JPH0792596A - Silver halide photographic sensitive material and its development processing method - Google Patents

Abstract

PURPOSE:To provide a silver halide photosensitive material high in sensitivity, and low in generation of the roller mark at the time of a high speed processing. CONSTITUTION:(1) In the silver halide photographic sensitive material having at least one layer of photosensitive silver halide emulsion layer on at least one side of a supporting body, the iron content in the gelatin incorporated in the emulsion layer is <=3.0 microgram per 1g gelatin and the average silver iodide content of the emulsion is <=3mol.%. (2) In a development processing method, above mentioned material is processed at <=35sec total processing time (Dry to Dry).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for developing the same, and more specifically, with high sensitivity,
Moreover, the present invention relates to a silver halide photographic light-sensitive material in which roller marks are less likely to occur during rapid processing and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, consumption of silver halide photographic light-sensitive materials has been increasing. For this reason, the number of silver halide photographic light-sensitive materials developed has increased, and there has been a strong demand for rapid processing. Even in the processing of an automatic processor, the processing time has been greatly shortened. For example, in the case of a roller-conveying type automatic developing machine, there is a method of increasing the roller-conveying speed in order to shorten the developing treatment time (comprising each step of developing, fixing, washing and drying). However, if the conveyance speed of the roller is increased, the photographic performance such as sensitivity, contrast and maximum density is deteriorated, and the film is insufficiently dried. In this case, a sufficient amount of a hardener may be added in advance in the step of coating the light-sensitive material to reduce the swelling amount of the emulsion layer or the surface protective layer during processing to accelerate the drying speed. Not only the performance is further deteriorated, but also roller marks are easily generated during processing.

On the other hand, in general, silver iodobromide emulsion has higher sensitivity than pure silver bromide emulsion, but has a drawback that roller marks are easily generated. This is considered to be due to the infectious development effect of iodine ions released during development, but the detailed mechanism is not clear.

[0004]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide light-sensitive material having high sensitivity and less generation of roller marks during rapid processing.

[0005]

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

In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, the content of iron in gelatin contained in the emulsion layer is 3.0 micrograms per gram of gelatin. A silver halide photographic light-sensitive material characterized in that the average silver iodide content of the emulsion is 3.0 mol% or less.

A development processing method characterized in that the silver halide photosensitive material is processed in a total processing time (Dry to Dry) of 35 seconds or less.

The present invention will be specifically described below.

The gelatin used in the present invention will be described.

First, the method for producing gelatin according to the present invention will be described.

The method for producing gelatin according to the present invention can be used, and it is described in detail, for example, in "Basic Silver Salt Photographs in Photographic Engineering" edited by The Photographic Society of Japan (Corona Corp.), pages 122-124.

The gelatin according to the present invention is produced from collagen, which is the main component of animal tissue. Examples of raw materials for photographic gelatin include cow bone, pig skin, and fish skin, but cow bone and cow skin are generally used.

There are two types of collagen treatment methods, an acid treatment method and a lime treatment method, but the lime treatment method is generally used as photographic gelatin, and the gelatin according to the present invention is also lime treated. Is preferred.

As an example, when gelatin is produced from beef bone by lime treatment, the production process is usually decalcification,
Lime treatment, extraction, filtration, concentration, gelation, and drying are performed in this order.

Minerals account for more than half of the decalcified and dried bovine bone, most of which is calcium phosphate. This is removed using dilute hydrochloric acid, leaving ossein, which is based on insoluble collagen. In order to reduce the hydrolysis loss of ossein by acid, the concentration of dilute hydrochloric acid is about 5% and the temperature is 15 ° C.
It is preferable to perform the treatment for about 4 to 7 days while keeping the temperature for about 4 to 7 days.
The decalcified ossein gelatin is thoroughly washed with water to remove excess acid, and neutralized with caustic soda at about 0.5 ° C or a lime suspension at about 0.5%.

The ossein removed by lime treatment decalcification is dipped in a suspension of 2-5% slaked lime for 70-100 days. This treatment changes the structure and chemical composition of collagen to form gelatin.

After the lime treatment, washing with water is performed for about 24 hours to remove lime. After that, neutralize with dilute hydrochloric acid of about 0.05 N for about 24 hours, and wash again with water for about 24 to 48 hours to perform a predetermined extraction p.
Set to H.

