DE1547822C3 - Process for preparing a silver halide photographic emulsion - Google Patents

Description

3 4

loren is the achievement of accurate and correct in which R _{1 is} an alkyl group, R _{2 is} hydrogen, a

. Findings doubtful. ', Alkyl or aralkyl group and M is an alkali or

It is also another process (compare the mean ammonium cation.

German patent specification 20 733), in which, according to a preferred embodiment of the Gelatin in the liquid phase is removed by using the photographic silver halide silver halide photographic emulsion of gelatin emulsion with water to an appropriate one Subjected to centrifugal separation, the silver concentration, generally up to 100 parts halide particles are separated. However, in 1 part is emulsion, diluted and a centrifugal of this Case in the practical application of the separation and redispersion of the process It is difficult to subject the silver halide particles to precipitated silver halide particles where sufficient uniform and persistent in one at the anionic surface-active compound of the Such a state to redisperse after having given formula above preferred the emulauf The bottom of the separator is fed under the action of the sion before the centrifugal separation Centrifugal force were deposited once. When Ver executes; however, it can also only do this If an insufficiently dispersed emulsion is used, 15 dispersion medium is added, for the preparation of a photosensitive emulsion- Typical examples of the anionic surface layer the photosensitive layer does not act as active compounds caused by the above uniform sensitive layer, and the general formula will be shown, potassium-numerous fog particles (particles that do not selectively 2-octyl-benzimidazoIsulfonate, potassium-2-dodecyl-benzo the action of actinic rays reduces 20 imidazole sulfonate, sodium 2-heptadecylbenzimidazole are) formed after development. Such sulfonate,. Sodium 1-methyl-2-heptadecyl-benzimide haze particles cause a so-called rear azole sulfonate, ammonium l-heptadecyl-2-methyl-

Ϊ j basic veil, which makes the distinction or dif- benzimidazole sulfonate and sodium l-benzyl-2-hepta-

delimitation of the image by actinic rays, decylbenzimidazole sulfonate.

For example, the image distribution of radioactive substances. Although by often known methods, the centrifugal separation process is occasionally carried out batchwise or continuously. For example, what is known as a good result can be obtained, in most centrifugal precipitation devices using cases a fogging takes place, so that this connection of a cylindrical separating tube, a centrifugal separating process is unreliable. Rotating or Rotating Device Type U.S. Patent 2,463,794 describes some beakers or a centrifugal separator equipped with a multiple cone separator of types of anionic surfactants. However, when using a turn. The size or value of sodium dodecyl sulfate or sodium alkylnaphthalene. Centrifugal acceleration for the separation is sulfonate (a typical compound according to the 35 appropriate depending on such factors, named .. USA. Patent) a considerable such as viscosity of the emulsion, the grain size of the amount of microscopic agglomerates of silver particles, the specific gravity of the particles of the halide grains found in the redispersed silver halide desirable processing or process velocity dispersion, and thus influences have been chosen in terms of speed or susceptibility or uptake numerous haze particles in development of a layer made of 40 by the ability of the emulsion grains to mechanically such a dispersion. If the value is too high, formed. ■. the precipitated materials are coagulated, where- " _{x The} object of the invention is to create a system made difficult by the redispersion, and in some cases

| _P method of making a gelatinous case severely cloudy or fogged

silver halide photographic emulsion causing 45 to occur. ·,.

After or during the centrifugal separation, the supernatant liquid is removed from the system using a centrifugal separator, fugal separation is enabled and a stable gelatinous , which are deposited on the wall of the separation haze formation and formation of coarse, as an aggregate 50 device, and the present grains is made possible. ''"■". Precipitates are collected and redispersed by means of mechanical devices. According to the invention, a method for dispersing devices is used. The general production of photographic silver halide means is water or a dilute gelatin emulsion, a gelatin-containing silver halide solution being used as the dispersing medium. If the emulsion is subjected to centrifugal separation, the presence of part of the gelaiine of the original and thus deposited silver halide grains in the borrowed emulsion is permitted, part of the presence of an anionic surface-active liquid alone or with part of the bond are redispersed, created, thereby dispersing media are used. However, it is characterized that the redispersion in the silver halide particles in such a dispersing medium does not sufficiently disperse the presence of a benzimidazole derivative of the formula 60, and it

■. . ''. '■ coarse grain masses remain, whereby after

_; N ^: Development of the emulsion layer often becomes fog

R ₁ - ^ SO _{: i} M forms when the anionic surface-active agent

^ N "\;. ' 'Binding according to the invention of the emulsion before

I χ "65 centrifugal separation has not been added. If

^ but the anionic surface-active compound

² according to the invention incorporated into the dispersing medium

as an anionic surface-active compound, has been brought about, the formation of coarse grain

prevented masses and the formation of fog is so limited that it gives practically no interference.

