JPH07261306A - Silver halide photographic element and its processing method - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic element high in sensitivity and improved in pressure characteristics and superior in rapid processing aptitude and preservability by incorporating minute inorganic particles treated with a silane coupling agent in at one of emulsion layers. CONSTITUTION:In the photographic element having at least one silver halide emulsion layer and at least one nonphotosensitive hydrophilic colloidal layer on a support, at least one of the emulsion layers contains the minute inorganic particles treated with the silane coupling agent. The minute inorganic particles are those comprising substantially an inorganic compound including B, Si, Al, Ti, In, Sn, Sb, Zn, Ni, Cu, Fe, Co, Mn, Mo, Nb, Zr, an alkali metal, alkaline earth metal, or/and the like, and the inorganic compound may be the one comprising any of each element or its optional combination or the oxide or phosphate of any of the elements.

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, excellent rapid processing suitability and storability and a processing method thereof.

[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. When the amount of gelatin used is reduced, the silver halide grains with high sensitivity become more and more weak against external pressure, and attempts have been made to improve the grain preparation method to overcome this, but high sensitivity and low fog have been tried. 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 buffering agent for the purpose of improving the pressure characteristics. JP-B-53-28086, Research Disclosure, Volume 195, 1
Issued in July 980, found 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. Although the deterioration of the physical properties of the film is surely small, there is a problem that the film may be cracked when the processed film is preserved after the image formation when added in an amount sufficient to produce the effect.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a silver halide photographic element having high sensitivity, improved pressure characteristics, excellent rapid processing suitability and storability, and a processing method thereof. To do.

[0007]

The above object of the present invention can be achieved by the following constitutions.

1. A photographic element having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, characterized in that at least one layer of said emulsion layer contains inorganic fine particles treated with a silane coupling agent. Silver halide photographic element.

2. 2. The silver halide photographic element as described in 1 above, wherein the silane coupling agent is a compound represented by the following general formula (I) or general formula (II).

General formula (I) Y- (L) n-Si≡ (OR) ₃ (wherein Y is an organic group, L is a divalent linking group, -Si≡ (OR) ₃
Represents an alkoxysilyl group. n represents 0 or 1. )

[0011]

[Chemical 2]

3. 2. The silver halide photographic element as described in 1 or 2 above, wherein the silver halide grains in the silver halide emulsion layer are tabular silver halide grains having an aspect ratio of 2 or more.

4. In a photographic element having at least one silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, at least one of the silver halide emulsion layers contains an inorganic fine particle treated with a silane coupling agent. A method of processing a silver halide photographic element, which comprises processing the silver photographic element in an automatic processor having a total processing time of 15 to 60 seconds.

5. 5. The method for processing a silver halide photographic element as described in 4 above, wherein the silane coupling agent as described in 4 above is a compound represented by the formula (I) or (II).

The present invention will be described in detail below.

The inorganic fine particles of the present invention have an average particle size of 0.005.
The fine particles are substantially composed of an inorganic compound having a particle size of -10 μm, preferably 0.01-0.4 μm. The elements contained in the inorganic compound include boron, silicon, aluminum, titanium, indium, tin, antimony, zinc, nickel, copper, iron, cobalt, manganese, molybdenum, niobium, zirconium, alkali metals, alkaline earth metals and the like. is there. The inorganic compound may be a compound consisting of these elements, or an oxide or phosphate thereof. Preferred compounds include colloidal silica, smectite,
Mica, zeolite, hydroxyapatite, tin oxide,
Examples include antimony oxide.

The inorganic fine particles used in the present invention are preferably used in the form of an aqueous dispersion. As its preparation method,
While stirring a predetermined amount of water with a high-speed stirrer having a sufficient shearing force, for example, a homomixer, an impeller, etc., inorganic fine particles can be added little by little and dispersed, or can be dispersed by further pulverizing with a ball mill. When preparing a dispersion, sodium pyrophosphate, sodium hexametaphosphate, polyphosphates such as sodium tripolyphosphate, trimethylolpropane, trimethylolethane, polyhydric alcohols such as trimethylolmethane, non-polyethylene glycol alkyl esters such as Ionic polymers or hydrophilic polymers such as gelatin, gelatin derivatives or dextrin, cyclodextrin, dextran, polyacrylamide, sodium polyacrylate, sodium polystyrene sulfonate, and acrylamide,
Copolymers containing 5% or more by weight of hydrophilic monomers such as 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid and styrenesulfonic acid, and dispersions of various known ionic and nonionic activators Agents can be added as appropriate.

