JPH0829914A - Silver halide photographic component and processing method therefor - Google Patents

Abstract

PURPOSE:To provide photographic component whose pressure properties are improved and which has high sensitivity, suitability for quick processing, film forming properties, and storability including picture forming function and provide a processing method for the component. CONSTITUTION:Regarding a photographic component having at least one layer of silver halide emulsion layers and a non-sensitive hydrophilic colloidal layer on a supporting body, the photographic component contains characteristically inorganic fine particles shelled with gelatin in at least one layer of the emulsion layers. A processing method for the silver halide photographic component characteristically involves processing the silver halide photographic component by an automatic developing machine in a total processing time of 15-60 seconds.

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 element, and more particularly to a silver halide photographic element having high sensitivity, improved pressure characteristics, rapid processing suitability and storability.

[0002]

2. Description of the Related Art In recent years, due to the progress of electronics, the access time to images has been dramatically shortened and silver halide photographic elements are required to be processed rapidly. Therefore, silver halide grains are also required to have high sensitivity, and tabular silver halide grains are often used. This is because flattening increases the projected area, increases the amount of light received per unit grain, and allows a large amount of sensitizing dyes to be adsorbed, and higher spectral sensitization is expected.
Regarding the use of the tabular silver halide grains described above in a silver halide photographic light-sensitive material using gelatin as a binder, U.S. Pat. Nos. 4,386,156, 4,399,215 and 4,414,304 are described.
No. 4,425,425 and so on.

On the other hand, in order to promote rapid processing, the amount of gelatin, which is a binder that has protected the above silver halide grains, is reduced to reduce the developing rate and fixing rate in photographic processing.
There is a demand for a technique for increasing the washing speed and the drying speed. Higher sensitivity silver halide grains became weaker with external pressure when the amount of gelatin used was reduced, and attempts have been made to improve the grain preparation method to overcome this, but high sensitivity and low fog have been attempted. At the same time, no silver halide grains having both high pressure resistance have been found yet.

On the other hand, it is known to add a latex which is soft and functions as a buffer for the purpose of improving the pressure characteristics, and Japanese Patent Publication No. 53-28086 and Research Disclosure, Volume 195, 198
Issued in July 0, listed in Item 19551 etc. Further, a technique of using a latex together with tabular silver halide grains is also described in JP-A-2-135335. However, in the above technology, when the amount of gelatin used is reduced and a large amount of latex is used in order to achieve a rapid processing, although the pressure resistance is improved, the physical properties of the film such as kutsuki are deteriorated and the level is improved to a satisfactory level. I haven't made it.

In order to solve such a problem, a technique for improving the pressure characteristics by adding colloidal silica to the emulsion layer is disclosed in Japanese Patent Laid-Open No.
4-214551, 4-340951, 5-53230, 5-53237, etc. According to this, the deterioration of the physical properties of the film is surely small, but when it is added to an effective amount, the film is cracked when the processed film is stored after image formation, which is a serious problem in practical use. As a means for improving this, Japanese Patent Application Laid-Open No. 6-95300 discloses a technique in which colloidal silica is surface-treated to introduce a functional group capable of crosslinking with gelatin. According to this, although the cracking of the film on storage was improved, it was found that it causes a decrease in sensitivity and a maximum concentration during storage.

[0006]

In order to solve the above problems, an object of the present invention is to improve sensitivity and pressure characteristics,
Further, it is to provide a photographic element excellent in rapid processing suitability and excellent in storability including film physical properties and photographic performance, and a processing method thereof.

[0007]

SUMMARY OF THE INVENTION In a photographic element having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, the above object of the present invention is to provide a gelatin in at least one of the emulsion layers. A photographic element characterized in that it contains inorganic fine particles shelled with a silver halide photographic element characterized in that the silver halide photographic element is processed in an automatic processor having a total processing time of 15 to 60 seconds. It is achieved by the processing method of.

In the above photographic element, the inorganic fine particles shelled with gelatin have a particle size of 1 to 300 nm, and the main components are silicon oxide, aluminum oxide, antimony oxide,
It is selected from titanium oxide, zinc oxide, zirconia oxide, tin oxide, vanadium oxide, yttrium oxide, and niobium oxide, and the silver halide grains in the emulsion layer are flat plates having an aspect ratio of 2 or more. It is a preferred embodiment of the present invention to be a silver halide photographic element characterized in that it is in the form of grains.

The present invention will be specifically described below.