The anionic surface-active compound according to the invention is preferably introduced into the emulsion to be subjected to centrifugal separation in an amount of 1 to 1000 mg per 100 ml of emulsion or in the dispersing medium in an amount of 2 to 500 mg per 100 ml of the dispersing medium.
If necessary, the emulsion redispersed in this way can be re-subjected to the treatment sequence of centrifugal separation and redispersion in one or more repetitions.

By adding the above surface active compounds, the silver halide photographic emulsion capable of centrifugal separation can be made had been subjected to be redispersed uniformly again without leaving any coarse Particles, the dispersion thus formed being stably maintained for a long period of time can. When a photosensitive prepared by applying the dispersion thus formed to a support Layer is developed and fixed, is the formation of unselectively reduced so-called veil particles similar to that of a common emulsion which is not subjected to centrifugal separation was. It also increases the sensitivity of the emulsion in which the anionic surfactant compound is incorporated, is not deteriorated by the centrifugal separation and redispersion.

That obtained by the method according to the invention. silver halide photographic emulsion is useful not only in electron microscopic ultramicroautoradiography, but also valuable for ultramicroautoradiography based on an optical microscope. In the latter In this case, the emulsion can be applied to the samples according to known procedures, for example by dipping the sample applied to a slide into the emulsion or by dripping on Emulsion on the sample.

The silver halide emulsion obtained by the process according to the invention can not only be used in Form of the original sol state, but also in the form of a photographic photosensitive Material obtained by applying the emulsion to a suitable support. and drying has been applied.

. Another example of the use of the emulsion according to the invention is the photographing of vacuum ultraviolet rays, especially their Spectra. ^ Ultraviolet rays of shorter wavelengths 2000 Å are referred to as vacuum ultraviolet rays. For photographic recording So-called Schumann plates were previously used for radiation of such short wavelengths used as photosensitive materials.

However, it is difficult to reproduce and reproduce in the case of such photographic materials to obtain stable materials. Instead of such a Schumann plate, the photographic material, which is the silver halide, of which the predominant part is the gelatin by the method according to of the invention has been removed, includes to apply. The latter method is photographic Layer essentially free of gelatin and can be easily reproduced with better reproducibility can be obtained.

In addition, the photosensitive emulsion prepared by the method according to the invention can be used with a suitable proportion of gelatin or some other hydrophilic high molecular weight Material to form a photographic light-sensitive emulsion are added, which for Manufacture of photographic light-sensitive materials by applying the emulsion to : suitable carriers can be used.

. In this case, by adding gelatin

ίο or some other hydrophilic high molecular weight Connection in such a way that the content of the binder is less than that of the original Silver halide emulsion before centrifugal separation is carried out is a photographic one light-sensitive material with a high silver halide content and a reduced binder content can be obtained. For black and white or color photographic light-sensitive materials, the formed with such a photographic photosensitive emulsion, the thickness of the Emulsion layer, which is necessary for achieving a desired image density, is therefore considerable be reduced. The photographic light-sensitive materials thus prepared have the following advantages:

1. The light scattering in the emulsion layer is reduced and the image sharpness is improved. ¹

2. The speed of developing, fixing, bleaching treatment, water washing and drying is enlarged, whereby the time required for the photographic treatments is effective can be reduced.

3. The tendency of photographic films or papers to curl before or after treatment be reduced.

The method according to the invention is as follows explained in more detail using examples.

example 1

A silver chlorobromide photographic emulsion containing silver halide particles having an average grain size of about 0.1 micron was prepared by an ordinary method in the presence of gelatin. The weight ratio of silver halide to gelatin in the emulsion was 100:55 and the gelatin concentration was about 9%. The emulsion (20 g), which was present at room temperature in a gel state was melted by heating to 40 ⁰ C. The following additives were added to the emulsion and the emulsion was diluted with 180 ml of distilled water.

