JPH0822100A - Silver halide photographic photosensitive material and its processing method - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic photosensitive material having high density and wide in exposure latitude for photographing of a line drawing, to obtain a silver halide photographic photosensitive material for development in a bright room having wide exposure latitude, less pinholes and high density, and to obtain a silver halide photographic photosensitive material for a scanner having a wide exposure latitude and less cracks in dots. CONSTITUTION:This silver halide photographic photosensitive material has at least one silver halide emulsion layer on a supporting body and whose gammavalue is >=10. In this photosensitive material, dyes are dispersed in layers containing a silver halide emulsion. This photosensitive material is processed in an automatic developing machine by a total processing time of 20 to 60sec with <=300ml replenishing amt. of the developer per 1m<2> of the photosensitive material. It is preferable to decrease the gamma value by 5-50% by dispersing the dyes in the silver halide emulsion.

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, and more particularly to a high-contrast silver halide photographic light-sensitive material for printing plate making.

[0002]

2. Description of the Related Art Conventionally, it has been known to form a photographic image with extremely high contrast and high contrast in a silver halide photographic light-sensitive material, and such photographic image formation is used in the field of photoengraving. For example, Japanese Patent Publication Sho 59-17825
Issue 59-17818, Issue 59-17819, Issue 59-17820, Issue 59
-17821, 59-17821, 59-17822, 59-17826 and the like disclose silver halide photographic light-sensitive materials containing a tetrazolium compound.

With these, it is possible to obtain a super-hard contrast with a gamma value of more than 10, but on the other hand, because the characteristic curve is well-cut, pinholes are drastically reduced when the exposure amount is lowered. There is a drawback that the number of lines increases or thin lines disappear.

For example, when a character original is photographed by using a plate-making camera, if a light-sensitive material having a sharp edge and good contrast is exposed, underexposure causes a rapid decrease in character density, fine lines disappear, and unreadable characters. In addition, if the film is made in a bright room, that is, a so-called reversal photosensitive material and underexposure is performed in order to lower the reticulation net percentage, the density of the pinhole due to dust or the like and the density of the portion where the film is adhered by the tape are rapidly lowered. Further, in the case of a material exposed by a laser beam such as a scanner photosensitive material, since the photosensitive material is in too high contrast, the gap of the laser beam is not blackened at the time of halftone dot formation, causing a problem of point cracking. As described above, the ultra-high contrast photosensitive material has a drawback that the latitude with respect to the fluctuation of the exposure amount becomes narrow.

Although these problems can be solved by using a soft-tone photosensitive material, the tetrazolium compound may be reduced in amount as a means for softening the softening material. However, the number of pinholes increased and the character density decreased. In addition, if adjustment is made by chemical aging, the fog increases and only the high density portion becomes soft. Further, in a system having a small amount of replenishment of development or a system having a short processing time, the tone was softened, but the density was greatly decreased, and the desired performance was not obtained.

Therefore, it is desired to develop a photosensitive material having a wide exposure latitude, a high contrast and a high density in the photosensitive material for printing plate making.

[0007]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having a wide exposure latitude and a high density in line drawing, and further to provide a bright-room return sensitization. The object of the present invention is to provide a silver halide photographic light-sensitive material having a wide exposure latitude and a small number of pinholes and a high concentration, and to provide a silver halide photographic light-sensitive material having a wide exposure latitude and a small dot cracking in a scanner light-sensitive material. .

[0008]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having a silver halide emulsion of at least one layer on a support and having a gamma value of 10 or more,
The gamma is lowered by dispersing a dye in the layer containing the silver halide emulsion, and the replenishing amount of the silver halide photographic light-sensitive material and the developing solution is 300 ml per 1 m ^2.
The following is achieved by a method of processing a silver halide photographic light-sensitive material, characterized in that the total processing time in an automatic processor is 20 to 60 seconds. The gamma value of the above silver halide emulsion is preferably reduced by 5 to 50% by dispersing a dye.

The present invention will be specifically described below.

The gamma-reducing dye used in the present invention is preferably a water-soluble dye. Examples of such water-soluble dyes include, but are not limited to, the following.