The raw material after the alkali extraction treatment is first immersed in warm water at an arbitrary temperature to extract gelatin. The extraction rate of gelatin depends on the pH and temperature at this time, but the immersion liquid is taken out as the first extraction solution when the extraction rate is lowered. Next, hot water having a temperature of 5 to 10 ° C. higher than that in the first extraction is added to the extraction residue to perform the second extraction.
After that, extraction is performed with hot water of high temperature successively and a total of about 5 to 6 times are performed. When used as photographic gelatin, it is preferable to select an appropriate extraction temperature according to the purpose.

The filtered extract gelatin solution, the impurities were filtered with a filter press to filter media cellulose pulp, increasing the transparency.

The gelatin solution after concentration and filtration can be concentrated to shorten the time and cost in the subsequent gelation and drying steps. Generally, the concentration is carried out at a temperature of 60 ° C. or lower to about 15 to 24% by using evaporation under reduced pressure.

The gelatin solution after gelling and drying and concentration is cooled, gelled, and shredded into an appropriate shape and size.
Then, it is dried by air drying. In order to prevent the melting of gelatin and shorten the drying time, it is preferable to use low-temperature air in the early stage of drying and then to dry it using air with a higher temperature.

Although alkali-treated gelatin has been described above, alkali-treated gelatin or acid-treated gelatin is used in the present invention, and modified gelatin typified by phthalated gelatin may be used.

The gelatin used in the emulsion layer of the present invention is deionized with an ion exchange resin or the like, and the iron content is 3.0 micrograms or less, preferably 2.0 micrograms or less, and more preferably 1 microgram per gram of gelatin. , Which has been processed so as to be 1.2 micrograms or less.

The iron content can be quantified by an analytical method represented by an atomic absorption method.

The gelatin according to the present invention can be subjected to hydrogen peroxide treatment as well as ion exchange treatment.

The gelatin of the present invention can produce the effects of the present invention by being used in all steps of the process for producing the light-sensitive material of the present invention, but preferably, it is used in the step of preparing an emulsion. is there.

The silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention includes normal crystal grains, that is, all isotropically grown grains such as cubes, octahedrons and tetrahedrons, or spherical grains. It may be a polyhedral crystal type or a twin crystal having plane defects such as twin planes, or a mixed type or a composite type thereof, but tabular silver halide grains are preferable. Is mentioned.

The grain size of these silver halide grains is 0.2 μm.
To 3.0 μm is preferable, and 0.3 μm to 2.0 μm is more preferable.

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

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
"Chimie et Physique Photographique" by P. Glafkides
Published by aul Montel (1967) or VL Zelikman et al. “Making
It can be prepared by the method described in And Coating Photographic Emulsion "Focal Press (1964).

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

The grain size distribution of the silver halide grains of the present invention is
Either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution may be used, and these may be used in combination. The crystal structure of silver halide may have different silver halide compositions inside and outside. For example, a core part of high silver iodide is coated with a shell layer of low silver iodide to form a clear two-layer structure. Or a core / shell type monodisperse emulsion having a structure of three or more layers in which shell layers having different silver iodide contents are provided.

The silver iodide content in the high iodine portion is 20 to 40 mol%,
Particularly preferably, it is 20 to 30 mol%. In the present invention, monodisperse means that the value (variation coefficient) obtained by dividing the variation (standard deviation) of particle diameter by the average particle diameter by 100 and showing as% is preferably within 30%, more preferably 20 Say it is within%.

The silver halide emulsion according to the present invention may have any halogen composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, etc., but it is highly sensitive to iodobromide. Silver is preferred, and the average silver iodide content is 3.0 mol% or less, particularly preferably 1.0 mol% or less.

A method for producing such a monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like. As a method for obtaining the above monodisperse emulsion, for example, a seed crystal may be used, and an emulsion obtained by supplying silver ions and halide ions to grow the seed crystal may be used. The production method of the above core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), British patent.
The methods described in 1,027,146, U.S. Pat. Nos. 3,505,068, 4,444,877, and JP-A-60-143331 can be referred to.

The average grain size of the tabular silver halide grains preferably used in the present invention is preferably 0.3 to 3.0 μm, particularly preferably 0.5 to 1.5 μm.

