JPH08220662A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material high in sensitivity and superior in rapid processing aptitude, such as sensitivity, pressure resistance, and graininess in the rapid processing. CONSTITUTION: The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on a support and the emulsion layer contains flat silver halide grains having an average aspect ratio of <=5, and a flatness degree of >=25, and a silver chloride content of >=50%.

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 having at least one light-sensitive silver halide emulsion layer on a support, and more specifically, it has high sensitivity and is excellent in ultra-rapid processability. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the consumption amount of silver halide photographic light-sensitive materials has been increasing and the number of processed silver halide photographic light-sensitive materials has increased. The demand for increase of is extremely high.

The above tendency can be said in any field of silver halide photographic light-sensitive materials, but especially in the field of medical X-ray photographic light-sensitive materials, due to a rapid increase in the number of diagnoses and an increase in inspection items, The number of X-ray photographs taken is increasing. On the other hand, rapid processing is desired because it is necessary to know the diagnosis result as soon as possible.

This is because it is necessary to obtain a diagnostic image in as short a time as possible in order to reduce the burden on the patient particularly in angiographic imaging and intraoperative imaging.

In order to satisfy the demands in the above-mentioned diagnostic field, further rapid processing by automating the steps such as photographing and carrying of the silver halide photographic light-sensitive material is required.

On the other hand, from the standpoint of environmental regulation, the amount of waste liquid of the processing liquid has been reduced to lower the replenishment rate. Such low replenishment,
When ultra-fast processing is performed, naturally, processing fluctuations and photographic performance deterioration occur.

[0007] There is a method of using a silver chloride silver halide grains as these measures, rapid developability, the influence of the halide ions in the developer is Br ^- or I ^- compared to the Cl ^- a developer in that small However, silver chloride grains have a drawback that sufficient sensitivity is difficult to obtain and satisfactory performance cannot be obtained.

In response to the demand for rapid processing, tabular silver halide grains have been used in recent years. Since the tabular silver halide grains have a large specific surface area and can adsorb a large amount of sensitizing dyes, the spectral sensitivity can be increased. Further, in the silver halide photographic light-sensitive material for X-rays, the crossover light can be remarkably reduced. The feature is that an image with less light scattering and high resolution can be obtained.

Therefore, a silver halide photographic light-sensitive material having high sensitivity and high image quality is expected by using such tabular grains, but the drawback of such tabular silver halide grains is that they are caused by pressure. The problem is that fogging occurs. This is a blackening due to bending when handling silver halide photographic light-sensitive materials, and streaky fog occurs when it is rubbed during transportation such as automatic imaging devices and automatic developing machines. In the case of silver halide photographic material,
It becomes a big problem in diagnosis. This tendency is remarkable especially in high-speed transportation in rapid processing. Therefore, it has been desired to develop a silver halide photographic light-sensitive material having high sensitivity and excellent rapid processability (sensitivity, pressure resistance, graininess in rapid processing).

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art and to achieve high sensitivity and rapid processing properties (sensitivity, pressure resistance and graininess in rapid processing). It is to provide a photographic light-sensitive material.

[0011]

In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer. Is a tabular grain having an average aspect ratio of 5 or less, a tabularity of 25 or more, and a silver chloride content of 50 mol% or more.

The silver halide photographic light-sensitive material as described above, wherein the weight ratio of silver / gelatin in the silver halide emulsion layer is 1 or more.

The present invention is achieved by the silver halide photographic light-sensitive material described in or characterized in that the amount of gelatin in the silver halide emulsion layer is 20% or more and 60% or less of the total amount of gelatin.

The present invention will be described in detail below.

Silver halide grains are generally prepared and used in the form of silver halide emulsions containing the grains.

The silver halide grains of the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention are silver halide grains having an average aspect ratio of 5 or less and a tabularity of 25 or more and containing silver chloride. The tabular grains have a ratio of 50 mol% or more. Particularly preferably, grains having an average aspect ratio of 2 or more and 4 or less and tabularity of 25 or more and 50 or less have a total projected area of 30% or more and 80% or less. Furthermore, the silver chloride content
It is 90 mol% or more.

