrophilic colloid when coloring non-photosensitive constituent layers. These liquids may be coated on a support or on a layer constituting a photosensitive material by a known method. The amount of each dye added to the coating solution is determined by the desired amount of anti-light scattering layer,
Alternatively, it can be determined in a conventional manner from the absorption concentration of the light absorption layer, the layer thickness, the absorbance of the dye, etc. Also,
The dyes (A) and (B) can be contained in the coating liquid in any proportion. In general, it is preferable that the total amount of dye added is 1 mg to 1000 mg per m ² of light-sensitive material, especially 30 mg.
The preferred amount added is in the range from mg to 600 mg. or,
It is also possible to combine with dyes other than those according to the invention. As the hydrophilic colloid, for example, gelatin, casein, polyvinyl alcohol, etc. can be used, and among them, gelatin is preferred. Other photographic additives such as coating aids and hardeners may be added to the dye dispersion prior to coating. For information on supports for photosensitive materials, coating methods, photographic additives, photographic emulsion manufacturing methods, photographic processing methods, etc., please refer to "Research Disclosures", for example.
(Research Disclosure) magazine No. 92, pages 107 to 110 (December 1971 issue) can be applied, and there are no particular limitations. (Example) The present invention will be described in more detail below with reference to Examples. The technical scope of the present invention is not limited in any way by the following examples, and various embodiments are possible. Example 1 In a system in which 60 g of gelatin was dissolved in 1 part of water and 30 ml of 10% saponin was added as a coating aid, a coating solution was prepared as shown in Table 1, kept at 35°C, and subjected to a 24-hour aging test. , spectroscopic absorption measurements were performed. The dyes shown below were used as comparative dyes.

[ka]

[ka]

[C] Spectral absorption measurement was performed using a two-luminous self-recording spectrophotometer UV-3000 manufactured by Shimadzu Corporation after diluting the above coating solution before and after aging at a certain ratio. The evaluation was performed by focusing on the amount of change in the absorption peak wavelength as the solution ages and the rate of change in absorbance at the absorption peak wavelength before and after the solution ages. The evaluation results are shown in Table 1. As is clear from Table 1, sample No. 1 of the present invention,
It can be seen that samples 2 and 3 have excellent solution stability over time.

[Table] Example 2 60 g of gelatin was dissolved in 1 part of water, 30 ml of 10% saponin was added as a coating aid, and 2,4-
A coating solution was prepared as shown in Table 2 in a system in which 30 ml of a 5% solution of dichloro-6-hydroxy-1,3,5-triazine Na salt was added. Samples were prepared by coating these coating solutions on a film base so that the gelatin content was 3.0 g/m ² .
As the film base, a 100 μm thick undercoated PET colorless transparent base was used. These samples were forcefully stored (stored for one week in a heated warehouse at 50° C.), and the spectral absorption characteristics of the coating films before and after the forced storage were measured using the spectrophotometer described above. The evaluation was performed by focusing on the rate of change in absorbance at the absorption peak wavelength before and after forced preservation of the coating film, and the loss of pigment after forced preservation. Dye loss after forced storage is determined visually by overlapping 10 sheets of the lowest density sample of the developer processing agent, and ○ indicates good dye removal, △ indicates slightly poor dye removal, and △ indicates poor dye removal. Evaluations were given based on the criteria marked with an x mark. Table 2 shows the rate of change in absorbance at the absorption peak wavelength and the results of dye removal. As is clear from Table 2, Samples Nos. 2, 4, and 6 showed little change in spectral absorption characteristics, indicating good dye removal.

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Claims (1)

[Scope of Claims] 1. A photographic material characterized by containing a dye represented by the following general formula (A) and a dye represented by the following general formula (B) in the same layer. General formula (A) [Formula, R ₁ and R ₃ are an alkyl group, a carboxyl group,
represents a group selected from an aryl group, an alkoxycarbonyl group and an aryloxycarbonyl group,
R ₂ and R ₄ represent a group selected from an alkyl group, an aryl group, an alkyl group substituted with a sulfonic acid group or a carboxyl group, and an aryl group substituted with a sulfonic acid group or a carboxyl group. ) General formula (B) [Chemical formula] (In the formula, R ₁ represents an alkyl group or an aralkyl group.
R ₂ represents a hydrogen atom, an alkyl group, or an alkoxy group. R ₃ represents a sulfoalkyl group or a sulfoaryl group. R ₄ represents an alkyl group, an aryl group, a carboxy group, or an alkoxycarbonyl group. ) 2 Containing an aldehyde compound in the layer containing the dye represented by the general formula (A) and the dye represented by the general formula (B) described in claim 1 and/or in the layer adjacent thereto. Photographic material featuring.