JPS6048747B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material with improved pressure exasperation and excellent photographic properties.

It is well known in the industry that photographic materials containing silver halide grains with large grain sizes and high sensitivity are more likely to cause agitation caused by applying mechanical pressure on the exposure side, that is, pressure agitation. There is. Emulsions containing high-sensitivity silver halide grains with relatively large grain sizes are often used in industrial and medical X-ray films. Pressure exasperation is likely to occur due to bending of the film. Furthermore, automatic exposure and development devices using mechanical conveyance have recently been widely used as medical X-ray photographic systems.
In such equipment, mechanical excess is inevitably applied to the film, and pressure surges often occur, especially in dry environments such as in winter. For example, if such development occurs in a medical X-ray film, depending on the location where the development occurs, it may lead to a doctor's misdiagnosis and may cause serious trouble to the patient and the doctor. Furthermore, in recent years, as processing speeds have increased, the amount of binder such as gelatin that protects silver halide film has been reduced.

As a result, pressure rage is becoming more likely to occur. U.S. Pat. No. 2,628,167, U.S. Pat. No. 2,759,822, U.S. Pat. No. 5,344,5235, U.S. Pat. No. 5,344,5235, U.S. Pat. No. 2,296,204, French Patent No. 2,296,204, and Japanese Patent Application Laid-Open No. 1983-107 are aimed at improving pressure rash.
12-inch and No. 50-116025, etc., for example, methods using thallium and methods using dyes are described, but the degree of improvement is insufficient, dye staining is severe, and other methods are described. It is difficult to say that these materials are necessarily suitable for silver halide photosensitive materials that mainly utilize high-frequency normal surface sensitivity in which silver halide grains have a large average grain size.

On the other hand, various attempts have been made to improve pressure attenuation by changing the physical properties of the binder in silver halide photographic materials.

For example, US Pat. No. 3,536,491, US Pat. No. 3,775,12
No. 8, No. 3003878, No. 2759821,
and Specification No. 377203, JP-A-53-332
No. 5, No. 50-56227, No. 50-147324, and No. 51-141625. However, even if pressure desensitization is improved using these techniques, the physical properties of the binder, such as stickiness on the film surface, dryness, and scratches, are significantly deteriorated and cannot be fundamentally improved. The first object of the present invention is to provide a silver halide photosensitive material with improved pressure attenuation.

A second object of the present invention is to provide a silver halide photosensitive material having excellent photographic properties. The purpose of the present invention is to add a water-soluble silver salt solution and a water-soluble halide solution to a silver halide grain suspension to prepare a silver halide emulsion by an ammonia method. The silver halide grains of are substantially composed of silver chloride, and 10-8 to 10-5 moles of water-soluble iridium salt are present per mole of silver halide in the emulsion by the time of coating the silver halide emulsion. Using a silver halide emulsion that is characterized by This is achieved by a silver oxide photographic material. In a preferred embodiment, the average grain size of silver halide grains consisting essentially of silver chloride in the suspension is 0.5 μm or less, and polyalkylene oxides are present in the emulsion by the time of coating. The amount of hydrophilic binder during coating or emulsion coating is 200 to 25 Da per mole of silver halide.

The present invention will be explained below. Silver halide grains consisting essentially of silver halide are prepared by conventional methods.

At this time, ammonia may or may not be present. For example, a water-soluble chloride such as a potassium iodide aqueous solution and a water-soluble silver salt aqueous solution of silver nitrate are added to an aqueous gelatin solution, or a mixture of a potassium iodide aqueous solution and a gelatin aqueous solution is added to an aqueous silver nitrate solution. Substantially a suspension of silver chloride can be prepared in advance by a method such as. The silver halide grains consisting essentially of silver iodide preferably have an average grain size of 0.5 μm or less.