Inorganic fine particles shelled with gelatin used in the present invention are characterized in that the inorganic fine particles are covered with a shell of gelatin which has been previously hardened with a crosslinking agent. The morphology may be shelled with cross-linked gelatin of inorganic fine particles one by one, or a plurality of inorganic fine particles may be alloyed with gelatin, resulting in being covered with cross-linked gelatin. . That is,
The present invention is clearly distinguished from the prior art in which the inorganic fine particles are simply added to the emulsion layer in that they are shelled with pre-crosslinked gelatin and then applied to the emulsion layer. The gelatin to be shelled may have an arbitrary thickness of 1 to 500 nm. Further, in order to enhance the affinity with gelatin to be shelled, the surface of the inorganic fine particles is treated with a silane coupling agent, an aluminate compound and / or a titanium compound described in JP-A Nos. 4-257849 and 6-95300. May be processed before shelling. Since the average particle size of the inorganic fine particles used does not impair the transparency of the photographic element,
1 to 300 nm is preferable. As the main component of the inorganic fine particles,
Silicon, aluminum, titanium, indium, tin, antimony, zinc, nickel, copper, iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium,
It is an oxide selected from yttrium, niobium, alkali metals, alkaline earth metals, etc. Among them, in terms of transparency and hardness, silicon oxide (colloidal silica), aluminum oxide, antimony oxide, titanium oxide, Zinc oxide, zirconium oxide, tin oxide, vanadium oxide, yttrium oxide, and niobium oxide are preferable. When these inorganic oxides are dispersed in water to form a sol,
The surface may be treated with alumina, yttrium, cerium or the like in order to enhance the water dispersion stability of itself.

As the cross-linking agent to be shelled, a hardening agent which can harden gelatin can be usually used, but aldehyde-based, triazine-based, vinyl sulfone-based and carboxy-active groups described in JP-A-63-61243 are used. It is preferred to use mold hardeners.

As the gelatin used, alkali-processed gelatin, acid-processed gelatin, phthalated gelatin and the like can be used. Considering dispersion stability, the calcium ion content of the gelatin is preferably 0 to 4000 ppm.

The method for preparing the inorganic fine particles shelled with gelatin used in the present invention will be described. After mixing the gelatin aqueous solution and the inorganic fine particle water dispersion, 30-80 ℃
The temperature is maintained at the above temperature, and the gelatin cross-linking agent is added little by little while stirring with a high-speed stirrer having a sufficient shearing force, such as a homomixer or an impeller, and then at the above temperature for 1 hour to 72 hours.
It is obtained by time dispersion. In addition, when dispersed, in order to prevent aggregation, polyphosphates such as sodium pyrophosphate, sodium hexametaphosphate, and sodium tripolyphosphate, sorbitol, trimethylolpropane, trimethylolethane, trimethylolmethane, and other polyhydric salts. A nonionic polymer such as alcohol or polyethylene glycol alkyl ester can be appropriately added.

Preferred synthetic examples are shown below.

[Synthesis Example 1 (B-1)] 260 g of alkali-treated gelatin was dissolved in 8750 ml of pure water. This was kept at 40 ° C., and 1000 g of colloidal silica partially modified with alumina (30 wt% aqueous solution: average particle size 14 nm) was added. While stirring the obtained solution with a homomixer at high speed, 220 ml of 3.7% formalin was added little by little over 1 minute, and then the mixture was stirred for 5 minutes.
I went on time. The resulting dispersion was filtered through a filter having a diameter of 3 μm to remove aggregates.

[Synthesis Example 2 (B-2)] The same as in Synthesis Example 1, partly modified with alumina, colloidal silica (30% by weight aqueous solution: average particle size 14 nm) was added to 1000 g of 3-glycidoxypropyl-
A dispersion liquid was prepared in the same manner as in Synthesis Example 1 except that 3.0 g of trimethoxysilane was added and stirred at 50 ° C. for 1 hour. However, the stirring temperature was 50 ° C. and the stirring time was 10 hours.

[Synthesis Example 3 (B-3)] A dispersion liquid was prepared in the same manner as in Synthesis Example 2 except that the following titanium compound (TI) was used as the silane coupling agent.

[Synthesis Example 4 (B-4)] The procedure of Synthesis Example 1 was repeated except that the curing agent was changed to the following compound (RH).
A dispersion was prepared.

[Synthesis Example 5 (B-5)] A dispersion was prepared in the same manner as in Synthesis Example 1 except that gelatin was changed to acid-treated gelatin.

[Synthesis Example 6 (B-6)] A dispersion liquid was prepared in the same manner as in Synthesis Example 1 except that the inorganic fine particles were changed to antimony pentoxide sol (average particle size 24 nm).

