JP3284370B2 - Silver halide photographic materials - Google Patents

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 material and, more particularly, to a silver halide photographic material having excellent dimensional stability in processing.

[0002]

BACKGROUND OF THE INVENTION Generally, gelatin is frequently used as a binder in silver halide photographic materials.

[0003] Gelatin has high swelling property and gelling ability,
Crosslinking with various hardeners is easy, and by adjusting the physical properties of the coating solution, a material that does not like high temperature, such as photosensitive silver halide, has extremely excellent properties for uniform coating over a large area. Binder.

In a silver halide photographic material, silver halide grains change to extremely hard metallic silver in a state where the gelatin layer has sufficiently absorbed water and swelled during development. Therefore, the emulsion layer does not return to its original state even after drying, and the size of the photosensitive material before and after processing may be different even if the photosensitive material is the same.

[0005] These prior arts are described, for example, in Research Disclosure 19951, JP-B-39-4272 and JP-B-39-1.
No. 7702, No. 43-13482, U.S. Patent No. 2,376,005, No. 2,76
3,625, 2,772,166, 2,852,386, 2,853,457
No. 3,397,988 and the like. Also, JP-A-59-
38741, 61-296348, 61-284756, 61-285446
For example, a method of incorporating micro oil droplets of paraffin or a vinyl polymer is disclosed in US Pat. However, it is still not sufficient, and further improvement is desired. In particular, development of a means for improving a phenomenon in which a dimensional difference before and after treatment greatly changes depending on environmental humidity has been desired.

On the other hand, Japanese Patent Application No. 2-244558 discloses a method in which a polymer latex is contained in a silver halide emulsion layer. According to these methods, a practically satisfactory level of dimensional stability before and after the treatment can be obtained in the range of 20% to 60% of humidity, but it can be further reduced under low humidity conditions, for example, 5 to 10% RH. The levels were still inadequate.

US Pat. No. 4,645,731 and the like disclose a silver halide photographic material having an undercoat layer using highly crystalline vinylidene chloride. However, the dimensional stability at ultra-low humidity is also completely improved. It wasn't something that made me sick.

Japanese Patent Application Laid-Open No. 1-230035 discloses a means for reducing the difference before and after processing at low humidity under special coating and drying conditions. However, this means further reduces the difference before and after processing at high humidity. It tends to expand in the direction of shrinking.

[0009]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide excellent dimensional stability, in particular, a small dimensional elongation before and after treatment at low humidity and a small dimensional before and after treatment even when the environmental humidity changes. An object of the present invention is to provide a silver halide photographic light-sensitive material having a small variation in difference.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to provide at least one photosensitive silver halide emulsion layer on a support, and the use of gelatin on the side containing the photosensitive silver halide emulsion layer with respect to the support. In a silver halide photographic light-sensitive material having a content of 2.9 g / m ² or less, in the step of coating or drying the layer containing the emulsion layer or a plurality of layers, the surface temperature of the coated layer is lower than the temperature of the contacting air. Within 5 minutes from the point when the temperature rises to 1 ° C lower, contact with air (dry air) having an absolute humidity of 0.5% or less and / or a relative humidity of 3 % or less for at least 5 seconds, and then air having a relative humidity of 40% or less This is achieved by a silver halide photographic light-sensitive material characterized in that it is wound into a roll under wet air) and manufactured .

In a preferred embodiment of the present invention, a silver halide photographic light-sensitive material is applied, dried, wound up in a roll, and then processed in air (environmental wind) having a relative humidity of less than 40%. And / or at least one of the packaging materials is packaged with a packaging material having a moisture content of 4% or less.

Hereinafter, the present invention will be described specifically.

As a level at which the dimensional stability before and after processing is satisfied, generally, when the size of the original is 60 cm, the dimensional difference before and after processing is within 20 μm, and the relative humidity is 5 to 60.
%, It is necessary that the difference before and after treatment is within 40 μm.

As a result of intensive studies, the present inventors have found that such a level of dimensional stability can be achieved by the present invention.

Incidentally, the above-mentioned techniques such as polymer latex addition or vinylidene chloride undercoating can be used in combination.

A particularly preferred condition of the dry air condition of the present invention is that the absolute humidity is 0.5% or less and the relative humidity is 3% or less, and the humidity condition air condition and the environmental wind condition are that the relative humidity is 35% or less. preferable.