If the silver iodide is larger than 0.5 μL, it is very difficult to contain silver iodide throughout the grain without leaking into the final grains, which is a problem for the purpose of the present invention. cannot be achieved. It is appropriate that the silver halide grains consisting essentially of silver oxide are composed of 70% or more of silver oxide,
Preferably, pure silver is used. Into the homogeneously dispersed silver halide suspension thus obtained, which consists essentially of silver iodide, is a halite solution, for example potassium bromide, or potassium bromide and sodium chloride, or potassium bromide. A single or mixed aqueous solution of potassium iodide, or potassium bromide, sodium chloride, and potassium iodide, and an aqueous solution of a water-soluble silver salt, such as silver nitrate, are added to prepare a silver-genide emulsion. At this time, in the present invention, it is essential to use the ammonia method; if other preparation methods, such as the neutral method, are used, silver halide is uniformly applied to the silver halide grains in the finished emulsion. It is extremely difficult to spread the light over the entire range, making it impossible to achieve the purpose of the present invention.
The ammonia method in the present invention means using an ammine silver complex salt solution produced by adding ammonia in an amount equal to or more than the complex salt forming amount to a water-soluble silver salt, adding ammonia to a halide solution, or mixing the above two solutions. Either by pre-containing ammonia in the tank, by adding the ammonia solution separately to the mixing tank, or by combining the above four forms in chronological order when mixing the solution dividedly or not. It includes the embodiments in which it is used. Incidentally, ammonium halides such as ammonium chloride and ammonium bromide may be used to prevent the ammonia molecules in the silver halide emulsion from being depleted into ammonium ions.

The solutions of silver nitrate and halide used in the present invention are each 0.0. It is practical for the addition time to be within 15 gin, and the emulsion according to the present invention can be prepared within that range.

Furthermore, it is possible to adjust the pH of the reaction tank during mixing by adding an acid such as acetic acid to the halide solution. The composition of the silver halide grains finally produced in the present invention is not particularly limited, but preferably Agl is 0.5 to 7 mol%, AgCl is 0 to 60 mol%, and the remainder is AgBr. is preferred.

Moreover, the average size of the particles is preferably 0.3 to 2.0. In the present invention, during the manufacturing process of the silver halide emulsion, a polyalkylene oxide, preferably a compound represented by the following general formula, is present in the emulsion in order to promote the growth of emulsion grains and maintain monodispersity. is preferred. *General formula NaO2C(CH2)20C0-(CH2CH2O)m
(CHCW) where Y is -SO3M or -COBCO
In OM, M is a group selected from a hydrogen atom, an alkali metal atom, an ammonium group, or a lower alkyl-substituted ammonium group, B is a chain or cyclic group forming an organic divalent linking group, and p is 1-10 m and n are each 0-50.

As specific representative examples of this compound, the following can be enumerated.

Mountain Polyisopropyleneoxy-polyethyleneoxydisuccinate sodium salt) 17 (CH2CH2
O)n -CO(CH2F2u02Na(2)Polyisopropyleneoxy-PolyethyleneO'+1.12Fl
lO/. :FO/. 1VIV/Iy Sare” /U,J-
~ /υ (3) Polyisopropylene oxydisulfonic acid ester sodium salt × CO2K oxydimalate potassium salt “+1.12FllO/. :FO/. 1VIV/Iysare' /U,J- ~ /υ (4) Polyisopropyleneoxy-polyethyleneoxydiphthalate potassium salt (5) Polyisopropyleneoxy-polyethyleneoxydiacetotartaric acid ester ammonium salt These polyalkylene oxides is preferably added to the emulsion in the step of producing silver halide grains consisting essentially of silver iodide,
The amount added is preferably 0.01 to 2y per mole of silver halide.