[Synthesis Example 7 (B-7)] A dispersion liquid was prepared in the same manner as in Synthesis Example 2 except that the inorganic fine particles were changed to antimony pentoxide sol (average particle size 24 nm).

[0022]

Embedded image

The amount of the inorganic fine particles shelled with gelatin used in the present invention is preferably 0.05 to 1.0 in terms of dry weight ratio to gelatin used as the binder of the layer to be added, particularly preferably 0.1 to It is 0.7. The above-mentioned inorganic fine particles may be used in combination.

In the present invention, the coating amount of the hydrophilic binder in the emulsion layer containing inorganic fine particles is preferably 2.0 g / m ² or less, and particularly preferably 1.0 g / m ² or less per one side of the support.
And the total hydrophilic binder amount of all layers on one side of the support is
It is preferably 3.0 g / m ² or less, and particularly preferably 2.5 g / m ² or less. However, the hydrophilic binder in the present invention is gelatin,
By hydrophilic colloid materials such as natural or synthetic hydrophilic polymers such as dextran, dextrin, polyacrylamide.

As the silver halide used in the photographic element of the present invention, tabular grains are preferably used in order to obtain high sensitivity. AgBr, AgCl, AgCl as silver halide composition
Although Br, AgClBrI, AgBrI, AgClBrI and the like can be arbitrarily used, AgBrI rich in AgBr composition is preferable.

Tabular grains are described in US Pat. No. 4,439,520,
No. 4,425,425, No. 4,414,304, etc., and the target tabular grain can be easily obtained. The tabular grains can be formed by epitaxially growing silver halide having a different composition on a specific surface site or by shelling. Further, in order to control the photosensitive nuclei, a transition line may be provided on the surface or inside of the tabular grains.

The tabular grains of the present invention are preferably tabular grains having an aspect ratio of 2 or more in 50% or more of the total projected area of all grains in the emulsion layer in which the tabular grains are used. Especially tabular grains account for 60% to 70% and 80%
The better the result, the better the result. Here, the aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of tabular grains and the distance between two parallel planes. In the present invention, the aspect ratio is preferably 2 or more and less than 20, and 3 or more and less than 16.

The tabular grains of the present invention preferably have a thickness of 0.5 μm or less, preferably 0.3 μm or less. The distribution of tabular grains is such that the coefficient of variation often used (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated by a circle by the diameter D) is 30% or less, particularly 20% or less. It is preferably a monodisperse emulsion. Further, two or more kinds of tabular grains and non-tabular grains of normal crystal may be mixed.

Ammonia, thioether compounds, thione compounds and the like can be used as a silver halide solvent in order to control grain growth during formation of tabular grains. Further, metal salts such as zinc, lead, thallium, iridium and rhodium can be made to coexist during physical aging and chemical aging.

For chemical sensitization, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, noble metal sensitization and combinations thereof are used. Examples of the sulfur sensitizer applicable in the present invention include U.S. Patents 1,574,944 and 2,410,689.
No., No. 2,278,947, No. 2,728,668, No. 3,501,313,
The sulfur sensitizers described in U.S. Pat. No. 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016 can be used. As a specific example, 1,3-
Diphenylthiourea, triethylthiourea, 1-ethyl, 3
Preferred examples include thiourea derivatives such as-(2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, organic polysulfide compounds, and simple sulfur. Incidentally, α-sulfur belonging to the orthorhombic system is preferable as the simple substance of sulfur.

The selenium sensitizers used in the chemical sensitization of the present invention include a wide variety of selenium compounds. For example, in this regard, U.S. Patents 1,574,944, 1,602,592, 1,
623,499, JP-A-60-150046, JP-A-4-25832, and JP-A-4-5832
-109240, 4-147250, etc. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenoate). Urea, N, N, N′-trimethyl-N′-heptafluoroselenourea, N, N, N′-trimethyl-N′-heptafluoropropylcarbonylselenourea, N, N, N′-trimethyl-N′- 4-nitrophenylcarbonyl selenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg , 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg,
Tri-p-triselenophosphate and the like) and selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. That is, US Patent 1,
574,944, 1,602,592, 1,623,499, 3,297,4
No. 46, No. 3,297,447, No. 3,320,069, No. 3,408,196
No. 3,408,197, 3,442,653, 3,420,670,
No. 3,591,385, French Patent No. 2693038, No. 2093209
No. 52-34491, 52-34492, 53-295, 53-295
57-22090, JP-A-59-180536, 59-185330, 59
-181337, 59-187338, 59-192241, 60-1500
46, 60-151637, 61-246738, JP 3-4221
No. 3, No. 3-24537, No. 3-111838, No. 3-116132, No. 3-1
48648, 3-237450, 4-16838, 4-25832,
4-32831, 4-96059, 4-109240, 4-140738
No. 4-140739, 4-147250, 4-149437, 4-
184331, 4-190225, 4-191729, 4-195035
No., British Patent Nos. 255846 and 861984. HESpencer
Etc.Journal of Photographic Science magazine, Vol. 31, 158-1
It is also disclosed in scientific literature such as page 69 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 mol to 10 ^-4 mol per mol of silver halide is used. In addition, the addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol, ethanol, and ethyl acetate alone or in a mixed solvent depending on the properties of the selenium compound to be used, or by previously mixing with a gelatin solution. Or the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent. The temperature of chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90 ° C. It is more preferably 45 ° C or higher and 80 ° C or lower.
The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

