JP3191189B2 - 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 light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which does not peel off when processed rapidly by an automatic processor and has good drying properties.

[0002]

2. Description of the Related Art In rapid processing of a silver halide photographic light-sensitive material by an automatic developing machine, improvement of the drying property of the light-sensitive material is an essential condition for shortening the time. For this reason, proposals have conventionally been made to reduce the amount of binder (mainly gelatin) in the hydrophilic colloid layer constituting the light-sensitive material and to reduce the drying load by reducing the swelling property of the film.

[0003] However, if the amount of gelatin is reduced until the drying property is accelerated, the pinhole-like shape will not be produced when the film is conveyed at high speed by an automatic processor.
(Point-like) film peeling may cause fatal failure.

[0004] This phenomenon is called a pick-off failure and includes a conventionally known stalinite failure (stardust failure),
This is a failure different from pinholes caused by dust adhesion.

In order to improve the pick-off failure, Japanese Patent Application No. 4-8684 filed by the same applicant as the present invention proposes a method (hard film) for lengthening the melting time of a photosensitive material in an aqueous alkaline solution. However, when the amount of gelatin is very small, it has been found that this means alone cannot solve the problem, and a new measure has been desired.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material which is excellent in drying property and free from pick-off failure in rapid processing by an automatic processor.

[0007]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
In a silver halide photographic material having at least one silver halide emulsion layer on one side of a support, the amount of gelatin per side of the silver halide photographic material is 1.5 g or more and 2.5 g or less per 1 m ² , The hydrophilic colloid layer on the side having the emulsion layer contains at least one of the compounds represented by the following general formula [I], and has a matte degree of the surface of the layer.
Achieved by a silver halide photographic light-sensitive material characterized in that it is not more than 20 mmHg.

General formula [I] Rf- (A) _n -Y (wherein, Rf represents a branched perfluoroalkenyl group having 3 to 30 carbon atoms, and A represents -O-, -COO-, -CON (R ₁ )
_{-, - SO 2 N (R} 1) - at least one containing a divalent group having 1 to 12 carbon atoms, R ₁ represents an alkyl group (e.g. methyl, ethyl of 1 to 5 carbon atoms binding, Propyl, butyl, pentyl group, etc.). n is 1 or 2 and Y is -COO
M, represents a -SO ₃ M -OSO ₃ M or -P = (O) (OM) 2. Here, M is a hydrogen atom, an alkali metal atom (e.g., sodium, potassium, etc.), an alkaline earth metal atom (e.g., calcium,
Barium, etc.) or a quaternary ammonium group (e.g., -NH ₄₎
Represents a cation. Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material according to the present invention is a light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a support. The amount of gelatin is 1.5 g / m ^{2 to} 2.5 g /
m ² and contains the fluorine-containing surfactant represented by the above general formula [I] on the side having the photosensitive silver halide emulsion layer.

Hereinafter, specific examples of the compound represented by the above general formula [I] will be shown.

[0011]

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These compounds can be synthesized, for example, by referring to the method described in JP-B-58-32200. or,
The following can also be obtained as commercial products.

I-6: Phagent 100 I-7: Phagent 110 I-8: Phagent 150 The amount of the compound of the above formula [I] used in the present invention, the silver halide photographic light-sensitive material according to the present invention The amount may be 0.05 mg to 100 mg, preferably 0.3 mg to 30 mg per 1 m ² on the side of the material having the silver halide emulsion layer. In order to add the compound of the general formula (I) to the hydrophilic layer of the photosensitive material,
It is preferable to dissolve it in water or a hydrophilic solvent such as methanol, ethanol, glycols, acetone or the like alone or in a mixed solvent and then add it. As the photographic constituent layer of the silver halide photographic light-sensitive material according to the present invention, on the side having a photosensitive silver halide emulsion layer, for example, an emulsion layer, an emulsion protective layer, an intermediate layer, a dye layer, a filter layer, an antistatic layer, etc. Is mentioned. On the other hand, the side having no photosensitive silver halide emulsion layer includes, for example, an antihalation layer, the same protective layer, an antistatic layer, an intermediate layer, and other backing layers.

The fluorinated surfactant represented by the general formula [I] according to the present invention is added to the hydrophilic colloid layer on the side having the photosensitive silver halide emulsion layer.

Preferred hydrophilic colloid layers are photosensitive silver halide emulsion layers and protective layers. Particularly preferred hydrophilic colloid layers include a protective layer on the outermost surface of a photosensitive material.