Composition IA; .- ;. ■

4-Hydroxy-6-methyl-l, 3,3a, 7-tetrazaindene, 1/100 mol / l in alcoholic

Solution 0.4 ml

Sodium chloride, 0.5 weight percent

aqueous solution 2 ml

Sodium 1-benzyl-2-heptadecyl-benzimidazole sulfonate (Ia), lweight pro-

cent aqueous solution 2 ml

The emulsion to which the above composition was added was made into a cylindrical

Centrifugal separation tube introduced and the centrifugal Subjected to separation for 15 minutes at 2000 rpm (centrifugal acceleration 1000 g). Almost the Total amount of. Silver halide particles were deposited on the bottom of the separator. The protruding Liquid was removed by decantation and the deposits became the redispersion medium added to the composition given below. /:.;

Composition IB

Sodium chloride, 0.5 percent strength by weight aqueous solution ............ i 0.8 ml

Sodium l-benzyl-2-heptadecylbenz- '. imidazole sulfonate (Ia), 1 weight percent aqueous solution 6 ml

made up to 80 ml with distilled water

With gentle stirring, the silver halide grains were easily dispersed in the liquid phase :,.,; . ■ - ■■ ·. . . ■ ..- .. ■

; ,, A drop of the photosensitive ones produced in this way Emulsion was placed on an electron microscope object with exclusion of light, consisting of a carrier film and a very thin cut applied to a carrier grid, which has a radioactive] sotop, e.g., tritium, was applied using a small syringe and allowed to dry. After placing the sample in a dark container and leaving it there for one month, wherein the photosensitive emulsion layer is given off by the radioactive isotope radioactive rays were sufficiently irradiated, the emulsion layer was kept for 4 minutes 20'C developed in a developer solution for X-ray films of the following chemical composition:

N-methyl-p-aminophenol sulfate 4.0 g

■ .. ■ Sodium sulfate (anhydrous) 60.0 g

Hydroquinone: · ....; 10.0 g

Sodium carbonate (monohydrate) .... 53.0g

Potassium bromide, 2.5 g

_: topped up with water to .......... 11

B e i s ρ i e 1 2

20 g of an emulsion as described in Example 1 were prepared. The emulsion was with the Liquid with the following composition added:

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1 / 100th mol / l in alcoholic

ίο solution ....: .'.... 0.4 ml

Sodium chloride, 0.5 weight percent

term aqueous solution 2 ml

Sodium - 2 - heptadecyl benzimidazole sulfonate, 1 weight percent aqueous'

. solution 4 ml

made up to 180 ml with distilled water

The emulsion was then subjected to centrifugal separation under the same conditions as in Example 1 described, subject.

The liquid of the composition given below was then used as a redispersing medium used and as carried out in Example 1, dispersed. . ·

Sodium chloride, 0.5 weight percent

aqueous solution 0.8 ml

. Sodium 2-heptadecylbenzimidazole sulfonate, 1 weight percent aqueous

Solution 12 ml

made up to 80 ml with distilled water

3 °

45

Ί: After fixing, washing and drying in the usual manner, when observing or photographing on a. Electron microscope, at a magnification of 5,000 to 1,000, found that haze-forming particles which form an undesirable background haze are sufficiently reduced and the developed silver image, which indicated the location of the radioactive isotope in the sample, was sufficiently differentiated and sharp, and there were almost none Gelatin was left over the sample film, the sample itself could be observed with sufficient image brightness.

If the surface active agent (Ia) has been removed from the composition IA and instead 40 of a l ° / o'g ^en ml aqueous solution of gelatin in the composition 1 B were used many large particle masses were present as well as numerous schleicrbildende particles, the undesirable a Background haze resulted; the images produced by the radioactive rays were not very different and also blurred.

If the gelatin-free, light-sensitive Silver chlorobromide emulsion used for microautoradiography on an electron microscope As in Example 1, good results were obtained. · -. ...

■ .- '. ■■ . ■■■■■■■ B eis ρ ie I 3'. . ■

20 g of the emulsion were prepared as described in Example 1.

The emulsion was mixed with a liquid of the composition given below.