The packaging material of the present invention generally includes a barrier bag and base paper for a sheet-shaped product, and a black polyethylene sheet and a photosensitive material for a roll-shaped product. There is a core base paper.

To reduce the water content to 4% or less, 55 ° C.
It can be obtained by adjusting the humidity at 20% RH for more than 24 hours.
Preferably, the water content is 3% or less. The moisture content can be measured by a commercially available product such as an infrared moisture meter and a wood moisture meter.

The amount of gelatin on the emulsion layer side of the light-sensitive material according to the present invention must be 2.9 g / m ² or less. 3.0
At g / m ² or more, the dimensional difference before and after the treatment at high humidity tends to be too small. It is preferably at most 2.7 g / m ² , particularly preferably at most 2.5 g / m ² .

There are no particular restrictions on the general additives, the well-known contrast agents, the method for producing silver halide grains, the sensitizing method, and the like according to the present invention.
Reference can be made to Japanese Patent Application No. 1-266640.

In the present invention, one or more antistatic layers can be provided on the backing side and / or the emulsion layer side of the support in order to prevent another physical property of the photosensitive material, that is, antistatic.

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

The antistatic layer is preferably an antistatic layer containing a reactant of a water-soluble conductive polymer, hydrophobic polymer particles and 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 sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups and polyethylene oxide groups. . Among these groups, a sulfonic acid group, a sulfate group, and a quaternary ammonium base are preferable. The conductive group requires 5% by weight or more per molecule of the water-soluble conductive polymer.

The water-soluble conductive polymer contains 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 and the like. Of these, a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, and an aldehyde group are preferably contained. 5% by weight of these groups per molecule of polymer
It is necessary that these are included. The number average molecular weight of the water-soluble conductive polymer is from 3000 to 100,000, preferably from 3500 to 50,000.

The metal oxide is preferably tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or a material obtained by doping these metal oxides with metal phosphorus, metal silver, or metal indium. Used. The average particle size of these metal oxides is 1
μ-0.01μ is preferred.

The undercoating layer which can be used in the present invention includes an undercoating layer using an organic solvent containing polyhydroxybenzenes described in JP-A-49-3972;
Nos. 52-104913, 59-19941, 59-19940, 5
9-18945, 51-112326, 51-117617, 51-5846
No. 9, No. 51-114120, No. 51-121323, No. 51-123139,
No. 51-114121, No. 52-139320, No. 52-65422, No. 52-1
09923, 52-119919, 55-65949, 57-128332
No. 59-19941 and the like, an aqueous latex subbing layer described in, for example, U.S. Pat.Nos. 2,698,235 and 2,779,6
No. 84, 425,421, 4,645,731 and the like.

The surface of the undercoat layer can be usually treated chemically or physically. Examples of the treatment include surface treatment such as 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 ozone oxidation treatment. .

The undercoat layer is distinguished from the coating layer according to the present invention, and there is no limitation on the coating timing and conditions.

In the present invention, a solid-dispersed dye may be contained in any of the hydrophilic colloid layers in addition to the ordinary water-soluble dye. The layer may be the outermost layer on the emulsion side, or may be added to the lower layer and / or the backing side of the emulsion layer for the purpose of preventing halation. Further, an appropriate amount may be added to the emulsion layer for adjusting irradiation. Of course, a plurality of layers may contain a plurality of types of solid disperse dyes.

The amount of the solid disperse dye to be added is preferably 5 mg / m ^{2 to 1} g / m ² , and more preferably 1 g / m ^2.
It is ^{0mg / m 2 ~800mg / m 2} .

Fine particles of the solid dispersion to be used are obtained by pulverizing the dye with a dispersing machine such as a ball mill or a sand mill, and dispersing water or hydrophilic colloid such as gelatin, sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate. , Saponin, nonylphenoxypolyethylene glycol, and the like, and can be dispersed.

The general formula of the solid disperse dye is described in US Pat.
Nos. 4,857,446 and the like, for example, those represented by general formulas [I] to [V] are preferably used.

The present invention can be applied to various photosensitive materials such as for printing, X-ray, general negative, general reversal, general positive, and direct positive, but requires extremely high dimensional stability. When applied to a printing photosensitive material to be used, a particularly remarkable effect can be obtained.

The development temperature of the silver halide photographic light-sensitive material according to the present invention is preferably 50 ° C. or lower, particularly preferably about 25 ° C. to 40 ° C., and the development processing time is generally completed within 2 minutes. However, it is also preferable to perform a rapid treatment for 5 to 60 seconds.