[0011]

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[0012]

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The dye-added layer is preferably an emulsion-containing layer, but it may be added to the outermost emulsion protective layer and diffused into the emulsion-containing layer. When a solid-dispersed dye is added, an emulsion-containing layer is preferred. The dye may be any dye that softens the tone with a light-sensitive material having a gamma of 10 or more. It is preferably 5 to 50%, more preferably 10 to 40%. The addition amount of the dye is preferably 10 mg or more, and more preferably 50 mg or more per 1 m ² .

The silver halide photographic light-sensitive material of the present invention preferably has a total amount of hydrophilic binders of 2.7 g / m ² or less on the side having the light-sensitive silver halide emulsion layer with respect to the support. . The case where the total amount of the hydrophilic binders on the side having the photosensitive silver halide emulsion layer with respect to the support is 2.5 g / m ² or less is particularly preferable.

There are no particular restrictions on other general additives and known contrast-increasing agents, as well as the method for producing silver halide grains and the method for sensitizing, which constitute the light-sensitive material of the present invention. These can be selected by referring to the descriptions of Kaihei 1-235035 and Japanese Patent Application No. 1-266640.

In the present invention, one or more antistatic layers may be provided on the support, for example, on the backing side and / or the emulsion layer side, for the purpose of antistatic property which is another physical property of the light-sensitive material. .

In this case, the surface resistance on the side provided with the antistatic layer is preferably 1.0 × 10 ¹² Ω or less at 25 ° C. and 50%, and particularly preferably 8 × 10 ¹¹ or less.

The antistatic layer is preferably an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of a curing agent, or an antistatic layer containing a metal oxide.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group polyethylene oxide group. Can be mentioned. Of these groups, a sulfonic acid group, a sulfuric acid ester group and a quaternary ammonium salt group are preferred. The amount of the conductive group is preferably 5% by weight or more per molecule of the water-soluble conductive polymer.

When a water-soluble conductive polymer containing a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinyl sulfone group or the like is used. Of these, those containing a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, and an aldehyde group are preferable. It is preferable that these groups are contained in an amount of 5% by weight or more per polymer molecule. The number average molecular weight of the water-soluble conductive polymer is preferably 3000 ~
It is 100000, and more preferably 3500 to 50000.

The metal oxide is preferably tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or a metal oxide, metal phosphorus, metal silver, or metal indium doped with these metal oxides. Used. The average particle size of these metal oxides is 1
μ to 0.01 μ is preferable.

As the undercoat layer which can be used in the present invention, an undercoat layer containing an organic solvent containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-49-11118.
No. 52, No. 52-104913, No. 59-19941, No. 59-19940, No. 5
9-18945, 51-112326, 51-117617, 51-5846
No. 9, 51-114120, 51-121323, 51-123139,
51-114121, 52-139320, 52-65422, 52-1
09923, 52-119919, 55-65949, 57-128332
No. 59-19941 and the like water-based latex undercoating layer, but also U.S. Pat.
Examples thereof include vinylidene chloride-based undercoating described in 9,684, 425,421, 4,645,731 and the like.

The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and surface activation treatment such as ozone oxidation treatment. .

There is no limitation on the coating timing and conditions of the undercoat layer and other coating layers.

In processing the silver halide photographic light-sensitive material of the present invention, the development temperature is preferably 50 ° C. or lower, and particularly 25 ° C.
The temperature is preferably about -40 ° C, and the development processing time is generally completed within 2 minutes, but it is particularly preferable to carry out rapid processing for 20 to 60 seconds, and the effect is large.

Further, the replenishment of the developing solution is preferably 300 ml or less, more preferably 200 ml or less per m ² of the light-sensitive material, and the effect is large.

[0027]

EXAMPLES Examples of the present invention will be specifically shown below, but it goes without saying that the present invention is not limited to these examples.

Example 1 (Emulsion preparation) 8 × 10 ^-5 mol / Agm of rhodium hexachloride complex was added to a silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide.
The solution added so that it became ol was added simultaneously to the gelatin solution while controlling the flow rate, and after desalting, the particle size was 0.13μ, silver bromide 1
A cubic crystal, monodisperse, silver chlorobromide emulsion E1 containing mol% was obtained. In the same manner as in E, the amount of rhodium hexachloride complex was adjusted to 9.
E2 was prepared as 5 × 10 ⁻⁵ mol / Ag mol.