Further, a nonionic polymer such as polyethylene glycol alkyl ester or a hydrophilic polymer such as gelatin, gelatin derivative or dextrin, cyclodextrin, dextran, polyacrylamide, sodium polyacrylate, sodium polystyrenesulfonate, and Acrylamide, 2-acrylamide-2
-A fine particle dispersion may be prepared by reacting with a copolymer containing 5% or more by weight of a water-soluble monomer such as methylpropanesulfonic acid, acrylic acid or styrenesulfonic acid to synthesize inorganic fine particles. Further, these compounds are commercially available in the form of powder or an aqueous dispersion and can be used.

The silane coupling agent used for the treatment of the above-mentioned inorganic fine particles is a compound having in one molecule both a group reactive with an inorganic substance and a group reactive with or compatible with an organic substance (organic functional group). If anything,
A compound represented by the following general formula (I), or a compound represented by the following general formula (I
Examples thereof include polymer type compounds represented by I).

General formula (I) Y- (L) n-Si≡ (OR) ₃ wherein Y is an organic group, L is a divalent organic linking group, and Si≡ (OR)
₃ represents an alkoxysilyl group. n represents 0 or 1. Examples of Y include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
Examples thereof include carboxyl group, hydroxy group, thiol group, amino group, vinyl group, active vinyl group, epoxy group, ureido group, vinyl sulfone group, N-methylol group and aziridine group. Examples of L include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene oxide group, an amide group, a sulfonamide group, a thioamide group, a thioether group, an ester group and the like. Examples of the substituent include an alkyl group, an alkylene group, an aryl group,
Heterocyclic group, carboxyl group, hydroxy group, thiol group, amino group, vinyl group, active vinyl group, epoxy group,
Examples thereof include ureido group, vinyl sulfone group, N-methylol group and aziridine group. R represents an alkoxide group having up to 12 carbon atoms. Specific examples of the silane coupling agent of the present invention are shown below, but the present invention is not limited thereto.

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

The above-mentioned silane coupling agent is commercially available and can be obtained from, for example, Shin-Etsu Chemical Toray Silicone, Chisso, Nippon Unicar.

As a method for treating the above-mentioned inorganic fine particles with a silane coupling agent, the powder of the inorganic fine particles is directly mixed with the silane coupling agent and stirred, and if necessary, heated, or the aqueous dispersion of the inorganic fine particles is subjected to silane coupling. Any of a method of adding an agent and stirring, and optionally heating, and a method of directly adding an aqueous dispersion of inorganic fine particles and a silane coupling agent to the coating liquid may be used. Treatment with a coupling agent gives better results.

The amount of the silane coupling agent added to the inorganic fine particles varies depending on what is used, but is preferably 0.2 to 20% by weight of the inorganic fine particles, more preferably 0.5 to 10%.
% By weight.

The inorganic fine particles used in the present invention are preferably used in a dry weight ratio of 0.05 to 1.0, particularly preferably 0.1 to 0.7, based on the gelatin used as the binder of the layer to be added. 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.

The total hydrophilic binder content of all layers on one side of the support is preferably 3.0 g / m ² or less, more preferably 2.5 g / m ² or less. However, the hydrophilic binder in the present invention,
It means a hydrophilic colloid substance such as a natural or synthetic hydrophilic polymer such as gelatin, dextran, dextrin, polyacrylamide.