[0036]

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

Example 1 (Emulsion preparation) A rhodium hexachloride complex was added to a silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide at 8 × 10 ^-5 mol / Agm.
ol solution was added simultaneously to the gelatin solution while controlling the flow rate, and after desalting, the particle size was 0.13 μm and the silver bromide 1
A cubic, monodisperse, silver chlorobromide emulsion containing mol% was obtained.

This emulsion is sulfur sensitized by a conventional method, and after adding 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene as a stabilizer, the gelatin becomes 1.2 g / m ^2. After adding gelatin as described above, the following additives were added to the emulsion coating solution E-
0 was prepared, and then an emulsion protective layer coating solution P-0, a backing layer coating solution B-0, and a backing protective layer coating solution BP-0 were prepared according to the following composition.

(Preparation of Emulsion Coating Solution) Compound (a) 1 mg / m ² NaOH (0.5N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² Saponin (20%) 0.5 cc / m ² sodium dodecylbenzenesulfonate 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 Latex La (particle size 0.2 μm ) 1.0 g / m ² styrene-maleic acid copolymer polymer (thickener) 90 mg / m ²

[0040]

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[0041]

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(Emulsion protective layer coating solution P-0) Gelatin 1.1 g / m ² compound (g) (1%) 25 cc / m ² compound (h) 120 mg / m ² Compound (Fa) 2 mg / m ² spherical single Dispersed silica (8 μm) 20 mg / m ² ３ (3 μm) 10 mg / m ² Compound (i) 100 mg / m ² Citric acid Adjusted to pH 6.0 Styrene-maleic acid copolymer polymer (thickener) 100 mg / m ² ( Backing layer coating solution B-0) Gelatin 1.0 g / m ² compound (j) 100 mg / m ² compound (k) 18 mg / m ² compound (l) 100 mg / m ² savonin (20%) 0.6 cc / m ² latex ( m) (particle size 0.2 μm) 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 (Backing protective layer coating solution BP-0) Gelatin 0.5 g / m ² compound (g) (1%) ² cc / m ² spherical polymethyl methacrylate (4 μ) 25 mg / m ² sodium chloride 70 mg / m ² glyoxal 22 mg / m ² Compound (o) 100 mg / m ²

[0043]

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[0044]

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[0045]

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As the undercoating process, JP-A-59-159
10 W / (m ² · min) on a 100 μm-thick polyethylene terephthalate base undercoated as shown in US Pat.
After applying a corona discharge, a roll fit coating pan and an air knife were applied with the following composition. The drying is 90 ° C., the overall heat transfer coefficient ^{25Kcal (m 2 · hr · ℃} )
For 30 minutes, and then at 140 ° C. for 90 seconds. The thickness of this layer after drying was 1 μm, and the surface resistivity of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0047]

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Ammonium sulfate 0.5 g / l polyethylene oxide compound (average molecular weight 606 g / l hardener 12 g / l

[0049]

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On this base, first, the emulsion layer and the emulsion protective layer were placed in the order of the emulsion layer side and the emulsion protective layer from the side closer to the support in the order of 30 mg formalin per 1 g of gelatin as a hardener by a slide hopper method while maintaining the temperature at 35 ° C. At the same time as adding it to the cold air set zone (5
° C), the backing layer and the backing protective layer were applied by a slide hopper while adding a hardening agent, and a cold air setting (5 ° C) was performed. At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. After the backing surface was applied, the film was conveyed in a state of non-contact with a roller and other members until winding. At this time, the coating speed was 150 m / min.

(Drying conditions) After setting, the mixture was dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin became 800%.
0% was dried with a drying air at 35 ° C. (30%), and the air was blown as it was. When the surface temperature reached 34 ° C., drying was performed for 1 minute with air under the drying air conditions shown in Table 1. At this time, the drying time is 50 seconds from the start of drying to the H ₂ O / Gel ratio of 800%, and 800% to 200%.
Is 35 seconds, and from 200% to the end of drying is 5 seconds.

The photosensitive material was wound up under the conditioned air conditions shown in Table 1 and then cut under the environmental wind shown in Table 1 and placed in a barrier bag conditioned at the same environment for 3 hours (at 50 ° C., 10% for 8 hours). After moistening
Sealed with cardboard (moisture conditioned 5% at 23 ° C for 2 hours at 40%).