This emulsion was sulfur-sensitized by a conventional method, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then the gelatin was adjusted to 1.2 g / m ² . After adding gelatin so that
-0 was prepared, and then emulsion protective layer coating solution P-0, backing layer coating solution B-0, backing protective layer coating solution BP-0.
Was prepared with the following composition. Table 1 shows the amount of dye in the emulsion layer and the emulsion protective layer, the type of emulsion, the amount of the compound (b) added, and the development processing conditions.

(Preparation of Emulsion Coating Solution) Compound (a) 1 mg / m ² NaOH (0.5N) adjusted to pH 5.6 Compound (b) Table 1 Compound (c) 30 mg / m ² saponin (20%) 0.5 cc / M ² sodium dodecylbenzene sulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg compound (f) 6 mg / m ² dye (D) Table 1 poly Ethyl acrylate latex 1.0 g / m ² Styrene-maleic acid copolymer polymer (thickener) 90 mg / m ²

[0031]

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[0032]

[Chemical 4]

(Emulsion Protective Layer Coating Solution P-0) Gelatin 1.1 g / m ² Compound (g) (1%) 25 cc / m ² Dye (D) Table 1 Spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3 μm) 10 mg / m ² compound (i) 100 mg / m ² compound (j) 5 mg / m ² citric acid adjusted to pH 6.0 (backing layer coating solution B-0) gelatin 1.0 g / m ² compound (k) 18 mg / M ² compound (l) 100 mg / m ² savonine (20%) 0.6 cc / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene-maleic acid copolymer polymer (thickener) 45 mg / m ² glyoxal 4 mg / m ² compound (n) 10 mg / m ² compound (p) 100 mg / m ² (backing protective layer coating solution BP-0) gelatin 0.5 g / m ² compound (g) (1%) 2 cc / M ² Spherical polymethylmethacrylate (4μ) 25mg / m ² Sodium chloride 70mg / m ² Glyoxal 22mg / m ² Compound (o) 100mg / m ²

[0034]

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[0035]

[Chemical 6]

[0036]

[Chemical 7]

As an undercoating process, the emulsion surface side is disclosed in JP-A-59-1.
After applying corona discharge at 10 W / (m ² · min) on a polyethylene terephthalate base with a thickness of 100 μm, which is shown in 9941, use a roll-fit coating pan and an air knife with the following composition. Applied. still,
Drying was carried out at 90 ° C. for 30 minutes under parallel flow drying conditions with an overall heat transfer coefficient of 25 Kcal (m ² · hr · ° C.), and subsequently at 140 ° C. for 90 seconds. The thickness of this layer after drying is 1 μm, and the surface resistivity of this layer is 23 ℃.
It was 1 × 10 ⁸ Ω at 5%.

[0038]

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Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 60 6 g / l Curing agent 12 g / l

[0040]

[Chemical 9]

On this base, formalin solution was used as a hardening agent solution in the order of emulsion layer and emulsion protective layer from the side closer to the support as the emulsion surface side at 35 ° C. in the order of 30 mg formalin solution per 1 g gelatin formalin solution. Simultaneous multi-layer coating while adding as much as possible
C.), the backing layer and the backing protective layer were also coated with a slide hopper while adding a hardening agent, and set with cold air (5.degree. C.). The coating liquid showed sufficient setting properties when passing through each set zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, the film was conveyed until it was wound up in a roller, without any contact with other parts. At this time, the coating speed was 100 m / min.

(Drying conditions) After setting, the product is dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin reaches 800%, and then 800 to 20.
Dry 0% with 35 ° C (30%) dry air, apply the air as it is, and 30 seconds after the surface temperature reaches 34 ° C (it is considered that the drying is completed), use air with the conditions shown in the table below. Min dried. At this time, the drying time is from the start of drying to the H ₂ O / Gel ratio of 800%
Is 50 seconds, 800% to 200% is 35 seconds, and 200% to completion of drying is 5 seconds.