The tabular silver halide grains according to the present invention are
The average value of particle diameter / thickness (called aspect ratio) (called average aspect ratio) is 2.0 or more, preferably 2.0
˜20.0, particularly preferably 2.2 to 8.0.

The average thickness of the tabular silver halide grains according to the present invention is preferably 0.5 μm or less, particularly preferably 0.3 μm.
It is the following.

The advantage of such tabular grains is that the spectral sensitization efficiency can be improved and the graininess and sharpness of images can be improved. For example, British Patent 2,112,157 and US Pat.
No. 20, No. 4,433,048, No. 4,414,310, No. 4,434,226, etc., and the emulsion can be prepared by the method described in these specifications.

In the present invention, the grain size of tabular silver halide grains is defined as the diameter of a circle having an area equal to the projected area of the grain from the observation of an electron micrograph of silver halide grains.

In the present invention, the thickness of a silver halide grain is defined as the minimum distance between two parallel planes constituting a tabular silver halide grain, that is, the distance between principal planes.

The thickness of the tabular silver halide grains can be determined from an electron micrograph of a silver halide grain shaded or an electron micrograph of a sample slice obtained by coating a support with a silver halide emulsion and drying. .

To obtain the average aspect ratio, the minimum
Measure 100 samples.

When a tabular silver halide emulsion is used in the silver halide emulsion of the present invention, the tabular silver halide grains account for 50% or more of the total silver halide grains, preferably 60% or more. , Particularly preferably 70% or more.

The tabular silver halide emulsion according to the present invention is preferably one which is monodisperse, and one in which the variation coefficient of grain size is within the range of 20% is particularly preferably used.

The method for producing the tabular silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like.

Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halide are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

The size and formation of tabular silver halide grains can be controlled by the temperature at the time of grain formation, silver potential, pH, addition rate of aqueous solution of silver salt and halide.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of chloride bromide and iodide.

When the tabular silver halide emulsion is produced,
If necessary, a silver halide solvent such as ammonia, thioether or thiourea can be used.

The above-mentioned emulsions are either surface latent image type that forms a latent image on the grain surface, internal latent image type that forms a latent image inside the grain, or type that forms a latent image on the surface and inside. You may. These emulsions may be prepared by using an iron salt, a cadmium salt, a lead salt, a zinc salt, a thallium salt, a ruthenium salt, an osmium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof at the stage of physical ripening or grain preparation. Good.

The emulsion may be subjected to a water washing method such as a Nudel water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
Particularly preferable desalting method is a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A-35-16086 or a method using G3, G8, etc., as an aggregation polymer agent described in JP-A-63-158644. Can be mentioned.

The silver halide emulsion of the present invention is preferably chemically sensitized.

As the sensitizing method of the silver halide emulsion according to the present invention, it is preferable to use chalcogen sensitization and gold sensitization together. Particularly, the combined use of gold sensitization and sulfur sensitization is preferable because not only the sensitizing effect is remarkable but also the fog suppressing effect is obtained.

For sulfur sensitization, sensitizers such as thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine can be used. Other U.S. Patents 1,574,944
No. 3,656,955, German Patent 1,422,869, Japanese Patent Sho 56
The sulfur sensitizers described in JP-A-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can be varied over a wide range under various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide.

For gold sensitization, gold sensitizers such as chloroauric acid salt, gold thiourea complex salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric amide, ammonium auro are used. Examples thereof include thiocyanate and pyridyl trichlorogold. The addition amount of these gold sensitizers can be varied over a wide range under various conditions, but as a guide, it is 5 × 10 ^{-7 to} 5 per mol of silver halide.
It is preferably ^{x10 -3} mol, more preferably 2x10 ^-6 to 4x10 ^-4 mol.

In the present invention, reduction sensitization and hydrogen sensitization methods can be used. Stannous salt as a reduction sensitizer,
Amines, formamine disulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives can be used.

The addition amount of the reduction sensitizer varies depending on the reducibility of the compound and the emulsion production conditions such as the type of silver halide and the dissolution conditions, but it is 1 × 10 ^-8 to 1 × per mol of silver halide.
A range of 10 ^-2 mol is suitable.

Further, in the present invention, selenium sensitization can be performed, and selenium sensitization can be used in combination with other sensitization methods.