Next, the degree of matting referred to in the present invention refers to the temperature of a silver halide photographic light-sensitive material (so-called raw film) that has been exposed to light.
After performing humidity control for 3 hours under the conditions of 23 ° C. and RH of 30% to 55%, the suction pressure is measured under the same conditions, and the value is expressed in mmHg.

A smoother (manufactured by Toei Denshi Kogyo Co., Ltd.) is used to measure the suction pressure, and the larger the value, the higher the matte degree.

According to the study of the present inventors, the matting agent particle size and the amount of the matting agent in the hydrophilic colloid layer of the light-sensitive material dominate the matting degree, and the matting degree on the surface of the layer is 20 mmHg.
It has been found that the following effects can be obtained satisfactorily by the following.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide,
Alternatively, it may be a silver iodochlorobromide emulsion containing a small amount of silver chloride.
The silver halide grains may be of any crystal type as long as they have the constitution of the present invention, for example, cubic, octahedral,
It may be a single crystal such as a tetradecahedron or a polytwin particle having various shapes.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention include, for example, those described in "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Paul Montel (1967) or VLZelikman et al. “Makin
g And Coting Photographic Emulsion "by Focal Press (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, and a control double jet method under solution conditions such as an acidic method, an ammonia method, and a neutral method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is preferably a monodisperse emulsion in which silver iodide is localized inside the grains. The term "monodisperse" as used herein refers to a silver halide in which at least 95% of the grains by number or weight are within ± 40%, preferably within ± 30% of the average grain diameter when the average grain diameter is measured by a conventional method. Particles.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a core portion of high silver iodide is covered with a shell layer of low silver iodide may be used.

The method for producing the above-mentioned monodispersed emulsion is known.
J. Phot. Sci, 12.242-251, (1963), JP-A-48-36890,
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Pat. Nos. 3,574,628, and 3,655,394.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is prepared by, for example, using a seed crystal as a method for obtaining the above monodisperse emulsion and supplying silver ions and halide ions using the seed crystal as a growth nucleus. An emulsion that has been grown may be used.

The method for producing the above-mentioned core / shell type emulsion is known, and is described, for example, in J. Phot. Sci, 24.198. (1976), US Pat.
Nos. 250, 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain diameter / grain thickness) of 3 or more. The advantages of such tabular grains are disclosed in, for example, British Patent No. 2,112,157, U.S. Pat.No. 4,414,310, and U.S. Pat.No. 4,434,226, as they can improve spectral sensitization efficiency and improve the graininess and sharpness of images. Emulsions can be prepared by the methods described in these publications.

The emulsions described above are either of a surface latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, or a latent image type in which a latent image is formed on both the surface and the inside. It may be an emulsion.

These emulsions may be used at the stage of physical ripening or grain preparation, for example, using cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof. You may.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

The emulsion used in the silver halide photographic material of the present invention can use various photographic additives before and after physical ripening or chemical ripening. As the compound used in such a step, for example, the aforementioned (RD) No. 1
7643, Nos. 18716 and 308119 (December 1989) can be used. The locations of these three (RD) are listed below.

Additives RD-17643 RD-18716 RD-308119 page classification page page classification Chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV 998 IV B dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surface activity Agents 26-27 XI 650 right 1005-6 XI Plasticizer 27 XII 650 right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogen of the present invention Examples of the support used for the silver halide photographic light-sensitive material include those described in the above (RD) .A suitable support is a plastic film or the like, and the surface of the support has good adhesion of the coating layer. For this purpose, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

The photographic processing of the light-sensitive material of the present invention can be carried out, for example, by the above-mentioned (RD) -17643, XX to XXI, pages 29 to 30, or 308, 119 to XX to XXI.
Treatment with a treatment solution as described in XXI, pp. 1011-1012 may be performed. This process may be a black and white photographic process for forming a silver image.

The processing temperature is usually in the range of 18 ° C. to 50 ° C.

As a developer in black-and-white photographic processing, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and aminophenols (for example, N-methyl-P-aminophenol) Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0038]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of non-light-sensitive emulsion A) A silver iodobromide emulsion having an average grain size of 0.3 μm (silver iodide content: 2 mol%) was used as a seed emulsion, and an average grain size of 1.0 μm was obtained by an ammonia method. Silver iodobromide emulsion (silver iodide content 3
Mol%) of a monodisperse emulsion was grown. Coefficient of variation (σ / r)
Was in the range of 0.15 to 0.20.

(Preparation of Photosensitive B Emulsion) A having an average particle size of 0.1 μm
Using a gBrI (AgI content 2 mol%) seed emulsion, an aqueous solution of ammoniacal AgNO _{3 and an} aqueous solution of potassium bromide were added by a double jet method, and AgBr having an average particle size of 0.25 μm was used.
A cubic monodisperse emulsion of I (average AgI content 0.1 mol%) was grown. The coefficient of variation (σ / r) was in the range of 0.15 to 0.20.