^ -Hydroxy-ö-methyl-l ^^ aJ-tetrazaindene, 1/100 mol / l in alcoholic
Solution ................. ·, ... ■ ..0.4ml

Sodium chloride, 0.5 weight percent

term aqueous solution 2 ml.

made up to 180 ml with distilled water

The emulsion was subjected to centrifugal separation under the conditions given in Example 1. The liquid of the following composition was used as the redispersing medium, and the same procedure as described in Example 1 was repeated to redisperse to reach.

Sodium chloride, oo weight percent ¹

'aqueous solution 0.8 ml

Sodium 1-benzyl-1-heptadecyl-benzimidazole sulfonate, l weight percent

aqueous solution 16 ml

made up to 80 ml with distilled water

309 638/17

Using the photosensitive emulsion thus obtained from which gelatin has been removed were were for one for ultramicroautoradiography certain sample for an electron microscope also gives a good result.

Example 4

In 20 g of the emulsion according to Example 1, the liquid with the composition given below brought in:

4-Hydroxy-6-methyl-l, 3,3a, 7-tetrazaindene, 1/100 mol / l in alcoholic

r Solution: ... 0.4ml

Sodium chloride, ©, weight percent

term aqueous solution 2 ml

Sodium l-benzyl-2-heptadecyl-benzimidazole sulforate, lweight percent

term aqueous solution 8 ml

made up to 180 ml with distilled water

The emulsion was subjected to centrifugal separation under the same conditions as specified in Example 1, subject. Before redispersing, 80 ml of a 0.005 percent strength by weight aqueous Na- as Trium chloride solution was added to the deposit and the redispersion procedure described in Example 1 was followed applied.

Using the photosensitive emulsion thus obtained from which gelatin has been removed was for a specimen intended for ultramicroautoradiography for an electron microscope fog was weak and good results were obtained.

35 Example 5

30 potassium bromide, 1 weight percent

aqueous solution 0.4 ml

Potassium 1-methyl-2-heptadecyl-benzimidazölsulfonat, 1 weight percent aqueous solution 12 ml

Gelatin ... .- '. ■ ... 1.5 g

topped up with distilled water

to 80ml

The thus obtained photographic photosensitive emulsion containing a decreased amount of gelatin was applied to a glass slide and gradually dried, whereby a photographic, light-sensitive material having a low fog was obtained that is used for ordinary autoradiography was suitable.

Examples. . .

A silver bromide iodide emulsion for color negative films became centrifugal separation under centrifugal acceleration subject to 1000 g. 20 g of the so deposited silver bromide iodide, 100 ml of supernatant liquid and 8 ml of a 1 percent strength by weight aqueous solution of sodium 1-benzyl-2-heptadecyl-benzimidazole sulfonate became uniform with a coupler dispersion having the following specified components redispersed by ultrasound treatment.

Coupler (indicated below) .. 15 g

Dibutyl phthalate 60 g

Saponin (5%) 30 ml

Gelatin .- 20 g

made up to 200 ml with distilled water

OH

A silver bromide iodide photographic emulsion containing silver halide particles averaging 0.2 microns in grain size was prepared in the presence of gelatin by an ordinary method. The emulsion contained gelatin at a concentration of about 2.5 percent by weight. The emulsion (200 g) was heated to 40 ⁰ C, with 4 ml of an aqueous solution lgewichtsprozentigen van potassium -1 - methyl-2-heptadecyl - benzimidazolsulf onate crosslinked and then subjected to centrifugal separation for 45 minutes at a centrifugal acceleration of 1000 g. After removing the over- '. The liquid of the composition given below was added to the precipitate and the liquid could be redispersed therein with gentle stirring.

CONHC ₁₈ H ₃₇

The components indicated above were dispargiert by stirring the system for 1 hour at 70 ⁰ C in a colloid mill.

This dispersion was made on a cellulose acetate film Applied to a dry thickness of 5 microns.

When the film obtained in the above-mentioned manner is in a color developing solution containing Ν, Ν-diethyl-p-phenylenediamine hydrochloride contains, developed for 10 minutes at 20 ° C and then the bleaching treatment, fixing and water washing was subjected to a sharp cyan image with a maximum optical density of over 3.5.