Here, the selenium sensitization is carried out by a conventionally known method. That is, it is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time.

As the selenium sensitizing method, selenium sensitization using an unstable selenium sensitizer described in JP-B-44-15748 is preferably used. As a specific unstable selenium sensitizer,
There are aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates. Particularly preferred unstable selenium compounds are shown below.

Colloidal Metal Selenium Organic Selenium Compound (Selenium Atom Double Bonded to Carbon Atom of Organic Compound by Covalent Bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanates b. Selenoureas (including enol type) For example, selenoureas, and methyl, ethyl, propyl,
Isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (βcarboxyethyl) -N, N'-
Aliphatic selenoureas such as dimethyl, N, N-dimethyl, diethyl, dimethyl, etc .; Aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl, etc .; Heterocycles having heterocyclic groups such as pyridyl, benzothiazolyl, etc. Cyclic selenoureas.

Particularly preferred selenoureas are N, N′-
It is a 4-substituted selenourea. Preferred substituents are R, RC
O-, ArCO-, R is an alkyl group or a perfluoroalkyl group (C number of 1 to 7 is preferable),
Ar is halogen or a phenyl group which may be substituted with a lower alkoxy group.

C. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to = C = Se, selenobenzophenone, d. Selenoamides For example, selenoamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl
-3-Selenobutyrate Other a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates For example, preferred types of tri-p-triselenophosphate, tri-n-butylselenophosphate labile selenium compounds are mentioned above, but these are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used.

Selenium sensitization using the non-labile selenium sensitizers described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles,
Diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-selenooxazolidinedione and derivatives thereof are included.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also effective.

The chemical ripening temperature of the emulsion according to the present invention is arbitrarily determined, but it is preferably in the range of 20 to 90 ° C, preferably 30 to 80 ° C, and more preferably 35 to 70 ° C.

In order to stop the chemical sensitization (chemical ripening) in the present invention, a method using a chemical ripening stopper is preferable in consideration of the stability of the emulsion. Examples of the chemical aging inhibitor include halides (eg potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene, etc.) is known. These are used alone or in combination of a plurality of compounds.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978),
No. 18716 (November 1979) and No. 308119 (December 1989)
Month). The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Supports that can be used in the light-sensitive material of the present invention include, for example, RD-17643, page 28 and RD-308119, 100.
Examples include those described on page 9.

A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, or ultraviolet irradiation in order to improve the adhesion of the coating layer.

The silver halide emulsion according to the present invention has a total processing time (dry t) from the start of development to the fixing, washing, and drying.
o Dry) is preferably 35 seconds or less.

The developing temperature is 18 to 50 ° C., particularly 30 to 45
℃ is preferable, and the developing time is from 6 seconds to 15
Seconds are preferred.

Development processing in the present invention is carried out according to US Pat.
No. 25779, No. 3515556, No. 3573914, No. 3647459
It is preferable to use a roller-conveying type automatic developing machine described in Japanese Patent No. 1269268 and the like.

[0076]

EXAMPLES Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

(Preparation of seed emulsion Em-1) [Solution A] Water 11.5l Potassium bromide 2.05g Ossein gelatin 100g [Solution B] Water 2.6l Potassium bromide 65g Potassium iodide 1.8g Ossein gelatin 55g 0.2N Sulfuric acid 38.5cc Water C 3.0 g Potassium bromide 950 g Potassium iodide 27 g Ocein gelatin 75 g [D liquid] Water 2.7 l Silver nitrate 95 g [E liquid] Water 3.2 l Silver nitrate 1410 g Put solution A in a reaction kettle at 60 ° C. The solution was kept warm and the other solution was added at 23 ° C. At this time, the solutions B and D were added by the control double jet method over 30 minutes, and then the solutions C and E were added by the control double jet method over 105 minutes. The stirring was performed at 500 rpm. The flow velocity is increased in proportion to the total surface area of the silver halide grains as the grains grow, new growth nuclei do not occur when the additive liquid flows in, and so-called Ostwald ripening occurs, resulting in a grain size distribution. Was added at a flow rate that did not spread. 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 using sulfuric acid.
It was adjusted to 0 ± 0.1.