This emulsion was dissolved immediately before chemical ripening, and when the temperature became constant, the following dyes (1) and (2) were added to obtain an emulsion (B). The dye amounts were each 90 mg / mol silver halide. Next, ammonium thiocyanate, chloroauric acid and hypo were added and subjected to chemical sensitization,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

[0042]

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(Backing layer) Backing lower layer coating solution Gelatin 400 g i-Amine-n-decylsulfosuccinate sodium 0.4 g Antihalation dye (1) 10 g Potassium polystyrene sulfonate (average molecular weight 150,000) 50 g Diethylene glycol 5.0 g Glyoxal 2.0 g Dye emulsified dispersion (the following content) 33g

[0044]

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Make up to 7 liters with water.

[Preparation method of dye emulsion dispersion]
10Kg of tricresyl phosphate 28l and ethyl acetate 85l
At 55 ° C. This is called an oil-based solution. On the other hand, 270 l of a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) was prepared. This is called an aqueous solution. Next, the oil-based solution and the aqueous-based solution were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was made up to 240 kg with water.

[0047]

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Backing upper layer coating solution Gelatin 400 g i-Amyl-n-decylsulfosuccinate sodium salt 10 g Antihalation dye (1) 10 g Polymethyl methacrylate (average particle size 6 μm) 12 g SAM-1 3.0 g SAM-2 0.75 g C ₈ F ₁₇ SO ₃ K 0.3g Griokizal 13.6g

[0049]

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Finish to 7 liters with water.

Red-Sensitive Silver Halide Emulsion Layer Coating Solution The above emulsions A and B were mixed at a silver ratio of 90:10, and the following was added per mol of silver halide to apply a red-sensitive silver halide emulsion. A liquid was prepared.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg 1,1-Dimethylol-1-bromo- 1-nitromethane 10mg potassium polystyrene sulfonate (average molecular weight 150,000) 10g

[0053]

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Emulsion surface side protective layer coating solution The following addition amounts were shown per 1 m ² of film.

Lime-treated inert gelatin Amount shown in Table 1 Sodium i-amyl-n-decylsulfosuccinate 27 mg Polymethyl methacrylate (average particle size 3 μm) Add the amount that gives the matte degree shown in Table 1 Silicon dioxide particles (Area average particle size) Diameter 1.2 μm) 10 mg Ludox AM (colloidal silica (manufactured by DuPont)) 50 mg 2-4-Dichloro-6-hydroxy-1,3,5-triazine sodium (2% aqueous solution) 5 mg Formalin (35%) 10 mg Glyoxal (40 %) 40 mg (Formalin and glyoxal are added in the amount that gives the melting time shown in Table 1 at a weight ratio of 1: 1) Topside 300 (manufactured by Permchem Asia Ltd.) 1 mg SAM-1 20 mg SAM-2 7.7 mg The present invention Fluorine-containing surfactants in amounts shown in Table 1

[0056]

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Preparation of Support A polyethylene terephthalate support having a thickness of 180 μm was biaxially stretched and heat-set on both sides, and then subjected to a corona discharge treatment. An undercoat latex (Compound of Synthesis Example 1) described in Example 1 of JP-A-59-18945 was further applied thereon.

Then, on one surface of the upper layer, the following compound described in JP-A-4-80744 by the same applicant as the present invention was applied as an antistatic layer.

Water-soluble conductive polymer (Ex. P4) 0.6 g / m ² Hydrophobic polymer (Ex. HP1) 0.5 g / m ² Curing agent (Ex. AH5) 2 × 10 ⁻³ mol / dm ² Application is 30 m / min. After application at a speed by a roll-fit coating pan and an air knife, activation treatment by corona discharge was performed again in the same manner as described above to obtain a support.

Coating of Sample On the side of the obtained support on which the antistatic layer was not coated, the above-mentioned silver halide emulsions A and B according to the present invention and the coating solution for the emulsion surface protective layer were coated.

On the side of the surface on which the antistatic layer was applied, the lower and upper backing layers described above were applied.

The amount of gelatin in the backing layer was 1.5 g for the lower layer.
/ m ² and the upper layer was 0.9 g / m ² at the same time by a slide hopper method. Samples were obtained by coating the emulsion layer and the protective layer so that the amounts of gelatin were as shown in Table 1.

The following evaluation was performed on the obtained film sample. The matting degree is shown in Table 1 by measuring the surface of the protective layer (on the emulsion layer side) by the method described above. According to the method of the present invention, the matte degree was 20 mmHg or less.