The term "aspect ratio" as used herein means, for a twin grain having two or more parallel twin planes, a projected image of the grain when the grain is projected from a direction perpendicular to the twin plane, It is the ratio (particle diameter / particle thickness ratio) of the diameter when converted into a circular image and the distance (particle thickness) between the surfaces of two particles parallel to the twin plane.

The tabularity is a value expressed by (diameter in terms of circle) / (particle thickness) ² .

The particle diameter can be obtained by, for example, magnifying the particle with an electron microscope at a magnification of 10,000 times to 50,000 times, and measuring the particle diameter on the print or the area at the time of projection. (The number of particles to be measured shall be 1000 or more indiscriminately.) The particle thickness can also be obtained by actually measuring electron micrographs.

The silver / gelatin weight ratio in the silver halide emulsion layer of the present invention is preferably 1 or more, more preferably 1 or more and 2 or less.

The weight ratio of gelatin in the silver halide emulsion layer to the total gelatin used in the silver halide photographic light-sensitive material of the present invention is preferably 20% or more and 60% or less.

The silver halide emulsion of the present invention can be produced by a known method. For example, any method such as an acidic method, a neutral method, or an ammonia method may be used, but a double jet method (simultaneous mixing method) is preferably used as a method of reacting a soluble silver salt and a soluble halogen salt. PAg in the liquid phase produced by silver halides as a form of simultaneous mixing method.
It is also possible to use a so-called controlled double-jet method for keeping the temperature constant. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In determining the addition rate, JP-A-54-4
You can refer to No. 8521 and No. 58-49938.

The silver halide emulsion used in the practice of the present invention is a noodle washing method and a flocculation method in order to remove soluble salts to obtain a pAg ion concentration suitable for chemical sensitization after the growth of silver halide grains is completed. A precipitation method or the like may be used, and a preferable washing method is, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a polymer described in JP-A-2-7037. A desalting method using a flocculant such as G-3 and G-8 can be used.

In the silver halide emulsion of the present invention, various hydrophilic colloids for wrapping silver halide are used as a binder. For this purpose, in addition to gelatin, synthetic polymers such as polyvinyl alcohol and polyacrylamide, and photographic binders such as colloidal albumin, polysaccharides and cellulose derivatives may be used.

In an embodiment of the present invention, the silver / gelatin weight ratio in the silver halide emulsion layer of the present invention is 1 or more, and the amount of gelatin in the silver halide emulsion layer is 20% of the total amount of gelatin. Above, it is below 60%.

In the case of chemical sensitization, usual sulfur sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used. More specific chemical sensitizers include allylthiocarbamide, thiourea, thiosulfate, sulfur sensitizers such as thioether and cystine, precious metal sensitizers such as potassium chloroaurate, aura thiosulfate and potassium chloroparadate. , Reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

The silver halide emulsions used in the practice of this invention may be spectrally sensitized with cyanine dyes and the like. The spectral sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of spectral sensitizing dyes is often used particularly for the purpose of supersensitization.

In the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening of the emulsion.

Examples of the compound that can be used in such a step include the above-mentioned Research Disclosure (RD).
17643, (RD) 18716 (November 1979) and (RD) 308119
No. (December 1989). The types and locations of the compounds described in these three (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Surfactant 26 to 7 XI 650 Right 1005 to 6 XI Antistatic agent 27 XII 650 right 1006 to 7 XIII plasticizer 27 XII 650 right 1006 XII slip agent 27 XII matting agent 28 XVI 650 right 1008 to 9 XVI binder 26 XXII 1009 to 4 XXII support 28 XVII 1009 XVII Photosensitization of the present invention Examples of the support that can be used as the material include (RD) 17643, page 28 and (RD) 308119 described above.
Examples of suitable supports include polyethylene terephthalate, and the surface of these supports is provided with a subbing layer to improve the adhesion of the coating layer, corona discharge, and ultraviolet rays. Irradiation may be performed.

The silver halide emulsion according to the present invention can be coated on one side or both sides of the support thus treated.

The light-sensitive material of the present invention may be optionally provided with an antihalation layer, an intermediate layer, a filter layer and the like.

In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. Coating methods include dip coating, roller coating, curtain coating, extrusion coating, slide coating
A hopper method or the like can be used. For details, the method described in "Coating Procedures" in Research Disclosure (RD) Vol. 176, pages 27-28, can be used.