After the addition was completed, the pH was adjusted to 6.0, and in order to remove excess salts, precipitation and desalting were carried out using an aqueous solution of demole (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, and additional gelatin was added.

The obtained emulsion had a grain size of 0.30 μm, {111}
The tetrahedral monodisperse grains were in the shape of a cube having 5% of the plane and the other of which were composed of {100} planes and the corners were slightly chipped and the silver iodide content was 2 mol%. This emulsion is designated as seed emulsion Em-1.

(Growth of Seed Emulsion) First, the following solutions were prepared. All amounts are given per mol of silver halide.

[Liquid J (reaction mother liquor)] Ocein gelatin 10 g Concentrated ammonia water 28 ml Glacial acetic acid 3 ml Water 600 ml [K liquid] Potassium bromide 5 g Potassium iodide 3 g Ocein gelatin 0.8 g Water 110 ml [L liquid] Odor Potassium iodide 90 g Ocein gelatin 2.0 g Water 240 ml [M liquid (0.75N)] Silver nitrate 9.9 g 28% ammonia solution 7.0 ml Water 110 ml [N liquid] Silver nitrate 130 g 28% ammonia water 100 ml Water 240 ml [O liquid] Odor Potassium iodide 94 g Water 165 ml [P liquid] Silver nitrate 9.9 g 28% aqueous ammonia solution 7.0 ml Water 110 ml J liquid was kept at 40 ° C. and stirred at 800 rpm with a stirrer. J
The pH of the solution was adjusted to 9.90 with acetic acid, and seed emulsion E was added to this.
0.119 mol of m-1 was collected per mol of silver halide and dispersed and suspended. Then, P liquid was added at a constant rate over 7 minutes to adjust pAg to 7.3. In addition, K liquid and M liquid can be used simultaneously
Added over minutes. At this time, pAg was fixed at 7.30.
In addition, using potassium bromide solution and acetic acid over 10 minutes
After adjusting the pH to 8.83 and the pH to 9.0, the L solution and the N solution were simultaneously added over 30 minutes. At this time, the inflow rate ratio at the start of addition and the end of addition was 1:10, and the flow rate was increased with time. In addition, the pH is adjusted from 8.83 to 8.0 in proportion to the inflow.
It was reduced to 0. In addition, when the L liquid and the N liquid were added by ⅔ of the total amount, the O liquid 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. Next, in order to remove excess salts, Demol (made by Kao Atlas)
Precipitation desalting is performed using an aqueous solution and an aqueous magnesium sulfate solution to remove excess salt, and additional gelatin is added to give an emulsion EM.
-1 was obtained.

The grains have an average silver iodide content of 2.6 mol%.
It was a monodisperse silver iodobromide emulsion having a rounded tetradecahedral type with an average grain size of 0.64 μm and a variation coefficient of 16%.

(Chemical sensitization of emulsion) Emulsion EM-1 obtained
1 mol of silver was taken and 210 mg and 1.5 mg of the following spectral sensitizing dyes (a) and (b) were added while stirring at a temperature of 48 ° C. Twenty minutes after the addition of the sensitizing dye, 52 mg of ammonium thiocyanate, 1.56 mg of chloroauric acid, and 14 mg of sodium thiosulfate were added as chemical sensitizers.

Then, 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene and 1-phenyl-5-mercaptotetrazole were added for stabilization and optimal chemical sensitization.

Then, ion-exchange treatment was performed to add gelatin having an iron content changed to 74 g per 1 mol of silver of the emulsion EM-1 as additional gelatin and set.
These gelatins are shown in Tables 1 and 2.

Sensitizing dye (a) 5,5-dichloro-9-ethyl-
3,3'-Di- (3-sulfopropyl) oxacarboxycyanine sodium salt sensitizing dye (b) 5,5-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di Anhydrous of-(4-sulfobutyl) benzimidazolocarbocyanine sodium salt.

(Preparation of Emulsion EM-2) Next, the potassium iodide in the solution K was removed and the amount of potassium bromide was adjusted to 7.2 g.
EM-1 except that pAg at the time of simultaneous addition of the solution was adjusted to 9.0
Emulsion EM-2 was prepared in exactly the same manner as in. Observation with a scanning electron microscope revealed that the particle shape of EM-2 was EM.
It was equivalent to -1.

Further, this EM-2 was chemically sensitized by the same method as that of EM-1.