As the silver halide used in the silver halide photographic element of the present invention, tabular grains are preferably used in order to obtain high sensitivity. AgBr as the silver halide composition,
AgCl, AgClBr, AgClBrI, AgBrI, AgClBrI and the like can be arbitrarily used, but 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 silver halide 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 when the proportion of tabular silver halide grains is
Increasing the ratio from 60% to 70%, and further to 80% gives preferable results. The aspect ratio as used herein means the ratio of the diameter of a circle having the same area as the projected area of tabular silver halide 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 silver halide grains of the present invention preferably have a thickness of 0.5 micron or less, preferably 0.3 micron or less. Also, the distribution of tabular silver halide grains has a coefficient of variation that is 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).
It is preferably a monodisperse emulsion having a content of 30% or less, particularly 20% or less. Further, two or more kinds of tabular silver halide grains and normal crystal non-tabular silver halide grains may be mixed.

In order to control the growth of tabular silver halide grains during the formation thereof, a silver halide solvent such as ammonia, a thioether compound or a thione compound can be used. Further, metal salts such as zinc, lead, thallium, iridium and rhodium can be made to coexist during physical aging and chemical aging.

In the case of chemical sensitization, ordinary sulfur sensitization,
Reduction sensitization, precious metal sensitization and combinations thereof are used. More specific chemical sensitizers include allyl thiocarbamide, thiourea, thiosulfate, sulfur sensitizers such as thioether and cystine, selenium sensitizers such as selenourea, potassium chloroaurate, and auras. Precious metal sensitizers such as thiosulfate and Potassium chloropalladate; reduction sensitizers such as tin chloride, phenylhydrazine and reductone can be mentioned.

The sensitizing dye to be used in the present invention may be added at any time during the formation of silver halide grains and after the formation, but before the desalting step is preferable. 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. Ultrasonic waves can also 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
Is preferred.

The surface layers of the silver halide photographic elements of the present invention can be used as slip agents in US Pat. Nos. 3,489,576 and 4,047,958.
In addition to the silicone compound described in JP-A-56-23139 and the colloidal silica described in JP-B-56-23139, paraffin 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 silver halide photographic element of the present invention.

Further, the constituent layers of the silver halide 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. As a desirable example of the monomer having a water-soluble group,
Acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic 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 etc.

When the silver halide photographic element of the present invention is used as a medical double-sided emulsion X-ray sensitive material, 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 those soluble in alkalis having a pH of 9 or higher and pH 7
The dye is not particularly limited as long as it is a dye having a poorly soluble structure, but the compound of the general formula (I) described in Japanese Patent Application No. 5-119113 is preferably used because of its good decolorizing property during development processing.

The silver halide photographic elements of this invention exhibit excellent performance in rapid development processing by automatic processors with total processing times of 15 to 60 seconds. In the rapid processing of the silver halide photographic element of the present invention, the temperature and time for developing, fixing, etc. are about 25-50.
25 seconds or less for each, preferably 30-40 ℃ 4 ~
15 seconds. The silver halide photographic element of the present invention is developed, fixed and 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 silver halide photographic element which has been developed, fixed and washed with water 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 emulsion layers and protective layers without impairing the pressure characteristics, so that the total processing time is 15-60 seconds in a rapid processing. Development processing can be carried out without impairing the development speed, the fixing speed, and the drying speed, but the effect is remarkable when the total processing time is 35 seconds or less.

[0047]

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

Preparation of Inorganic Fine Particles of the Present Invention Inorganic fine particles (R-1) Colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd.) in an aqueous dispersion, a silane coupling agent I-8 was added to the solid content of the colloidal silica. 2% by weight, and after thorough stirring and mixing, the mixture was heat treated in a closed system at 90 ° C. for 5 hours while continuing stirring to obtain the desired product.

Inorganic fine particles (R-2) Colloidal silica (Snowtex U manufactured by Nissan Kagaku Co., Ltd.)
To the aqueous dispersion of P), 3% by weight of the silane coupling agent II-1 was added to the solid content of colloidal silica, and the mixture was sufficiently stirred and mixed, and then heat-treated in a closed system at 90 ° C for 5 hours while continuing stirring. I got a thing.