The processing of the silver halide photographic light-sensitive material of the present invention is carried out, for example, by RD- of Research Disclosure mentioned above.
17643, XX to XXI, pages 29 to 30, or 308119, XX to XX
I, pp. 1011-1012, may be treated with a treatment solution.

As processing agents for black and white photographic processing, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone),
Aminophenols (for example, N-methyl-4-aminophenol) and the like can be used alone or in combination. For the developer, known agents such as preservatives, alkaline agents, pH buffers, antifoggants, film hardening agents, development accelerators, surfactants, defoamers, color tones, water softeners, solubilizers, etc. You may use an agent, a viscosity imparting agent, etc. as needed.

A fixing agent such as thiosulfate or thiocyanate is used for the fixing solution. Further, a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. Other preservatives, pH adjusters,
A water softener may be included.

In the present invention, the rapid processing property refers to the sensitivity, pressure resistance and graininess of the photographic performance under the rapid processing conditions of a total processing time (Dry to Dry) of 40 seconds or less.

The term "development process time" or "development time" in the present invention means the next fixing solution after the tip of the photosensitive material to be processed is immersed in the developing tank solution of an automatic developing machine (hereinafter referred to as "developing machine"). "Fixing time" is the time until immersion in
The time from dipping in the fixing tank liquid to dipping in the next washing tank liquid (stabilizing liquid), "washing time" means the time of dipping in the washing tank liquid. Also, "drying time"
Is usually in the automatic processor 35 ℃ ~ 100 ℃, preferably 40
A drying zone to which hot air of ℃ ~ 80 ° C is blown is installed, and it means the time to enter the drying zone. In the development processing of the present invention, the development time is 3 seconds to 15 seconds, preferably 3 seconds to 10 seconds. The developing temperature is preferably 25 ° C to 50 ° C,
30-40 degreeC is more preferable. Fixing temperature and time is 20 ℃ to 50 ℃
The temperature is preferably 2 seconds to 12 seconds, and more preferably 30 ° C to 40 ° C for 2 seconds to 10 seconds. Washing or stabilizing bath temperature and time is 0-50
The temperature is preferably 2 seconds to 15 seconds. More preferably, it is 2 to 8 seconds at 15 to 40 ° C.

According to the method of the present invention, the developed, fixed and washed (or stabilized) silver halide photographic material is dried through a squeeze roller for squeezing the washing water.

The drying is carried out at 40 ° C to 100 ° C, and the drying time is appropriately changed depending on the environmental temperature, but it is usually 3 seconds to 12 seconds, particularly preferably 40 ° C to 80 ° C for 3 seconds to 8 seconds. is there.

A far infrared heater is preferably used as the heat source.

In the present invention, processing can be carried out with a developing time of 10 seconds or less and a developer replenishment amount of 200 ml or less per square meter of the silver halide photographic light-sensitive material.

In addition, in implementing the present invention, various techniques used by photographic techniques can be applied.

[0045]

Embodiments of the present invention will be described below. Of course, the present invention is not limited to the examples described below.

Example 1 (Preparation of silver chloride emulsion) Preparation of EM-1 (pure AgCl tabular grains) <Solution A> High methionine gelatin (methionine 59.7 mM per 1 g of gelatin) 90 g CaCl ₂ .H ₂ O 440 g distilled water <Solution B> Silver nitrate 1017 g 1800 ml with distilled water At 40 ° C, adjust the pH of solution A to 5.1 in a mixing stirrer as shown in Japanese Patent Publication Nos. 58-58288 and 58-58289. , Of solution B
Twenty-nine milliliters (ml) was added over 4 minutes.

Further, the addition rate was linearly accelerated over 55 minutes (9.32 times from the start to the end), during which the solution B was added.
Was added. 4, 16 and 36 minutes after the start of addition of the solution B, 30 ml of a 37 mmol (mM) adenine solution was added. Ten
After 3 minutes, 3.78 g of a 3 molar (M) CaCl ₂ solution was added. During the addition of the adenine and CaCl ₂ solution, the inflow of silver nitrate was stopped for 1 minute and the additives were mixed evenly. During this period, the pH was controlled to be constant by adding caustic soda or nitric acid.

Approximately 3000 particles of EM-1 were observed and measured by an electron microscope and the shape was analyzed. As a result, they were tabular particles having an average aspect ratio of 9.1 and a tabularity of 40.