Silver halide grains manufactured in the present invention in which a water-soluble iridium salt is present until the time of coating include the presence of the water-soluble iridium salt in the above amount in the emulsion during at least a part of the process up to coating. This is a silver halide grain of an emulsion produced by

Various compounds can be used as the water-soluble iridium salt used in the present invention, but typical specific examples useful in the present invention include iridium chloride (IrCl, and IrCl4
), potassium chloroiridate and ammonium chloroiridate. These compounds may be added as an aqueous solution before coating, and it is particularly desirable to add them during particle formation or physical ripening. The amount of the water-soluble iridium compound used in preparing the silver halide emulsion as described above is 10
-° to 10-゜mol is suitable, preferably 10-''
~10-6 mol. When the amount of the water-soluble iridium salt added per mole of silver halide is less than 10-[deg.] mole, no effect is observed, and when it is more than 10-5 mole, a disconcerting effect is observed at high illuminance. The water-soluble iridium salt may be added according to a known method. Hydrophilic binders used in the present invention include gelatin, gelatin derivatives such as phthalated gelatin, water-soluble cellulose derivatives, and polymers bonded with polyvinyl alcohol and other hydrophilic synthetic or natural polymer compounds. included.

The appropriate amount of addition is 200y to 25y per mole of silver halide. In the case of silver halide photosensitive materials not produced according to the present invention, significant pressure attenuation occurs when the hydrophilic binder is less than 150y, but in the silver halide photosensitive materials produced according to the present invention, pressure attenuation is difficult to occur. .

That is, in the silver halide photosensitive material produced according to the present invention, pressure desensitization is less likely to occur even if the amount of the hydrophilic binder that protects the silver is small. The amount of this hydrophilic binder is only on the side containing silver, and in the case of a double-sided film, it is the total amount on both sides. The silver halide emulsion according to the present invention can be gold-sulfur-mulched, selenium-mulched, noble metal-mulched, reduced-mulched and/or hydrogen-mulched.

Further, it is optional to add various photographic additives to the silver halide emulsion according to the present invention, for example, development accelerators such as thioether compounds, quaternary ammonia salts, and polyalkylene oxide compounds may be added. Antifoggants or stabilizers which are preferred and may optionally be used include azaindenes, thiazolium salts, sulfocatechols, urazoles, nitrones, nitroindazoles, mercaptotetrazoles, polycarboxylic acids,
One or more appropriately selected compounds among polyvinylpyrrolidone compounds, polyoxyaryl compounds, etc. are included.

The silver halide emulsion according to the present invention uses cyanine dyes, merocyanine dyes, etc. singly or in combination of two or more, so that the adsorption average total coverage of the dyes on the silver halide grain surfaces of the silver halide emulsion according to the present invention is achieved. Spectral brightening is possible in a small region where the ratio is less than 60%.

Furthermore, optionally used gelatin hardening agents include aldehydes, ethyleneimines, epoxies, sulfonyl chlorides, vinyl sulfonic acids, isocyanates, carbodiimides, active olefins, active halogens, aziridines, or Compounds that block these active functional groups are included.

In addition, wetting agents such as hydroxyalkanes or water-dispersible fine particle polymer compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc. can be added, and coating aids such as saponin and sulfosuccinates can be added. It is optional to include various photographic additives such as additives. The silver halide emulsion according to the present invention can be applied in at least a single layer to a suitable support such as a glass plate, cellulose acetate, cellulose nitrate, polystyrene, a polyester film such as polyethylene phthalate, a polycarbonate film, a polyacid film, etc. If necessary, a required number of auxiliary layers can be provided and applied by a conventional method to obtain a photographic material.

The silver halide photographic material to which the present invention can be applied may be, for example, a black-and-white photographic material, a color photographic material, a false color photographic material, and may be for general use, printing use, X-ray use, In addition to photographic materials used for various uses such as those for radiation, mechanically all kinds of photographic materials such as negative type, positive type, and diffusion transfer type can be mentioned.

The present invention will be explained below with reference to examples, but the embodiments of the present invention are not limited thereby. [Example 1] Solutions with the following formulations were prepared, and 11 types of emulsions (silver oxide content: 2 mol %) were produced in the following manner.