The tellurium sensitizers and sensitization methods used in the chemical sensitization of the present invention are described in US Pat. No. 1,623,499.
Issue 3,320,069, Issue 3,772,031, Issue 3,531,289,
No. 3,655,394, British Patent No. 235,211, No. 1,121,496
No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,
No. 958, JP-A-4-204640, and JP-A-4-333043. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-dimethyl. -N'phenyl tellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, , Telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotellocyanates, and the like. The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

In the present invention, it is also preferable to use reduction sensitization together. The reduction sensitization is preferably performed during the growth of silver halide grains. As the method of applying during the growth, not only the method of performing reduction sensitization while the silver halide grains are growing, but also the method of performing reduction sensitization with the growth of silver halide grains being interrupted and then performing the reduction sensitization Also included are methods of growing the perceived silver halide grains.

As the gold sensitizer used in the present invention, in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like, gold complexes of thioureas, rhodanines and other various compounds can be mentioned. .

The amount of the sulfur sensitizer, selenium sensitizer, tellurium sensitizer, reduction sensitizer and gold sensitizer used depends on the type of silver halide emulsion, the type of compound used and the ripening conditions. Although it is not so, usually, it is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the present invention, the sulfur sensitizer, the selenium sensitizer, the tellurium sensitizer, the reduction sensitizer and the gold sensitizer are added by dissolving them in water or alcohols, other inorganic or organic solvents, and then dissolving them. Or in the form of a dispersion obtained by emulsification and dispersion using a water-insoluble solvent or a medium such as gelatin.

The sensitizing dye used in the present invention may be added at any time during the formation of the silver halide grains and after the formation but before the coating, but it is preferably before the completion of the desalting step. The pH of the reaction liquid (usually in the reaction kettle) at the time of addition is preferably in the range of 4 to 10. More preferably, it is within the range of pH 6-9. The pAg in the reaction solution (reaction vessel) is preferably 5-11.

The sensitizing dye used in the present invention is optional. For example, a cyanine dye can be preferably used. In that case, the compounds of S-1 to S-124 represented by the general formulas (I) to (III) described in JP-A No. 1-100533 can be preferably used.

When the above-mentioned sensitizing dye is added, 2
You may use together 1 or more types. In this case, two or more sensitizing dyes may be mixed and added at the same time, or may be added separately at different times. The addition amount is 1 to 1000 mg, preferably 5 to 500 mg per mol of silver. Furthermore, it is preferable to add potassium iodide before adding these sensitizing dyes and then add it.

The sensitizing dye used in the present invention can be directly dispersed in the emulsion. Further, these may be dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added in the form of a solution. Also, ultrasonic waves can be used for dissolution. Further, the water-insoluble sensitizing dye may be added as a fine particle dispersion by high speed impeller dispersion without being dissolved in water.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 4,142,894 are used.
No. 4,396,706 homopolymer of polymethylmethacrylate or polymer of methylmethacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, strontium sulfate, fine particles of inorganic compounds such as barium sulfate. Can be used. The particle size is 0.6-10 μm, especially 1-5 μm
It is preferred that

In the surface layer of the photographic element of the present invention, in addition to the silicone compounds described in US Pat. Nos. 3,489,576 and 4,047,958 and the colloidal silica described in Japanese Patent Publication No. 56-23139, paraffin is used as a slip agent. Wax, higher fatty acid ester, starch derivative and the like can be used. Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be added as plasticizers to the constituent layers of the photographic element of the present invention. Further, the constituent layers of the photographic element of the present invention may contain a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, styrene, etc., a styrene-butadiene copolymer, a polymer or a copolymer comprising a monomer having an active methylene group, a water-soluble group or a crosslinkable group with gelatin is preferable. Can be used. In particular, in order to enhance the affinity with gelatin as a binder, a copolymer with a monomer having a water-soluble group mainly composed of an alkyl ester of acrylic acid, a hydrophobic monomer such as styrene, or a crosslinkable group with gelatin is most preferable. Used.
Desirable examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid and 2-acrylamide-2.
-Methyl propane sulfonic acid, styrene sulfonic acid and the like, and preferable examples of the monomer having a crosslinkable group with gelatin are glycidyl acrylate, glycidyl methacrylate and N-methylol acrylamide.