(Preparation of Hexagonal Tabular Twin Crystal Seed Emulsion Em-2) A hexagonal tabular seed emulsion was prepared by the following method.

[0090] [A _2] ossein gelatin 24.2g Distilled water _{9657ml HO (CH 2 CH 2 O} ) m- (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2) nH ( molecular weight 1700, m + n ≒ 5.7) (10% ethanol aqueous solution) 6.78ml KBr 10.8g 10% nitric acid 114ml [B ₂ ] 2.5N AgNO ₃ aqueous solution 2825ml [C ₂ ] KBr 824g KI 23.5g Distilled water to 2825ml [D ₂ ] 1.75N KBr aqueous solution 464.3 ml of each of solution B ₂ and solution C ₂ was simultaneously mixed with solution A ₂ by using a mixing stirrer shown in Japanese Patent Publication Nos. 58-58288 and 58-58289 at a silver potential control amount of 35 ° C. It takes 2 minutes to add
Nucleation was performed.

After stopping the addition of solution B ₂ and solution C ₂ ,
It takes 60 minutes to raise the temperature of solution A ₂ to 60 ° C,
After adjusting the pH to 5.0 with 3% KOH, the solution B ₂ and the solution C were again adjusted.
₂ was added by the double jet method at a flow rate of 55.4 ml / min for 42 minutes. This temperature rise from 35 ° C. to 60 ° C. and solution B ₂ , C ₂
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the re-simultaneous mixing by the method was controlled to +5 mv and +12 mv, respectively, using the solution D ₂ .

After completion of the addition, the pH was adjusted to 6 with 3% KOH and immediately desalted and washed with water in the same manner as Em-1.
This seed emulsion Em-2 has a total projected area of silver halide grains.
90% or more consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, the average thickness of hexagonal tabular grains was 0.05 μm, and the average diameter (circular diameter conversion) was 0.55 μm. .

(Preparation of Monodisperse Twin Crystal Emulsion EM-3) Monodisperse twin crystal emulsion EM-3 was prepared using the following four kinds of solutions.

[0094] [E _2] ossein gelatin _{29.4g HO (CH 2 CH 2 O} ) m- (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2) nH ( molecular weight 1700, m + n ≒ 5.7) ( 2.5% seed emulsion Em-2 0.588 mol equivalent Distilled water to 4800 ml.

[F ₂ ] 1404.2 g of silver nitrate Distilled water to 2360 ml.

[G ₂ ] Potassium bromide 968.0 g Potassium iodide 20.6 g Distilled water to 2360 ml.

[H ₂ ] 1.75N KBr Aqueous Solution At a silver potential control amount of 60 ° C. below, a solution A ₂ was mixed with a solution B ₂ using a mixing stirrer disclosed in Japanese Patent Publication Nos. 58-58288 and 58-58289. The total amount of the solution C ₂ was 111 by the simultaneous mixing method at a flow rate of 21.26 ml / min.
It took a minute and additional growth was performed.

During this period, the silver potential was controlled to be +25 mV by using the solution D.

After completion of the addition, desalting was carried out using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts, and 92.2 g of ion-exchanged gelatin shown in Tables 1 and 2 was added. An aqueous gelatin solution containing the mixture was added to make 2500 ml, and the mixture was redispersed with stirring.

When EM-3 was observed and measured by an electron microscope and the formation was analyzed, the average particle diameter (converted to a circle diameter) was 1.
The average particle thickness was 04 μm, 0.26 μm, and the distribution was 18%.

Emulsion EM-4 was prepared in exactly the same manner as EM-3 except that the amount of potassium bromide in the [F ₂ ] solution used in Emulsion EM-3 was 982.8 g and the formulation was changed except for potassium iodide. Next, these Em-3 and EM-4 were chemically sensitized by the same method as EM-1.