In emulsions in which silver iodide is precipitated, additional precipitation of silver halide is carried out when the average grain size of the silver iodide grains reaches 0.5 μm. (A-1) An ammoniacal silver nitrate aqueous solution prepared by adding 2.1 mol of ammonia per 1 mol of silver to 609 silver nitrate and making up to 300 cc with water.

(A-2) Silver nitrate aqueous solution prepared by adding 609 silver nitrate to 300 cc with water.

(B-1) Potassium bromide-gelatin aqueous solution prepared by adding 48 Da of potassium bromide and 5 Da of inert gelatin to 300 cc with water.

(B-2) Potassium iodobromide-gelatin aqueous solution prepared by adding 5 g of inert gelatin to 48 g of potassium bromide and 1.2 g of potassium iodide and adding water to make 300 cc.

(C-1) 1.2y (7) 5y of inert gelatin was added to potassium chloride, and 0.5cc of a 10% aqueous solution of polyisopropyleneoxy-polyethyleneoxydisuccinate sodium salt was further added and the volume was made up to 200cc with water. Potassium iodide-gelatin aqueous solution.

(C-2) Potassium iodide aqueous solution prepared by adding 1.2 Da of potassium chloride to 20 cc of water.

(C-3) An aqueous gelatin solution prepared by adding 0.5% of a 10% aqueous solution of polyisopropyleneoxy-polyethyleneoxydisuccinate sodium salt to 5y inert gelatin and making up to 200 cc with water.

(D-1) An aqueous solution of 1×10 −6 mol of potassium hexanechloroiridate made up to 5 cc with water.

1 (Note that the above-mentioned Example 1 was used as the polyisopropyleneoxy-polyethyleneoxydisuccinate ester.

) Production of emulsion 1 (C-1) was added to the reaction tank, and the number of revolutions was 300 times.
18 cc of (A-1) was added in 3 strokes while stirring with a propeller type stirrer and keeping the reaction temperature at 55°C.

After 1 minute, the remainder of (A-1) and (B-1) were added (A-1) and (B-1) were added.
-1) required two pieces, and (B-1) required one piece.

Five minutes after the addition of (A-1), the mixture was neutralized with acetic acid to adjust the pH to 6, and desalted using a known method. Production of Emulsion 2 In the production of Emulsion 1 above, after addition of the remainder of (A-1) 1
After beating for 3 minutes, (D-1) was added for 30 seconds, and then
Emulsion 1 was prepared in the same manner as Emulsion 1 except that acetic acid was added after 1 minute.

Preparation of Emulsion 3 Emulsion 3 was prepared in exactly the same manner as Emulsion 2 except that the polyisopropyleneoxy-polyethyleneoxydisuccinate sodium salt was removed.

Emulsion 4 was produced under the same conditions as Emulsion 1 (C-3) except that a reaction tank was added.

Production of Emulsion 5 In the production of Emulsion 4, 1 minute 3 after adding the remainder of (A-1).
Emulsion 4 was used except for adding (D-1) three times after brewing.
It was manufactured in exactly the same way.

Production of emulsion 6 (C-3) was added to the reaction tank, and the remaining 2 powders of (A-1) and (
One drop of B-1) was added.

Furthermore, 5 minutes after the start of the reaction, (C-2) was added over 1 minute.

The other conditions were the same as in Emulsion 1. Production of Emulsion 7 In the production of Emulsion 6, 1 minute 3 after adding the remainder of (A-1).
Emulsion 6 was produced in the same manner as Emulsion 6 except that (D-1) was added three times after the addition.

Production of emulsion 8 (C-1) was added to the reaction tank, and stirred using a propeller type stirrer with a rotation speed of 30 rotations/min. While maintaining the reaction temperature at 65°C, 18 cc of (A-2) was added to the reaction tank at 30° C. 1 minute after adding (A-2
) and 10 portions of (B-1) were added.