When the photographic element of the present invention is used as a double-sided emulsion X-ray sensitive material for medical use, it is preferable to provide a transverse light blocking layer for the purpose of improving image sharpness. The transverse light blocking layer contains a solid fine particle dispersion of a dye for the purpose of absorbing transverse light. Examples of such dyes include
There is no particular limitation as long as it is a dye having a structure which is soluble in an alkali having a pH of 9 or more and hardly soluble in a pH of 7 or less, but the general formula described in Japanese Patent Application No. 5-119113 is preferred because of its good decolorizing property during development processing. The compound of (I) is preferably used.

The photographic elements of the present invention exhibit excellent performance in rapid development processing on automatic processors with total processing times of 15 to 60 seconds, with 30 seconds or less providing the most desirable results. In the rapid processing of the present invention, the temperature and time for developing, fixing, etc. are each 25 seconds or less at about 25 to 50 ° C., preferably
It is 4 to 15 seconds at 30 to 40 ° C. In the present invention, the photographic element is developed, fixed and then washed with water. Here, in the water washing step, a water-saving treatment can be performed by using a countercurrent water washing method of two or three stages. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. In the present invention, the developed, fixed and washed photographic element is dried through a squeeze roller. Dry at 40-80 ℃, 4 ~
It takes 30 seconds. With the total processing time in the present invention, after inserting the leading end of the film into the insertion port of the automatic developing machine, the developing tank, the transition portion, the fixing tank, the transition portion, the washing tank, the transition portion,
It is the total time for the leading edge of the film to come out of the drying outlet after passing through the drying section. The silver halide photographic element of the present invention can reduce the amount of gelatin used as a binder for the emulsion layer and the protective layer without impairing the pressure characteristics, so that the development speed can be increased even in the rapid processing with a total processing time of 15 to 60 seconds. The developing process can be performed without impairing the fixing speed and the drying speed.

[0047]

The present invention will be described with reference to the following examples.

Example 1 A seed emulsion used in Examples and a method for preparing the emulsion will be described.

(Preparation of seed emulsion-1) A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N Aqueous silver nitrate solution 2825ml C1 Potassium bromide 824g Potassium iodide 23.5g Finish to 2825ml with water D1 1.75N Potassium bromide aqueous solution Mixing stirrer as described in JP-B-58-58288 and 58-58289 at the following silver potential control amount 35 ° C Solution A1 using solution B1 and solution C1 each 464.3 m
1 was added by the double-sided mixing method over 1.5 minutes to perform nucleation.

After the addition of the solutions B1 and C1 was stopped, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then add the solution B1 again. Solution C1 was mixed by the simultaneous mixing method at a flow rate of 55.4 ml / min.
Added for 2 minutes. This temperature rise from 35 ° C to 60 ° C and solution B
The silver potentials (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during re-simultaneous mixing by 1 and C1 were controlled to +8 mv and +16 mv, respectively, using the solution D1.

After the completion of the addition, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of silver halide grains.
It was confirmed by an electron microscope that the hexagonal tabular grains of 2.0 had an average thickness of 0.06 μm and an average grain size (converted to a circle diameter) of 0.59 μm. The variation coefficient of thickness is 40
%, And the coefficient of variation in the distance between twin planes was 42%.

(Preparation of Em-1) A tabular emulsion having a core / shell structure was prepared by using the seed emulsion-1 and the following four kinds of solutions.

A2 ossein gelatin 11.7 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-1 equivalent to 10.10 mol B2 ossein gelatin 5.9 g potassium bromide 6.2 g Potassium iodide 0.8g Finished to 145ml with water C2 Silver nitrate 10.1g Finished to 145ml with water D2 Ocein gelatin 6.1g Potassium bromide 94g Finished to 304ml with water E2 Silver nitrate 137g Finished to 304ml with water A2 vigorously stirred A2 Solution B2 and solution C2 were added to the solution by the double jet method in 58 minutes. Next, in the same liquid, D2
Solution and E2 solution were added by the double jet method for 48 minutes. During this period, pH was kept at 5.8 and pAg was kept at 8.7.

