JPH0627931B2 - Silver halide light-sensitive material containing dye - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide light-sensitive material in which halation and irradiation are prevented.

(Prior Art and Problems Thereof) A photographic material is a photosensitive grain (eg, a silver halide grain) dispersed at the interface between the photosensitive layer and the support or when the incident light passes through the photosensitive layer. Etc.) causes light reflection, light scattering, light diffusion, etc., and the resulting image has extremely poor sharpness. Therefore, in order to prevent these developments, the hydrophilic colloid layer is colored with a dye to prevent irradiation, or a so-called antihalation layer for coloring the back surface of the support is provided to reflect or scatter reflected light. It is known to improve the sharpness of an image by absorbing light, diffused light and the like. The dyes used for this purpose must be used in combination with the dyes in order to obtain spectral absorption characteristics according to the purpose of use, and must also satisfy the following conditions.

1) Photochemically inert.

2) Do not leave harmful color on the photographic light-sensitive material after being decolorized or dissolved and removed in the course of photographic processing.

3) Manufacturing of photosensitive material In the coating process, the dye contained in the coating liquid is decomposed, and the dye concentration does not change at the start and end of coating.

Many efforts have been made by those skilled in the art to find these conditions. Oxonol dyes containing a pyrazolone nucleus as described in, for example, British Patent 506,385, U.S. Patents 3,247,127, 3,653,905 and 2,533,47.
There are other oxonol dyes as described in No. 2 and the like.

However, although these dyes have a good anti-scattering effect, few of them are completely decolorized, leaving a slight stain on the processed film. On the contrary, many dyes that are completely decolorized are unstable, and the instability is increased by using a combination of dyes, and the dye contained in the coating solution is decomposed in the manufacturing process of the photosensitive material. Depending on things such as the dye concentration at the beginning and end of coating,
It often has the drawback of varying the absorption range.

(Object of the Invention) Accordingly, an object of the present invention is to provide a silver halide light-sensitive material containing a dye, which has a good decoloring property and has a very small fluctuation in dye concentration from the start to the end of coating in the process of manufacturing the light-sensitive material. Especially.

(Structure of the Invention) That is, the present invention is a silver halide photosensitive material characterized by containing a dye represented by the following general formula (I), a dye represented by the following general formula (II) and an aldehyde compound in the same layer. It is a material.

General formula (I) General formula (II) [Wherein R ₁ and R ₃ represent a group selected from an alkyl group, a carboxyl group, an aryl group, an alkoxycarbonyl group and an aryloxycarbonyl group, and R ₂ and R ₄ represent an alkyl group, an aryl group, a sulfonic acid group or It represents a group selected from an alkyl group substituted with a carboxyl group, a sulfonic acid group or an aryl group substituted with a carboxyl group. The dyes of the general formulas (I) and (II) of the present invention may be contained in the emulsion layer, or may be contained in the constituent layer containing the other hydrophilic colloid. When it is contained, a mordant is unnecessary, which is most advantageous.

Specific examples of the dyes represented by formulas (I) and (II) used in the present invention are shown below. The present invention is not limited to these compounds.

Dye belonging to general formula (I) A-1 A-2 A-3 A-4 A-5 A-6 Dye B-1 belonging to the general formula (II) B-2 B-3 B-4 B-5 B-6 Examples of the aldehyde compound used in the present invention include those disclosed in
-Aldehydes such as those described in 56931, specifically, compounds that generate formalin as a decomposition product of formalin and dimethylurea trimethylolmelamine, mucochloric acid, mucobromic acid, mucophenoxycycloric acid , Glyoxal, 2,3-dihydroxy-
Examples thereof include 1,4-dioxane and glutaraldehyde.

Specific examples of the particularly preferable aldehyde compounds used in the present invention are shown below, but the present invention is not limited to these compounds.

C-1 HCHO C-2 C-3 (CHO) ₂ C-4 C-5 The addition amount of these compounds is 1
It is preferable to add 1 mg to 10 g, and the range of 10 mg to 1 g is particularly preferable.

In the light-sensitive material of the present invention, the dye can be incorporated into the hydrophilic colloid layer by a usual method. That is, the dye is made into an aqueous solution of an appropriate concentration, and this is added to the silver halide emulsion solution when coloring the emulsion layer, or to the aqueous solution of the hydrophilic colloid when coloring the non-photosensitive constituent layer. These liquids may be applied onto a support or onto a layer to be a photosensitive material by a known method. The amount of each dye added to the coating solution is determined in the usual way from the desired absorption concentration of the light scattering prevention layer, the layer thickness, the absorbance of the dye, and the like.

Generally, it is preferable to add 1 mg to 1000 mg per 1 m ² of the light-sensitive material with all the added dyes, especially 30 mg to 600 mg.
The range is the preferable addition amount. It is also possible to combine with a dye other than the present invention. As a hydrophilic colloid,
For example, gelatin, casein, polyvinyl alcohol,
Although gelatin can be used, gelatin is preferable. Prior to coating, other photographic additives such as coating aids and curing agents may be added to the dye dispersion.