Inorganic fine particles (R-3) To a powder of synthetic smectite (Lucentite SWN manufactured by Coop Chemical Co., Ltd.), 1% by weight of the stock solution of the silane coupling agent I-6 was added to the solid content of smectite, and the mixture was sufficiently mixed. After kneading, heat treatment was carried out at 120 ° C. for 3 hours. 2% by weight of pure water and sodium dodecylbenzenesulfonate as a dispersion stabilizer were added to the mixture, and the mixture was uniformly dispersed by a homogenizer to obtain a 10% aqueous dispersion.

Next, the seed emulsion used in the examples and the method for preparing the emulsion will be described.

(Preparation of Seed Emulsion 1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml KBr 10.8 g 10% nitric acid 114 ml B1 2.5N AgNO ₃ aqueous solution 2825 ml C1 KBr 824 g KI 23.5 g 2825 ml of D1 1.75N KBr aqueous solution with water At the following silver potential control amount of 35 ° C., a solution A1 was added to solution B1 and solution C1 using a mixing stirrer disclosed in Japanese Patent Publication Nos. 58-58288 and 58-58289.
Nucleation was carried out by adding 464.3 ml of each of the above by the simultaneous mixing method over 2 minutes.

After stopping the addition of the solutions B1 and C1, 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 added by the double jet method at a flow rate of 55.4 ml / min each for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 35 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mv using the solution D1. And was controlled to be +16 mv.

After the addition was completed, 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 consists of 2.0 hexagonal tabular grains. The average thickness of hexagonal tabular grains is 0.06μm, the average diameter (circle diameter conversion) is 0.59μm, the variation coefficient of thickness is 25%, the variation coefficient of the distance between twin planes is 29%. It was confirmed with an electron microscope.

Preparation of Em-1 A tabular emulsion having a core / shell structure was prepared by using 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 0.15 mol equivalent 550 ml with water B2 ossein gelatin 5.9 g potassium bromide 5.0 g iodine Potassium bromide 2.5g Water 145ml C2 silver nitrate 10.1g Water 145ml D2 ossein gelatin 6.1g Potassium bromide 94g Water 304ml E1 Silver nitrate 137g Water 304ml Vigorous stirring of solution A2 and solution B2 by double jet method And C2 solution were added in 58 minutes. Next, in the same liquid, D2
Solution and E1 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 the addition is complete, in order to remove excess salts, Demol (made by Kao Atlas)
Precipitation desalting was carried out using an aqueous solution and an aqueous magnesium sulfate solution to obtain an emulsion having an average silver iodide content of pAg 8.5 and pH 5.85 of about 1.6 mol% at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that the average grain size was 0.96 μm, the grain size distribution was 18%, and 81% of the projected area was from the {111} plane and the {100} plane. It was a tabular silver halide grain. The ratio of {111} planes to {100} planes in the tabular silver halide grains was 86:14.

The tabular silver halide grains had a distribution width of 15% and an aspect ratio of 4.5.

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

A3 ossein gelatin 100 g potassium bromide 2.05 g with water 11.5 l B3 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2 N sulfuric acid 38.5 ml water 2.6 l C3 ossein gelatin 75 g potassium bromide 950 g 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 B3 and D3 to control solution A3 kept at 60 ° C over 30 minutes. Then, the C3 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 treatment was carried out by the method described in JP-B-35-16086 in order to remove excess salts.

Observation of this seed emulsion with an electron microscope revealed that 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.

A4 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 B4 ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g 110 ml with water C4 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 ml G1 Silver nitrate 9.9 g Ammonia water (28%) 110 ml A4 solution was kept at 40 ° C. with 7.0 ml water and stirred at 800 rpm with a stirrer.
The pH of solution A4 was adjusted to 9.90 with acetic acid, seed emulsion-3 was sampled 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 B4 and solution D4 were simultaneously added 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 C4 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. or,
The pH was decreased from 8.83 to 8.00 in proportion to the flow rate ratio. Further, when the C4 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,
14 with a rounded aspect ratio of 1.0 with an average grain size of 0.40 μm and an average silver iodide content of 2 mol% and a grain size distribution of 14%
A surface monodisperse core / shell type emulsion was obtained.