After completion of the addition, desalting and precipitation were carried out in the same manner as the seed emulsion-1 to obtain an emulsion having an average silver iodide content of pAg 8.5 and pH 5.85 of about 0.5 mol% at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that tabular silver halide grains having an average grain size of 0.96 μm in 81% of the projected area and a broad grain size distribution of 19% and an average aspect ratio of 4.5. Met. The average distance between twin planes (a) is 0.
The coefficient of variation of (a) was 28%.

(Preparation of seed emulsion-2) Seed emulsion-2 was prepared as follows.

A4 ossein gelatin 100g potassium bromide 2.05g 11.5l with water B4 ossein gelatin 55g potassium bromide 65g potassium iodide 1.8g 0.2N sulfuric acid 38.5ml 2.6l C4 ossein gelatin with water 75g potassium bromide 950g iodine Potassium iodide 27 g Water 3.0 l D3 silver nitrate 95 g Water 2.7 l E2 Silver nitrate 1410 g Water 3.2 l Add solution B4 and D3 to control solution A4 solution kept at 60 ° C over 30 minutes. Then, C4 and E2 solutions were added by the control double jet method over 105 minutes. The stirring was performed at 500 rpm. The flow rate was such that new nuclei did not occur with the growth of particles, and so-called Ostwald ripening occurred, and the particle size distribution did not broaden. When the silver ionic liquid and the halide ionic liquid were added, the pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then desalting was carried out by the method described in JP-B-35-16086 in order to remove excess salts.

When the seed emulsion was observed by an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and a distribution of 17% with slightly rounded corners.

(Preparation of Em-2) A monodisperse core / shell type emulsion was prepared by using seed emulsion-2 and the following seven kinds of solutions.

A5 ossein gelatin 10 g Ammonia water (28%) 28 ml Glacial acetic acid 3 ml Seed emulsion-3 0.119 mol equivalent 600 ml with water B5 ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g 110 ml with water C5 ossein gelatin 2.0 g Potassium bromide 90 g Water 240 ml D4 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Water 110 ml E3 Silver nitrate 130 g Ammonia water (28%) 100 ml Water 240 ml F1 Potassium bromide 94 g Water 165 g G1 Silver nitrate 9.9 g Ammonia water (28%) 110 ml A5 solution was kept warm at 40 ° C. with 7.0 ml water and stirred at 800 rpm with a stirrer.
The pH of solution A5 was adjusted to 9.90 with acetic acid, seed emulsion-3 was collected and dispersed and suspended, and then solution G1 was added at a constant rate over 7 minutes to adjust the pH to 7.3. Further, solution B5 and solution D4 were added simultaneously over 20 minutes. At this time, pAg was kept constant at 7.3.
Using potassium bromide solution and acetic acid for another 10 minutes
After adjusting the pH to 8.83 and the pH to 9.0, the C5 solution and the E3 solution were simultaneously added over 30 minutes.

At this time, the flow rate ratio at the time of addition and at the end of addition was 1:10, and the flow rate was increased with time.
The pH was decreased from 8.83 to 8.00 in proportion to the flow rate ratio. When the C5 solution and the E3 solution were added by 2/3 of the total amount, the F1 solution was additionally injected and added at a constant rate over 8 minutes. At this time, pAg rose from 9.0 to 11.0. Further, acetic acid was added to adjust the pH to 6.0.

Then, in the same manner as when the Em-1 emulsion was prepared,
The average grain size is 0.40 μm, the average silver iodide content is 2 mol%, the grain size distribution is 14%, and the rounded average aspect ratio is 1.
A 14-sided monodisperse core / shell emulsion of 2 was obtained. The resulting emulsions (Em-1 and Em-2) were each heated to 60 ° C. and a predetermined amount of the spectral sensitizing dye was added as a solid fine particle dispersion, followed by adenine, ammonium thiocyanate and gold chloride. A mixed aqueous solution of acid and sodium thiosulfate and a solution obtained by dissolving triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol are added, and further 60
After a minute, a silver iodide fine grain emulsion was added and ripening was carried out for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above additives and their addition amounts (per mol of AgX) are shown below.

Spectral sensitizing dye (A) 120 mg Spectral sensitizing dye (B) 2.0 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide fine particles 280 mg 4 -Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-99437.
It was prepared according to the method described in No. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high speed stirrer (dissolver) at 500 rpm for 30 to 120 minutes.