The emulsions EM-1 to EM-4 thus obtained were added with the additives described below to prepare emulsion layer coating solutions. At the same time, a protective layer coating solution described below was also prepared. The coating amount was 2.0 g / m ^{2 on} one side and the amount with gelatin was 3.1 g / m ² using two slide hopper type coaters at a speed of 80 m / min on both sides of the support simultaneously. Application was performed and drying was performed for 2 minutes and 20 seconds to obtain a sample. The iron content of the gelatin used in the protective layer coating solution was changed by ion exchange treatment.
There are various types of gelatin, and these are shown in Tables 1 and 2. As the support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, butyl methacrylate 40 wt% 3
An aqueous copolymer dispersion obtained by diluting the copolymer of seed monomers to a concentration of 10 wt% was used as the undercoat liquid 17
A blue colored polyethylene terephthalate film base with a density of 0.15 for a 5 μm X-ray film was used.

The additives used in the emulsion are as follows.
The addition amount is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1 , 3-Dihydroxybenzene-4-sulfonic acid ammonium salt 4g

[0105]

[Chemical 1]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg diethylene glycol 7 g dextran (average molecular weight 60,000) 600 mg sodium polyacrylate (average molecular weight 3.6 2.5 g Next, the following was prepared as a protective layer coating liquid. The additive is shown in the amount per liter of coating liquid.

Ion exchange treated gelatin 68 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (matting having an area average particle size of 1.2 μm Agent) 0.5 g Ludox AM (DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 8.5 mg Glyoxal 40% aqueous solution (hardener) 2.0 ml Dye emulsion dispersion 1.2 g

[0108]

[Chemical 2]

Method for Preparing Dye Emulsion Dispersion 100 g of the following dye was dissolved in a solvent consisting of 280 ml of tricresyl phosphate and 850 ml of ethyl acetate at 55 ° C. This is called an oil solution.

On the other hand, an anionic surfactant (AS) was added to 13.5
2.7 l of a 9.3% zetilan aqueous solution containing g was prepared. This is called an aqueous solution. Next, the oil-based solution, the water-based solution, and a dispersion pot were charged, and dispersion was performed while maintaining the liquid temperature at 40 ° C. Phenol and 1,1-dimethylol-bromo-1-nitromethane were added to the obtained dispersion in appropriate amounts, and the mixture was adjusted to 2.4 Kg with water.

[0111]

[Chemical 3]

The coated samples Nos. 1 to 40 thus obtained were evaluated for sensitometry and roller marks.

(1) Sensitometry (Evaluation of Photographic Performance) In sensitometry, a sample was sandwiched between two intensifying screens (KO-250 Konica Corporation), and a tube voltage of 80 kv was applied via an aluminum wedge.
p, tube current 100 mA, 0.1 second X-ray irradiation. SRX-503
(Konica Corp.) was modified and SR-DF (Konica Corp.) was used as the treating agent, and the processing time was dry to dry for 30 seconds (development 35 ° C, fixing 33 ° C, washing with water 20 ℃, dry 50 ℃), the sensitivity was determined. The sensitivity was expressed by the reciprocal of the exposure amount that gives a density of fog +0.5, and was shown as a relative sensitivity with the sensitivity of Sample No. 1 being 100.

(2) Evaluation of roller mark property The pressure mark = roller mark by the roller of the automatic processor was evaluated as follows. That is, the treatment was carried out by the same treatment method as that for sensitometry in the state of uniform exposure so that the blackened density after treatment was 0.8 to 1.2. The roller marks generated at that time were visually evaluated and classified into the following 5 grades.

5: No generation of roller marks 4: Very slight occurrence 3: Some occurrence (within practical use permit) 2: Many occurrences (outside of practical use permit) 1: Very large occurrence 1: Contamination of residual color Many results are not practical. The results obtained above are shown in Tables 1 and 2.

[0116]

[Table 1]

[0117]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the iron content in the emulsion layer was 3.0 per 1 g of gelatin.
It can be seen that the use of gelatin of not more than μg not only improves the photographic performance (especially the sensitivity, Dmax), but also significantly suppresses the generation of roller marks due to ultra-rapid processing.

[0119]

According to the present invention, it is possible to provide a silver halide light-sensitive material having high sensitivity and less generation of roller marks during rapid processing.

Claims (2)

[Claims] 1. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, the iron content in gelatin contained in the emulsion layer is 3.0 per gram of gelatin. A silver halide photographic light-sensitive material characterized in that it is less than microgram and the average silver iodide content of the emulsion is less than 3.0 mol%. 2. A development processing method, wherein the silver halide light-sensitive material of claim 1 is processed in a total processing time (Dry to Dry) of 35 seconds or less.