After the addition was completed, desalination was performed using a known method. (This production uses a neutral method, so neutralization is not required.) Production of emulsion 9 In production of emulsion 8 (after adding the remainder of (A-2)) 1 minute 3
Emulsion 8 except that (D-1) was added for 30 seconds after 0 seconds.
It was manufactured in the same manner.

Production of emulsion 10 (C-3) was added to the reaction tank, and the remainder of (A-2) was added to No. 2α,
(B-2) was added over 1 minute.

The other conditions were the same as in Emulsion 8.

Production of Emulsion 11 In the production of Emulsion 10, 1 minute 3 after adding the remainder of (A-2)
Emulsion 10 except that (D-1) was added at 3 times after the addition.
It was manufactured in the same manner.

After emulsions 1 to 11 were each subjected to gold-sulfur enrichment, 100y of gelatin was added per mole of silver halide, and commonly used inhibitors, stabilizers, and coating aids were added to adjust the amount of coated silver. It was coated on a polyethylene phthalate film support at a concentration of 50 mgA/100d and dried.

Each sample was kept at a constant temperature and humidity of 25° C. and 50% relative humidity for about 1 hour, and bent about 280 degrees with a radius of curvature of 2Crf1 under that condition.

After 3 minutes of bending, exposure was carried out for 10-2 seconds using an optical wedge with a tungsten lamp as the light source, and further, using Konishiroku Photo Industry's XD-90 developer, the temperature was 35°C.
After the three-layer development process, normal fixing and drying were performed. Further, blackening was measured using a PDA-65 densitometer manufactured by Roku Konishi Photo Industry, and several results were obtained with blackening density between 0.5 and 1.5. Let the density difference between the part and the part that was not folded be ΔD, divide ΔD by each density D, and calculate the average value ΔD/
I got a D. This value was used as a measure of desensitization due to bending. In other words, the smaller this value is, the smaller the desensitization caused by the pressure caused by bending. The results are shown in Table 1. As shown in Table 1, it can be seen that Emulsions 2 and 3 according to the invention have improved pressure attenuation compared to Emulsions 1 and 4 to 11.

[Example 2] Emulsions 1 and 2 prepared in Example 1 were gold-sulfur sensitized, and then 100y
, 150y, 200y, 300y, and 500y of gelatin, and the commonly used inhibitors, stabilizers, and coating aids were added to each to give a coated silver amount of 50mgAg/100d.
It was coated on a polyethylene terephthalate film support and dried.

Each sample was subjected to a pressure test in the same manner as in Example 1, and the results are shown in Table 2.

In addition, these samples were exposed for 0.1 seconds using a tungsten lamp as the light source, and developed at 35°C with XD-90 developer manufactured by Konishiroku Photo Industry, followed by normal fixing and drying. A sample for sensitometry was obtained.

Claims (1)

[Scope of Claims] 1. In a silver halide emulsion prepared by an ammonia method by adding a water-soluble silver salt solution and a water-soluble halide solution to a silver halide grain suspension, the suspension The silver halide grains therein are substantially composed of silver iodide, and by the time of coating the silver halide emulsion, 10^-^8 to 10^-^5 mol of water is dissolved per 1 mol of silver halide in the emulsion. 1. A silver halide photographic light-sensitive material comprising a silver halide emulsion characterized by the presence of an iridium salt. 2. The silver halide photographic material according to claim 1, wherein the silver halide grains consisting essentially of silver iodide have an average grain size of 0.5 μm or less. 3. The silver halide photographic material according to claim 1 or 2, wherein a polyalkylene oxide is present in the emulsion before the silver halide emulsion is coated. 4. The silver halide photographic material according to claims 1 to 3, wherein the amount of hydrophilic binder in the silver halide emulsion used in the silver halide photographic material is 200 to 25 g per mole of silver halide. .