Sensitizing dye (A) 5,5'-dichloro-9-ethyl
-3,3'-di- (sulfopropyl) oxacarbocyanine-sodium salt anhydride Sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,1 '
-Diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt Anhydrate The following coating solutions were under-coated and colored in blue.
A transverse light-shielding layer, an emulsion layer, and an emulsion protective layer were applied in this order from the bottom to both sides of a 175 μm polyethylene terephthalate support, and dried.

(Preparation of sample) First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 50 mg / m ² gelatin 0.4 g / m ² sodium dodecylbenzenesulfonate 5 mg / m ² compound (I) 5 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² latex (L) 0.2 g / m ² polystyrene sulfone Potassium acid salt 50 mg / m ² Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Potassium tetrachloropalladate 100 mg / m ² compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl- Catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate (molecular weight 600,000) 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3-dihydroxybenzene-4-sulfonic acid ammonium 500 mg / m ² 2-mercaptobenzimidazole-5-sodium sulphonate 5 mg / m ² compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² Inorganic fine particles of the present invention (Table 1) 0.5 g / m ² latex (L) 0.4 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² sorbitol 0.1 g / m ² However, the gelatin was adjusted to 1.2 g / m ² .

Third layer (protective layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 50 mg / m ² Matting agent consisting of polymethylmethacrylate (area average particle size) Diameter 7.0 μm) 50 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg / m ² Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis-vinylsulfonyl methyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² dextrin (average molecular weight 5000) 0.2 g / m ² sodium polyacrylate 30 mg / m ² Inorganic fine particles of the present invention (see Table 1) 0.5 g / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15mg / m ² compound (O) 50mg / m ² compound (S-2) 5mg / m 2 compound (F 1) 3mg / m ² Compound (F-2) 2mg / m 2 Compound ^{(F-3) 1mg / m} 2

[0070]

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[0071]

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[0072]

[Chemical 4]

The coating amount of the material was for one side, and the coated silver amount was adjusted to be 1.6 g / m ² for one side.

(Evaluation of sensitivity and storability) The obtained sample was divided into two, and one was stored at 23 ° C. and 55% RH for 7 days. (Storage condition I) The rest was stored at 23 ° C. and 55% RH for 4 days as a substitute for storability, and then stored in a moisture-proof bag in the temperature and humidity environment and stored at 55 ° C. for 3 days. (Storage condition II) Both of the obtained samples were sandwiched with an intensifying screen KO-250 for X-ray photography, irradiated with X-rays through a penetrometer type B, and then a roller-conveying type automatic processor (SRX-501: Konica Corporation). Manufactured by the following).
Processing was performed with the fixer under the following conditions.

Current image 35 ° C 14.0 seconds Fixed temperature 34 ° C 9.7 seconds Water wash 26 ° C 9.0 seconds Squeeze 2.4 seconds Dry 55 ° C 8.3 seconds Total (Dry To Dry) 43.4 seconds Developer formulation Part-A (12l finish) Potassium hydroxide 450g Potassium sulfite (50% solution) 2280g Diethylenetetraamine pentaacetic acid 120g Sodium bicarbonate 132g 5-Methylbenzotriazole 1.2g 1-Phenyl-5-mercaptotetrazole 0.2g Hydroquinone 340g Add water to finish to 5000ml Part -B (for 12l finish) Glacial acetic acid 170g Triethylene glycol 185g 1-Phenyl-3-pyrazolidone 22g 5-Nitroindazole 0.4g Starter glacial acetic acid 120g Potassium bromide 225g Add water to finish to 1.0l Fixer formulation Part-A (For 18l finish) Ammonium thiosulfate (70wt / vol%) 6000g Sodium sulfite 110g Sodium acetate ・ trihydrate 450g Nato citrate Um 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulphate 800 g To prepare the developer, add Part A and Part B to about 5 l of water at the same time while stirring and dissolving. Add 12 liters of water and finish with glacial acetic acid.
The H was adjusted to 10.40. This is used as a development replenisher.

20 ml / l of the above-mentioned starter was added to 1 liter of this development replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and Part B to approximately 5 liters of water.
Was simultaneously added, water was added while stirring and dissolving to make 18 l, and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is the fixing replenisher.

The sensitivity was expressed as a relative value with the reciprocal of the exposure energy amount required for sample 1 to give a density of fog + 1.0 as 100. The maximum density is the blackening density obtained when the sample is exposed to light.

(Evaluation of pressure resistance) The obtained sample was left under the condition of 23 ° C. and 40% RH for 2 hours, and then using a continuous load scratch tester (HEIDON-18 type) manufactured by Shinto Scientific Co., Ltd. After rubbing the surface of the sample with a continuous load of 0 to 200 g using a sapphire needle having a diameter of 0.1 mm, the same development processing as above was performed without exposing, and the load at which the blackening density became fog +0.1 was determined. That is, the larger this value, the better the pressure resistance.