The support of the light-sensitive material, the coating method, the photographic additives, the manufacturing method of the photographic emulsion, the photographic processing method and the like are described, for example, in "Research Disclosures" No. 92.
The materials described on pages 107 to 110 (December 1971) and the like can be applied and are not particularly limited.

(Example) Hereinafter, the present invention will be described more specifically with reference to Examples. The technical scope of the present invention is not limited to the following examples, and various embodiments are possible.

Example 60 g of gelatin was dissolved in water 1 and 10% was used as a spreading agent.
30 ml of saponin, 2,4-dichloro-6- as a hardening agent
30 ml of 5% solution of hydroxy-1,3,5-triazine Na salt
In the addition system, a coating solution was prepared as shown in Table I. For comparison, dyes Y-1, Y-2 and Y- which are not included in the present invention are used.
3 was used. Each coating solution was divided into 2 parts, 1 part was immediately applied and dried, and the remaining 1 part was allowed to stand for 10 hours at 40 ° C and then applied (gelatin was applied on the film base so as to contain 30 mg per 100 cm ^2). Were dried and samples Nos. 1 to 11 were prepared as shown in Table I. As the support, a polyethylene terephthalate film having a thickness of 100 μ and undercoating was used. Three of these samples were superposed and visually observed to examine the color variation over time.
The color variation was examined by the absorption wavelength range and the absorption concentration. For both, there is almost no change ○ For those with some changes △ For those with large changes × For even larger ×
Displayed with a cross.

Y-1 Y-2 Y-3 On the support on the opposite side of the layer (backing layer) containing the dyes of Samples No. 1 to No. 11, the following silver halide photographic emulsion for bright room was coated so that the coated silver amount was 35 mg / 100 cm ^2. And then dried to prepare a light-sensitive sample for a light room. The emulsion is silver chlorobromide with a silver bromide content of 1 mol% and a grain size of about 0.1.
A monodisperse emulsion of μ was prepared and prepared. The sample thus obtained was exposed with a P-627FM manufactured by Dainippon Screen Co., Ltd. through a manuscript having an unexposed portion for evaluating the degree of contamination and a portion for evaluating the quality of blank characters, and a Mitsubishi papermaking machine DF3 was used.
30 was treated with Mitsubishi Papermaking Developer MRA-CD101 at 35 ° C. for 20 seconds and with an identification liquid MRA-CF701 at 35 ° C. for 20 seconds, and further washed with water and dried by a usual method. The quality of clear characters is 50% of halftone dots in the original document by the same printer through a multi-burning original document in which the character original document (8th to 12th character), mylar base (halftone negative), two film bases, and sample are stacked in this order. Exposure from the original side so that it is reproduced to 100%, and development processing is performed to obtain sharpness and resolution of each blank character to 100%.
I looked it up with a magnifying glass.

Nuki character quality is evaluated comprehensively by the above-mentioned measurement,
The symbols ◯, Δ, and × are displayed. ◯ is an excellent level that the Mincho Gothic type is reproduced up to 8th grade, △ is also reproduced only up to 10th grade, × is also reproduced only at 12th grade or lower and it is extremely It is of a poor level. The color contamination after the treatment was visually determined by overlapping 10 unexposed portions of the treated sample. Regarding the safelight property, after exposing with the same printer through the halftone dot original, the light with the brightness of 200 lux of Toshiba's fading prevention fluorescent lamp (FLR40SW-DL-X) as a safelight light from the backing surface is exposed for 60 minutes and developed. After the treatment, a comparison was made with a light which was not exposed to safelight light, and those with changes were marked with X, and those without change were marked with a circle.

The results are shown in Table I.

As is apparent from Table I, Samples 7 and 8 in which the aldehyde compound was added to the combination of the dyes of the present invention had excellent nuqui-character quality and thus had an excellent antihalation effect, and there was no color contamination after processing. It is also clear that the stability of the coating solution over time is excellent and the safelight safety is also excellent.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-49-19825 (JP, A) JP-A-57-112750 (JP, A) JP-A-55-161233 (JP, A) JP-A 61- 267758 (JP, A) JP 62-491 (JP, B2)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material comprising a dye represented by the following general formula (I), a dye represented by the following general formula (II) and an aldehyde compound in the same layer. General formula (I) General formula (II) (In the formula, R ₁ and R ₃ represent a group selected from an alkyl group, a carboxyl group, an aryl group, an alkoxycarbonyl group and an aryloxycarbonyl group, and R ₂ and R ₄ represent an alkyl group, an aryl group, a sulfonic acid group or It represents a group selected from an alkyl group substituted with a carboxyl group, a sulfonic acid group or an aryl group substituted with a carboxyl group.)