With each emulsion thus obtained kept at 50 ° C., an AgI fine grain emulsion having an average particle size of 0.06 μm was added per mol of silver.
After adding 6.0 × 10 ^-4 mol, 360 mg of the following sensitizing dye (A)
/ Mol Ag and (B) 3.6 mg / mol Ag were added, and then ammonium thiocyanate was added at 7.0 × 10 ⁻⁴ per mol of silver.
4-Hydroxy-6-methyl-1,3,3, chemical sensitization was performed by adding chloroauric acid and an appropriate amount of sodium thiosulfate.
Stabilization was performed at 1.0 × 10 ^-2 mol per mol of 3a, 7-tetrazaindene silver.

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 anhydride (preparation of sample) 1st layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180mg / M ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Second layer (emulsion layer) Compound (G) 50 mg / m ² t in which the following various additives are added to each emulsion obtained above. -Butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 350 mg / m ² Styrene-maleic anhydride copolymer 800 mg / m ² trimethylolpropane 350 mg / m ² Diethylene glycol 500 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-sulfonic acid sodium 0.5 mg / m ² compound (H) 25 mg / m ² n-C ₄ H ₉ OCH ₂ C H (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Sodium pyrophosphate 30 mg / m ² Inorganic fine particles of the present invention Latex (L) 0.3 g / m ² Dextrin (average molecular weight 1,000) 0.2 g / m ² However, the gelatin was prepared to be 0.8 g / m ² .

Third Layer (Protective Layer) Gelatin 0.8 g / m ² Polymethylmethacrylate matting agent (area average particle size 7.0 μm) 10 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy- 1,3,5-Triazine sodium salt 30 mg / m ² Bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.5 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² polysiloxane (S1) 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) 15 mg / m ² compound (S-2) 5 mg / m ² C _{9 F 19 -O- (CH 2 CH 2} O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) [(CH 2 CH 2 O) 15 -H] 2mg / m 2

[0071]

[Chemical 6]

[0072]

[Chemical 7]

The above coating solution was applied on both sides of a 175 μm thick polyethylene terephthalate support, which had been subjected to a subbing treatment and which had been subjected to an undercoating treatment, from below to form a transverse light-shielding layer, an emulsion layer, and an emulsion protective layer, which were simultaneously layered and dried. As shown below,
Created 7.

The amount of the material applied was for one side, and the coating silver amount was adjusted to be 1.5 g / m ² for one side.

1) Evaluation of Sensitivity The obtained sample was sandwiched between intensifying screens for X-ray photography KO-250, irradiated with X-rays through a penetrometer type B, and then a roller transport type automatic processor (SRX-501: Konica ( (Produced by K.K.) was used to perform rapid processing under the following conditions with a developer and a fixer having the following compositions.

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 finishing) Ammonium thiosulfate (70wt / vol%) 6000g Sodium sulfite 110g Sodium acetate ・ trihydrate 450g Na citrate Thorium 50g Gluconic acid 70g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Part-B (for 18l finishing) Aluminum sulfate 800g To prepare the developer, add Part A and Part B to approximately 5l of water at the same time. , Add water while stirring and dissolve to make 12l p with glacial acetic acid
The H was adjusted to 10.40. This is used as a development replenisher.

20 ml / l of the aforesaid starter was added to 1 liter of this developer replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part-A and Part- to approximately 5 liters of water.
B was added at the same time, 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 amount of exposure energy required for Sample 1 to give a density of fog + 1.0 as 100.

2) Evaluation of pressure resistance After leaving the obtained sample under conditions of 23 ° C. and 40% RH for 2 hours, continuous load scratch tester (HEIDON-18 manufactured by Shinto Kagaku Co., Ltd.)
Mold) and rubbing the surface of the sample with a continuous load of 0-200 g with a sapphire needle with a diameter of 0.1 mm, and then performing the same development processing as above without exposing it, and applying a load at which the blackening density becomes fog +0.1. I asked. That is, the larger this value, the better the pressure resistance.