(Evaluation method of melting time) 1 cm × 2
A film sample cut into 1.5 cm N was kept at 60 ° C.
It was immersed in an aOH aqueous solution without stirring, and the time until the emulsion layer was eluted was measured and defined as a melting time (minute).

(Evaluation Method of Drying Property) After exposing the film sample to the maximum density with tungsten light, the automatic developing machine SRX- was modified so that the transport speed of the automatic developing machine was 30 seconds by Dry to Dry processing. The treatment was performed using 1001 (manufactured by Konica Corporation).

The film was touched by hand at the outlet of the dried film, and the degree of drying was evaluated in the following four ranks. In addition,
The atmosphere at the time of evaluation was 23 ° C. and RH 60%.

A: very good drying property B: good drying property C: poor drying property D: very poor drying property

(Evaluation method of pick-off) After uniform exposure was applied to the entire surface so as to obtain a density of 3.0, 10 pieces of four-piece size samples were continuously processed using the same automatic developing machine as in the evaluation of dryness, and pick-off was performed. Was evaluated. The pick-off was based on the following criteria as an average value for 10 pieces of quarter size.

A: very good B: good C: poor D: very poor

Next, the compositions of the developing solution and the fixing solution used in the present invention are shown.

Developer Formulation Part-A (for 15 liter finishing) Potassium hydroxide 470 g Potassium sulfite (50% solution) 3000 g Diethylenetriaminepentaacetic acid 45 g Sodium bicarbonate 150 g 5-Methylbenzenetriazole 2.0 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 390 g Add water to make 5000 ml Part-B (for finishing 15 l) Glacial acetic acid 220 g Triethylene glycol 200 g 1-phenyl-3-pyrazolidone 27 g 5-nitroindazole 0.45 g n-acetyl-D, L-penicillamine 0.15 g Part-C (for 15l finish) Glutaraldehyde 50g Fixer formulation Part-A (for 19l finish) Ammonium thiosulfate (70wt / vol%) 4000g Sodium sulfite 175g Sodium acetate / trihydrate 400g Sodium citrate 50g Gluconic acid 38g Boric acid 30g Glacial acetic acid 140g Part-B (for finishing 19l) Aneninium sulfate 65g Sulfuric acid (50wt%) 105g Starter formula (for 1 liter finishing) (Use 2.0 ml per 1 liter of developing solution.) Glacial acetic acid 138 g Potassium bromide 325 g 5-methylbenzotriazole 1.5 g Make up to 1 liter with pure water.

The results obtained are shown in Table 1 below.

[0073]

[Table 1]

As is clear from the table, the sample of the present invention has a low matte degree on the surface and has excellent drying properties and no pick-off failure despite the melting time being not different from the comparison. Is shown.

It can be seen that the pick-off cannot be improved with the comparative compound even if the matte degree is reduced in the same manner as in the present invention.

Example 2 A film sample was prepared in exactly the same manner as in Example 1. However, a sample was prepared and evaluated in the same manner as in Example 1 except that the particle size of the photosensitive silver halide emulsion particles was 0.3 μm and the spectral sensitizing dye was changed to the following (3). Table 2 shows the obtained results.
Shown in As is clear from the table, even in silver halide photographic light-sensitive materials which have been changed to spectral sensitizing dyes to make them infrared-sensitive,
It can be seen that the method according to the present invention can provide a photosensitive material with less pick-off failure.

[0077]

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[0078]

[Table 2]

[0079]

According to the present invention, a silver halide photographic light-sensitive material free of film peeling (pick-off failure) upon rapid processing by an automatic processor and having a high drying property can be obtained.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support, the amount of gelatin per one side of the silver halide photographic light-sensitive material is 1 m ² per 1.5g to 2.5 g or less, the hydrophilic colloid layer on the side having the emulsion layer contains at least one compound represented by the following general formula [I], and the matte degree of the surface of the layer is 20 mmHg or less. A silver halide photographic light-sensitive material comprising: In the general formula (I) Rf- (A) _n -Y (wherein, Rf represents a perfluoro alkenyl group branched, A is -O -, - COO -, - CON (R 1) -, - SO 2 N Represents a divalent group having 1 to 12 carbon atoms containing at least one (R ₁ )-bond, R ₁ represents an alkyl group having 1 to 5 carbon atoms, and n is 1
Or 2, and Y is -COOM, -SO ₃ M -OSO ₃ M or -P = (O)
(OM) represents ₂ . Where M is a hydrogen atom, an alkali metal atom,
Represents an alkaline earth metal atom or a quaternary ammonium group. )