EM-2 to EM-4 (pure AgCl tabular grains)
Preparation of EM-1 In the preparation method of EM-1, pure silver chloride having different particle diameters and particle thicknesses by changing the time of addition of the first 29 ml of solution B, the temperature of solution A, and the silver ion potential during addition of solution B. Tabular grains EM-2 to EM-4 were prepared. The average aspect ratio and tabularity are shown in Table 1.

Preparation of EM-5 (AgBr _0.10 Cl _0.90 tabular grain) <Solution C> High methionine gelatin (methionine 59.7 mM per 1 g of gelatin) 103 g 4,5,6-triaminopyrimidine 343 g NaCl 246 g NaBr 48 g with distilled water 6000 ml <Solution D> Silver nitrate 793 g Distilled water to 2000 ml At 40 ° C, the pH of solution C in the mixing stirrer shown in JP-B-58-58288 and 58-58289 is adjusted to 5.6. ,
6 ml of solution D was added over 1 minute. Then accelerate linearly over another 55 minutes (9.8 times from start to finish)
During which time the entire amount of Solution D was added. Gelatin solution 411 ml was added 1, 15 and 18 minutes after the start of addition of the solution D. After 5 and 18 minutes 1371 g of 4M NaCl solution and 20 mM
343 g of 4,5,6-triaminopyrimidine solution was added. During the addition of the above raw materials, the inflow of silver nitrate was stopped for 1 minute, and the additives were uniformly mixed. During this period, the pH was controlled to be constant by adding caustic soda or nitric acid.

Approximately 3000 particles of EM-5 were observed and measured by an electron microscope, and the shape was analyzed.
It was a tabular grain with a tabularity of 15 and a tabularity of 125.

Preparation of EM-6 to EM-9 (AgBr _0.10 Cl _0.90 tabular grains) In the preparation method of EM-5, the grains were prepared by changing the temperature of solution C, pH, and silver ion potential during addition of solution D. diameter,
AgBr _0.10 Cl _0.90 tabular grains EM-6 with different grain thickness
EM-9 was prepared. The average aspect ratio and tabularity of these are shown in Table 1.

Preparation of EM-10 (AgBr _0.50 Cl _0.50 tabular grain) Preparation was carried out in the same manner as EM-5 except that 192 g of NaBr was further added to the mixer.

Approximately 3000 particles of EM-10 were observed and measured by an electron microscope, and the shape was analyzed.
It was a tabular grain having a tabularity of 15 and a tabularity of 118.

Preparation of EM-11 to EM-15 (AgBr _0.50 Cl _0.50 tabular grains) In the preparation method of EM-10, grains were prepared by changing the temperature of solution C, pH, and silver ion potential during addition of solution D. diameter,
AgBr _0.50 Cl _0.50 tabular grains with different grain thickness EM-11 ~
EM-15 was prepared. The average aspect ratio and tabularity of these are shown in Table 1.

Preparation of EM-16 (AgBr _0.60 Cl _0.40 tabular grain) Preparation was carried out in the same manner as EM-5 except that 240 g of NaBr was further added to the mixer.

Approximately 3000 particles of EM-16 were observed and measured by an electron microscope, and the shape was analyzed.
It was a tabular grain having an average degree of 40 and 4.5.

[0058]

[Table 1]

After completion of addition, each emulsion was subjected to precipitation desalting using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts, and an aqueous gelatin solution containing 92.2 g of ossein gelatin was added. The mixture was redispersed with stirring as 2500 ml.

Next, after each emulsion thus obtained was heated to 50 ° C., the following spectral sensitizing dyes (A) and (B) were added per mol of silver, respectively.
After adding 300 mg and 15 mg, ammonium thiocyanate salt was added at 7.0 × 10 ^-4 mol per mol of silver, chloroauric acid and sodium thiosulfate were added for optimum chemical ripening, and silver iodide fine grain emulsion was mixed with 1 mol of silver. 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 3 after addition of 3 × 10 ^-3 mol per
Stabilized at × 10 ^-2 mol.