This photosensitive material was wound at 40 ° C. at 23 ° C., then cut in the same environment, and placed in a barrier bag conditioned for 3 hours under the same environment (at 23 ° C. after conditioning at 40 ° C. 10% for 8 hours). Sealed with cardboard (40% conditioned for 2 hours).

In the light-sensitive material prepared as described above, the coated silver amount was 4.0 g / m ² and the gelatin amount was 2.
It was 0 g / m ² .

The evaluation was performed as follows. A bright room printer P-627FM (manufactured by Dainippon Screen Co., Ltd.) was used to expose through a document containing fine line patterns and pictures and processed under the following conditions.

(Processing Conditions) (1) (2) (3) Development 28 ° C. 30 seconds 35 ° C. 15 seconds 35 ° C. 15 seconds Fixing 28 ° C. 20 seconds 35 ° C. 10 seconds 35 ° C. 10 seconds Rinse room temperature 15 seconds Room temperature 10 seconds Room temperature 10 seconds Dry 40 ℃ 35 seconds 50 ℃ 15 seconds 50 ℃ 15 seconds Developer replenishment amount 400ml / m ² 400ml / m ² 200ml / m ² [Developer formulation] (Composition A) Pure water (ion exchange water) 150ml Diethylene glycol 50g Potassium sulfite (55% W / V aqueous solution) 50.5 ml Potassium carbonate 40 g Hydroquinone 14 g 5-Methylbenzotriazole 500 mg 1-Phenyl-5-mercaptotetrazole 20 mg Potassium hydroxide Amount to bring the pH of the working solution to 10.4 Potassium bromide 2.5 g Sulfite Soda 14.66 g Dimezone S 1.4 g Diethylenetriamine-5-acetic acid (40% w / v aqueous solution) 3.63 g 2-Mercaptopicoxanthin 60 mg (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 mg Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90 % Aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter.

[Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2.0 g Acetic acid (90% W / V aqueous solution) 13.6ml (Composition B) Pure water (ion exchanged water) 17ml Sulfuric acid (50% W / V aqueous solution) 4.7g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 26.5g Fixing When the liquid was used, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter. The fixer pH was about 4.3.

In the evaluation of the light-sensitive material, the replenishment amount of the developing solution is 20.
It carried out when it became liter. The automatic developing machine has a developing tank
A 10 liter one was used.

Table 1 shows the sample preparation conditions.

[0050]

[Table 1]

The developed sample was evaluated as follows.

(Pinhole) Pinholes due to dust and dust in the blackened portion when the proper exposure is performed so that a halftone dot area of 50% is returned and a halftone dot area of 50% is formed on the photosensitive material in five stages. evaluated. In this evaluation, a level of 3 or more is a level that can be practically used.

On the (gamma) characteristic curve, density 1.0 and density 3.0
Gamma is displayed with the inclination of.

(Density) The density at the time of proper exposure in pinhole evaluation is shown, and 3.5 or more is a practical level.

(Relative Sensitivity) The relative sensitivity at the time of proper exposure in pinhole evaluation is shown.

Table 2 shows the above evaluation results.

[0057]

[Table 2]

From the results shown in Table 2, in the sample softened by adding the dye according to the present invention, the pinhole was improved without lowering the density, and the rapid processing and the reduction of the replenishment amount of the development were possible. It turns out that a big improvement can be made.

[0059]

According to the present invention, there is provided a silver halide photographic light-sensitive material having a wide exposure latitude and a high density in line drawing, and a bright room reversal light-sensitive material having a wide exposure latitude and a small number of pinholes. It was possible to provide a silver photographic light-sensitive material and also a silver halide photographic light-sensitive material having a wide exposure latitude and less dot cracking in the scanner light-sensitive material.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one layer of a silver halide emulsion on a support and having a gamma value of 10 or more, by dispersing a dye in the layer containing the silver halide emulsion. A silver halide photographic light-sensitive material characterized by decreasing gamma. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the gamma value is reduced by 5 to 50% by dispersing a dye in a layer containing a silver halide emulsion. 3. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 1 or 2 at a replenishing amount of a developer of 300 ml or less per 1 m ² . 4. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to any one of claims 1 to 3 in a total processing time of 20 to 60 seconds in an automatic processor.