Claims (4)

1 2 reduce, thereby obtaining numerous advantages Claims: · will. The sensitivity of a photographic silver I. Process for the preparation of a photographic halide emulsion to visible light and see silver halide emulsion being gelatinous to radioactive rays of high energy containing silver halide emulsion of a centrifugal used in many technical fields. So became separation is subject to and so deposited in the fields of biochemistry, research, the which silver halide grains in the presence of a fundamental medicine or the like. Generally a car radio anionic Surface-active compound graphic method used in which the be spergiert, characterized in that one io distribution or spreading one with a radiodie Redispersion in the presence of a benzimide-active substance provided as a display material azole derivative of the formula compound of a photographic opposite emulsion sensitive to radioactive rays N ■■ ' ' was drawn to show the behavior of the R ₁ -. SO ₃ M, 15 indicator material provided connection in the living ^N "N ■■ · ■■ '! To examine the organism. The technique in which ; · '■■' ■ 'the autoradiographic procedure on microscopic D pical samples are used, is called »micro- ² '"'autoradiography" and is used in observation in which R _{1 is} an alkyl group, R _{2 is} hydrogen, 20 attention and monitoring of the material transition between an alkyl or aralkyl group and M an alkali see the cells or within a cell im or ammonium cation, particularly suitable as an anionic living organism. Recently surface-active connection. a new process was developed in which 2. The method according to claim 1, characterized in that the microautoradiographic method is used for samples draws that the anionic, surface-active 25 is carried out for the electron microscope. the Connection of the photographic silver halide electron microscopic observation of living emulsion in an amount of 1 to 1000 mg per 100 ml systems, especially the fine structures of Add emulsion before centrifugal separation. Cells, turned out to be very useful and therefore became 3. The method according to claim 1 and 2, characterized in biological or medical fields in characterized in that the emulsion is practiced before the 30 large scale. If it is possible Centrifugal separation with up to 100 parts of water is the distribution of a special one, with a radioauf 1 part of the emulsion diluted. active nuclide indicator (a radioactive mar- 4. The method according to claim 1 to 3, characterized kieren compound) provided compound of a characterized in that one can recognize the redispersing medium image in an electron microscope, for redispersing the silver halide grains. 35 can be the metabolism and function of anyone Water used. Part of it that forms the fine structure of a cell 'can be recognized so that such information from ^{1 are of} great value. The application of microautoradiography on However, 40 electron microscopy samples using conventional photographic emulsions is The invention relates-to a method for associated with great difficulties. The through a Manufacture of a photographic silver halide electron microscope to observe samples must emulsion, with a gelatin-containing silver halide namely sufficient permeability to emulsion is subjected to centrifugal separation 45 via electron beams. The permeable and the silver halide grains so deposited in the absence of gelatin against electron beams is ever? Presence of an anionic surface-active agent but low. If a gelatin-containing silver halide bond can be redispersed. genidemulsion applied to the sample as a coating In a photographic emulsion with a will, a gelatin film remains on the sample after the Silver halide as a photosensitive component 50 back development and fixing and makes it more difficult is mostly gelatine as a protective colloid for the fine observation of the developed silver image as well as the Silver halide crystals are used. In some cases sample yourself. However, the presence of gelatin is after- There has therefore been no lack of attempts to get on the share connected. For example, the presence of an electron microscope sample is not gelatin or only to leave a very thin film of gelatin on the gelatin when using the photographic 55, photosensitive material in the so-called For example, a method is known in which electron microscopic ultramicroautoradiograph gelatin before or after development, e.g. B. by phie, whereby the ultramicroautoradiography on samples removes a proteolytic enzyme (cf. for the electron microscope, followed by example IC. Hampton et al, Journal of Bioeine electron microscopic examination follows, 60 physical and Biochemical Cytology, vol. 10, p. 140, or in a photographic recording by and R. J. P r ζ y b yt s k i, “Experimental Cell Resin ultraviolets Rays with extraordinarily short arch ", vol. 24, p. 183). However, since such a Wavelengths, d. H. so-called vacuum ultraviolet method is feared that the location of the radiate, undesirable. In addition, it is usually possible to distribute the radioactive indicator reduced silver pure indicated by lowering the gelatin content in the compound shown photographic emulsion and by rising image easily from its original position during tion of the content of silver halide, the thickness of the treatment can be moved or shifted Emulsion layers in photographic materials or that something of the reduced silver image