(Evaluation of cracks) The obtained sample was 35 mm ×
A blackened sample was prepared by cutting out to a size of 135 mm, exposing it to light, and performing the same development processing as above. Place this in a container filled with silica gel and seal it in an absolutely dry state (~ 0% RH).
It was stored at 45 ° C for 7 days. Cracked sample (length 1
mm or more) was evaluated. It should be noted that under the above storage conditions, it is necessary that even one crack does not occur.

Evaluation: Good: No occurrence X: Occurrence results are shown in Table 1.

[0082]

[Table 1]

As is clear from the results shown in Table 1, the present invention provides a photographic element having improved pressure characteristics and excellent storage stability.

Example 2 The samples Nos. 1 to 12 prepared in Example 1 were subjected to the following treatments to evaluate roller marks and dryness as pressure resistance.

The automatic processor is the SRX-501 used in Example 1.
(Manufactured by Konica Co., Ltd.) which was modified to increase the transportation speed, and the developing solution and the fixing solution were processed under the following conditions using Example 1. The results are shown in Table 2. As for the roller marks, the results of treating under the conditions of Example 1 are also shown.

Development temperature 38 ° C. Fixing temperature 37 ° C. Drying temperature 57 ° C. Replenishment amount Developer 7.0 ml / 10 × 12 inches Fixer 7.0 ml / 10 × 12 inches Total processing time 25 seconds (evaluation of roller mark) Sample 10 × The above process was performed after uniformly exposing the 12-inch size so that the blackening density was 1.0. However, the development rack used at this time,
The transfer rack from development to fixing was intentionally fatigued. That is, the rollers in each rack are fatigued, so about 10
Unevenness of about μm was formed on the entire surface. Due to the pressure caused by this unevenness in the processed sample, many fine spot-like density unevenness occurred in the sample with poor pressure resistance. This level was visually evaluated by the following ranks.

5: No spots are generated 4: Slight spots are generated but no problem in practical use 3: Small amount of spots is generated but an allowable limit level which is not generated in a normal rack 2: Spots are generated And sometimes occurs even in normal racks. 1: Many spots. It is always generated even in normal racks (Evaluation of dryness) The dryness of the sample when 10 × 12 inch samples were continuously processed according to the above-mentioned processing conditions was sensory evaluated by touch on the basis of the following ranks. . However, the environmental conditions of the test were evaluated at 30 ° C and 80% RH assuming a hot and humid place. Further, in the processing of Example 1, the replenishment amount was 14.0% of the developer.
ml / 10 × 12 inch and fixer 14.0 ml / 10 × 12 inch.

The samples were continuously processed so that the short side was in the carrying direction of the processing.

Even at the 3: 30th sheet, the sample was completely dried. There is no problem with the feeling of touching. When the sample is touched at the 2: 30th sheet, it feels slightly cold, but the continuously processed samples do not stick to each other. Practically acceptable level: The sample at the 30th sheet is obviously wet. In some cases, the continuously processed samples are stuck to each other at a level at which they cannot be put to practical use Condition 1: Processing conditions of Example 1 Condition 2: Main processing conditions

[0090]

[Table 2]

As can be seen from the results in Tables 1 and 2, the present invention provides a photographic element having rapid processability, improved pressure characteristics and excellent storage stability.

[0092]

According to the present invention, it is possible to provide a photographic element having high sensitivity, improved pressure characteristics, and excellent storability including rapid processing suitability, film physical properties and photographic performance, and a processing method thereof.

Claims (4)

[Claims] 1. A photographic element having at least one silver halide emulsion layer and a light-insensitive hydrophilic colloid layer on a support, wherein at least one of said emulsion layers contains inorganic fine particles shelled with gelatin. A featured silver halide photographic element. 2. The inorganic fine particles shelled with gelatin have a particle size of 1 to 300 nm, and the main component is silicon oxide,
2. An aluminum oxide, an antimony oxide, a titanium oxide, a zinc oxide, a zirconia oxide, a tin oxide, a vanadium oxide, a yttrium oxide, or a niobium oxide. Silver halide photographic element. 3. The silver halide photographic element according to claim 1, wherein the silver halide grains in the emulsion layer are tabular grains having an aspect ratio of 2 or more. 4. A method of processing a silver halide photographic element, which comprises processing the silver halide photographic element according to claims 1 to 3 in an automatic processor having a total processing time of 15 to 60 seconds.