3) Evaluation of cracks The obtained sample was cut into a size of 35 mm × 135 mm, exposed to light and subjected to the same development treatment as above to prepare a blackened sample. This was put in a container containing silica gel, hermetically sealed, and stored in an absolutely dry state (∼0% RH) at 30 ° C for 7 days. The presence or absence of cracks (having a length of 1 mm or more) in the stored samples was evaluated. It should be noted that under the above storage conditions, it is necessary that even one crack does not occur.

Evaluation ◯: No occurrence X: Occurrence results are shown below.

[0083]

[Table 1]

Comparison a: Colloidal silica (Nissan Chemical Co., Ltd.)
Snowtex C) As is clear from the above results, the sample of the present invention provides a silver halide photographic element having high sensitivity, improved pressure characteristics, and excellent storage stability, and the silver halide photograph is rapidly produced. It can be seen that the processability is excellent.

Example 2 Sample Nos. 1 to 6 prepared in Example 1 were subjected to the following treatments to evaluate the roller mark as the pressure resistance and the dryness.

The automatic processor is the SRX-501 used in Example 1.
(Konica Co., Ltd.) was modified to increase the transport speed, and the developing solution and 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.

[0087] Evaluation of Roller Mark The sample was uniformly exposed in a size of 10 × 12 inches so that the blackening density was 1.0, and then the above treatment was performed. However,
The developing rack used at this time and the developing rack used for fixing were those which were intentionally fatigued. That is, due to fatigue of the rollers of each rack, unevenness of about 10 μm was formed on the entire surface. Due to the pressure caused by the unevenness in the processed sample, many fine spot-like concentration rams were generated in the sample having poor pressure resistance.

This level was visually evaluated by the following ranks.

5 No spots are generated 4 A few spots are generated, which is not a problem in practical use 3 A few spots are generated, but an allowable limit level 2 which is not usually generated in a rack 2 spots are usually generated Occasionally occurs on racks 1 Many spots occur. Evaluation of dryness that is always generated even in a rack A sensory evaluation was performed on the dryness of a sample when 10 × 12 inch samples were continuously processed according to the above-mentioned processing conditions by touching the following ranks. However, the environmental conditions of the test were evaluated at 30 ° C. and 80% RH, assuming a hot and humid place.

The samples were continuously processed with the short side being the carrying direction of the processing.

Even after the 30th sheet, the sample was completely dried. There is no problem with the feeling of touching. 2 When the sample is touched on the 30th sheet, it feels slightly cold, but the continuously processed samples do not stick to each other. Practically acceptable level 1 The sample is obviously wet when it is touched. Depending on the case, the level at which the continuously processed samples stick to each other and cannot be put to practical use is shown below.

[0092]

[Table 2]

As is clear from Table 2, the samples of the present invention are
It can be seen that a silver halide photographic element having excellent suitability for rapid processing of 35 seconds or less, improved pressure characteristics, and excellent storage stability can be obtained.

[0094]

INDUSTRIAL APPLICABILITY The silver halide photographic element and its processing method according to the present invention have high sensitivity, improved pressure characteristics, and excellent processing suitability and storage stability.

Claims (5)

[Claims] 1. A photographic element having at least one silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, wherein at least one layer of the emulsion layer contains inorganic fine particles treated with a silane coupling agent. A silver halide photographic element characterized in that 2. The silver halide photographic element according to claim 1, wherein the silane coupling agent is a compound represented by the following general formula (I) or general formula (II). General formula (I) Y- (L) n-Si≡ (OR) ₃ (wherein Y is an organic group, L is a divalent linking group, -Si≡ (OR) ₃
Represents an alkoxysilyl group. n represents 0 or 1. ) [Chemical 1] 3. The silver halide photographic element according to claim 1, wherein the silver halide grains in the silver halide emulsion layer are tabular silver halide grains having an aspect ratio of 2 or more. 4. A photographic element having at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, wherein at least one layer of the silver halide emulsion layer is an inorganic fine particle treated with a silane coupling agent. A method of processing a silver halide photographic element, which comprises processing the silver halide photographic element containing the above with an automatic processor having a total processing time of 15 to 60 seconds. 5. The processing of a silver halide photographic element according to claim 4, wherein the silane coupling agent according to claim 4 is a compound represented by the general formula (I) or (II). Method.