Spectral sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous Spectral sensitizing dye (B) 5, 5'-di- (butoxycarbonyl) -1,1'-diethyl-3,
3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydrous (preparation of sample) Various additives described below were added to each emulsion to prepare an emulsion coating solution. The amount of addition is shown in an amount per mole of silver halide.

T-Butylcatechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol 5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-sulfone Ammonium acid 2.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate
1.5 mg

[0063]

Embedded image

N-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂
1 g (Preparation of protective layer liquid) Next, the additives added to the protective layer are as follows. The added amount is shown as an amount per 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an area average particle size of 7 μm 7 mg Colloidal silica (average particle size 0.013 μm) 70 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg Bis-vinyl Sulfonyl methyl ether 36g

[0066]

Embedded image

Samples 1 to 33 were prepared by uniformly coating both surfaces of the above coating solution on a blue-colored polyethylene terephthalate film having a thickness of 175 μm and having been subjected to undercoating, and drying. At this time, the amount of silver attached to one surface of each sample and the amount of gelatin per one surface were adjusted to the amounts shown in Table 2.

(Evaluation of Sensitometry) The obtained sample was sandwiched between X-ray fluorescent intensifying screens XG-S (manufactured by Konica Corp.), and X was passed through a penetrometer type B (manufactured by Konica Medical Corp.). After irradiating the line, the development temperature is measured by using the automatic processor SRX-503 and processing solution SR-DF (both manufactured by Konica Corporation)
The treatment was carried out at 35 ° C. for a total treatment time of 45 seconds. At this time, the replenishment amount of the processing solution was 210 ml / m ^{2 for} both the developing solution and the fixing solution.

The sensitivity was shown as a relative value with the reciprocal of the X-ray dose necessary for obtaining the density of Sample 1 being +1.0 as the minimum value.

(Evaluation of ultra-rapid processability) After irradiating each sample with X-rays as in the case of sensitometry, an automatic processor SRX-503 was used.
Was processed so that the following processing time was obtained. The above-mentioned SR-DF was used as the processing liquid, and the replenishing amount was 125 ml / m ² for both the developing liquid and the fixing liquid, and the sensitivity was measured in the same manner as above.

Development time: 8 seconds Fixing time: 6.3 seconds Washing time: 3.4 seconds Washing-drying (squeeze): 2 seconds Drying time: 5.3 seconds Total processing time: 25 seconds (evaluation of pressure resistance) 13 mm × 35 mm Sample for about 1 hour, 23
The temperature was kept constant at 42 ° C. and a relative humidity of 42%, and under these conditions, it was bent at a radius of curvature of 4 mm and developed without being exposed. The density difference between the density of the blackened portion and the density of the fog produced by the bending at this time was set as ΔD, which was used as a standard for the pressure fog.
That is, the smaller this value is, the better the pressure resistance is.

(Evaluation of Graininess) For each sample, one surface was exposed to light and the graininess was visually evaluated using a developed sample of 20 cm × 20 cm in the area of blackening density of 0.6 to 0.8. It was evaluated according to the evaluation criteria.

5: Very good 4: Good 3: Practical: 2: Practical range but rough: 1: Roughly severely unusable These results are summarized in Tables 2 and 3.

[0074]

[Table 2]

[0075]

[Table 3]

From Tables 2 and 3, Sample No. using Emulsion No. 3 was used.
6-9, sample Nos. 14-16 using emulsion No. 7, emulsion No. 8
Nos. 17 to 19 using Emulsion, and Sample No. 2 using Emulsion No. 13
Sample Nos. 29 to 31 using No. 7, 28 and Emulsion No. 14 are superior in sensitivity to the comparative silver halide photographic light-sensitive material, and are superior in sensitivity, pressure resistance and graininess in rapid processing. .

[0077]

From the above results, according to the invention, a silver halide photographic light-sensitive material having high sensitivity and excellent rapid processability (sensitivity, pressure resistance and graininess in rapid processing) was obtained.

Claims (3)

[Claims] 1. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the average aspect ratio of silver halide grains contained in said silver halide emulsion layer. Is a tabular grain having a grain ratio of 5 or less and a tabularity of 25 or more and a silver chloride content of 50 mol% or more. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the weight ratio of silver / gelatin in the silver halide emulsion layer is 1 or more. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the amount of gelatin in the silver halide emulsion layer is 20% or more and 60% or less of the total amount of gelatin. .