In the light-sensitive material prepared as described above, the coated silver amount was 3.5 g / m ² .

The dimensional stability of the evaluation sample prepared as described above was evaluated as follows.

(Dimensional Stability) A sample was cut into a size of 30 cm × 60 cm, and two fine lines were image-exposed at an interval of 60 cm using a light room printer P-627FM (manufactured by Dainippon Screen Co., Ltd.) and developed. The thing was the manuscript. This manuscript, unexposed sample (same size as manuscript), printer and automatic developing machine
After 2 hours of humidity control at% RH, the unexposed sample adheres to the original
(Side-to-Side) Exposure and processing with an automatic processor. After the developed sample was conditioned for 2 hours, it was superimposed on the original document, and the distance between the fine lines was measured using a loupe with a scale.

The measurement was carried out at n = 6, the average value was obtained, and (a)
And

The same experiment was performed at 23 ° C. and 60% RH, and this value was defined as (b).

Further, the difference between (a) and (b) (dependence on environmental humidity) was taken, and this value was taken as (c).

When the values (a) and (b) exceed ± 20 μm, a dimensional deviation is recognized. If the value of (c) is within 40 μm, the dimensional difference before and after the treatment is at a level that is hardly recognized at 5 to 60%.

(Standard processing conditions) Developing 28 ° C. 30 seconds Fixing 28 ° C. 20 seconds Water washing Room temperature 15 seconds Drying 40 ° C. 35 seconds [Developer formulation] (Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2g Diethylene glycol 50g Potassium sulfite (55% W / V aqueous solution) 100ml Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to bring pH of used solution to 10.9 Potassium bromide 4.5 g (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 Water 500 ml when using a developer The above composition A and composition B were dissolved in this order, and finished to 1 liter for use.

[Formulation of Fixing Solution] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 5.6 g sodium acetate trihydrate 27.8 g boric acid 9.8 g sodium citrate dihydrate 2.0 g acetic acid (90 % W / V aqueous solution) 6.4 ml (Composition B) Pure water (ion-exchanged water) 28 ml Sulfuric acid (50% W / V aqueous solution) 6.7 g Aluminum sulfate (aqueous solution whose content in terms of Al ₂ O ₃ is 8.1% W / V) 25.31 g When the fixing solution was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 liter. This fixer p
H was about 4.4.

The results are shown in Table 1.

[0063]

[Table 1]

From the results shown in Table 1, the drying conditions of the present invention are 5 to 5.
It can be seen that good dimensional stability before and after the treatment is exhibited over the 60% range.

Example 2 In the present invention, the moisture content of the packaging material is preferably 4% or less. In the samples of Examples 1 to 9, the moisture content of the packaging material was 3% and 2%. The evaluation was performed in the same manner as in Example 1.

Table 2 shows the results.

[0067]

[Table 2]

From the results in Table 2, it can be seen that the dimensional stability before and after the treatment is increased by lowering the moisture content of the packaging material. Particularly, the samples No. 7 to 9 under the drying conditions according to the present invention can obtain good results. I understand.

[0069]

According to the present invention, a silver halide photographic photosensitive material having excellent dimensional stability, in particular, a small dimensional elongation before and after processing at low humidity and a small change in dimensional difference before and after processing even when the environmental humidity changes. Material could be provided.

Claims (3)

(57) [Claims] 1. A support having at least one photosensitive silver halide emulsion layer on a support, wherein the gelatin content on the side containing the photosensitive silver halide emulsion layer relative to the support is 2.
In a silver halide photographic light-sensitive material of 9 g / m ² or less,
In the step of coating and drying a layer or a plurality of layers including the emulsion layer, the absolute humidity is 0.5% or less within 5 minutes after the surface temperature of the coated layer rises to 1 ° C. lower than the temperature of the contacting air. And / or contact with air (dry air) with a relative humidity of 3 % or less for at least 5 seconds or more.
A silver halide photographic light-sensitive material manufactured by winding into a roll under 40% or less of air (humidified air). 2. The method according to claim 1, wherein the silver halide photographic light-sensitive material is applied, dried, wound up in a roll, and then processed under air (environmental wind) having a relative humidity of less than 40%. 2. The silver halide photographic light-sensitive material according to item 1. 3. At least one of the packaging materials has a moisture content of 4%.
請 characterized in that it is packaged by the following packaging material
3. The silver halide photographic material according to claim 1 or 2 .