DE1547858A1 - Photographic material and photographic process which produce a visible reversal image in contact with an exposed silver halide emulsion - Google Patents

Description

In contact with an exposed silver halide emulsion Photographic Material Producing a Visible Reversal Image And Photographic Process

The invention relates to new photographic materials and processes, and more particularly to diffusion transfer materials, the methods of making such materials as well as new methods of developing photographic materials.

Diffusion transfer materials and processes are in the Photography known; one of the main uses for such materials consists in copying paper, Documents, books and the like. Such copying processes use a light-sensitive silver halide containing emulsion in a suitable manner, usually.

Dr Ha / Ma

by

9 0 9 8 4 9/11 9 1

through reflex imprint of a printed surface exposed to form a negative latent image of the article. This exposed emulsion is then in presence certain chemicals brought into contact with the top of a non-photosensitive emulsion, which contains silver stains or the like, which serve as precipitation nuclei · As a result, one obtains a a sheet containing a direct negative image and a sheet containing a reverse image or positive image of the object Arc. The negative is discarded and the positive is retained as a photocopy of the original.

A similar process has been used to make a direct print from ordinary negative photographic materials used when a useful positive is desired as quickly as possible. This system found special for processing photosensitive negative materials, which come in the form of rolls, e.g. 16 mm, 35 mm, 70 mm, 5 inch and 9 inch films are used for motion pictures and for aerial surveillance »In this system, the surface of a specially prepared, non-photosensitive strip with the surface of the exposed Photosensitive emulsion brought into contact in the presence of certain chemicals, so that the film is underneath Formation of a negative is developed while equal

909849 /

side on the non-photosensitive strip Immediate observation a fositing image is created.

The non-photosensitive strip is one with one Gelatin emulsion coated flexible carrier; the Emulsion contains microscopic parts of the precipitation nuclei. These whimsical particles become precipitation nuclei or Called seed centers because of the difference between the exposed, light-sensitive emulsion and the emulsion of the second stripe diffusing silver complex is reduced to metallic silver in the presence of these nucleiThese tiny particles thus act as nuclei for the formation of metallic silver

These diffusion transfer methods are used so-called single-bath developer carried out, i.e. with Reagents containing both a developer and a silver halide solvent or fixing agent. In places where the Fegatirmaterial hardly or not at all exposed, very little silver halide is reduced to metallic silver by the developer and the solvent complexes with the silver halide in the negative emulsion. This silver complex migrates into the second emulsion over the surface, or

diffused 909849/1191

diffuses into this second emulsion, with which eioh the light-sensitive emulsion is in contact · The Complexes are then made in the presence of the coagulation germs reduced to metallic silver · At a point on the negative where the negative emulsion is not struck by light and is therefore clear, the nucleation centers thus cause heavy silver deposition on the second Stripes · In places where the light-sensitive emulsion was heavily exposed, practically all of the silver halide is reduced to silver before it can be dissolved by the solvent, so that the second stripe in places where the negative is dark or contains a lot of reduced silver, contains only a little silver · In the diffusion transfer process described is obtained thus a positive copy during the development of the negative image

The well-known diffusion transfer positive materials have in the Hegel only a low resolving power. Increasing the resolution would result in a more useful positive material. In addition, for this Materials used a common gelatin emulsia, which in all cases does not allow a sufficient amount of the processing agent to pass through for the development of the photosensitive emulsion when it is used as a processing mat

909849/1191 It

It would therefore be desirable to have a second strip, which after the diffusion transfer process a positive or Reversal results and so much linbad developer at the same time permeates fully as necessary to develop the negative material · Such a material would facilitate the rapid processing of photographic negative material enable with simultaneous creation of a positive image. A positive copy would thus be obtained with a proportionate high resolution for immediate evaluation and from the negative material further could then be used Positive copies can be made.

The invention provides a new diffusion transfer material with higher resolution for the positive images than was previously available. You invention also creates a web saturable with a single bath developer »which simultaneously develops an exposed silver halide emulsion and to form a visible positive image can be used on the surface of this web.

You invention also includes the creation of methods for Production of positive materials with high resolution as well as new development methods

course

S0 9 8 k 9/1 1 9 \

Expressed in terms of course, the material according to the invention exists from a substrate that is permeable to single-bath developers, coagulation nuclei on its surface, during the The rest of the substrate is essentially free of such germs This substrate forms a visible positive image, when brewed in contact with a silver halide emulsion while in contact with a single bath developer is being developed.

6-em according to an embodiment of the invention are shown on the surface of permeable for single-bath developers Substrates deposited in a vacuum Lower Sole germs » These substrates can either be hydrophilic, such as those normally used as the base for photographic emulsions gelatin used, or they can be in the form of a sheet material. In any case, the inventive method enables the substrate to form a visible positive image by surface contact during the Development of an exposed emulsion containing over halide

The method according to the invention for producing finished products Fixed images consists of making an exposed silver halide emulsion with the surface of a substrate and brings it into contact with one-bath developer, creates a visible positive image on the substrate and the silver

909849/1191

halide emulsion

halidemulaion developed with the substrate Coated with precipitation germs and for single bath devolatilizers is permeable.

The material according to the invention has a higher resolution power than was previously achievable with diffusion transfer materials of the type described. if besides the substrate is a sheet-like material, If the process is more economical because the web contains a visible positive image for immediate viewing, while so far such tracks had little or no usefulness after development of the silver halide emulsion The invention thus not only creates new photographic materials, but also enables the use of Substrates that were previously not brewable for diffusion transfer processes

"Silver halide ^{emulsions 11} and" silver halide-containing emulsions "are customary photosensitive silver halides, in particular emulsions containing silver bromide and iodide and mixtures thereof. ! rager upset who when the

Emulsion 909849/1191

Emulsion for projection purposes, e.g. as a slide or negative should be used, transparent and opaque if the emulsion is reflected with Light, e.g. in a fume cupboard, is to be exposed. Such silver halide emulsions are in use exposed either with partial energy or with electromagnetic energy, e.g. visible light, gamma radiation, beta radiation and the like, so that the emulsion becomes dark when treated with a developer at the exposed areas. You developable parts of the Emulsions thereby form a latent image and a silver halide emulsion containing a latent image becomes hereinafter referred to as exposed silver halide emulsion.

In the following description of the invention, the surface which carries the precipitation nuclei is called "Substrate *. Of course, this substrate must be permeable to mobile aqueous liquids, i.e. it must at least allow aqueous liquids to pass freely into its surface and, if necessary, it can be permeable to aqueous liquids through its entire depth. An example of a permeable The substrate is a coating of hydrophilic material, e.g. gelatin, polyvinyl alcohol, gum arabic, polyethylene

909849/1191

-.9 - ■

ozyden or the like on an acetate support film or on paper · In the case of the acetate carrier film coated with gelatin The gelatin allows aqueous liquids to diffuse into its surface and is therefore suitable for aqueous liquids Liquids permeable · Of course, the hydrophilic layer can also be applied to a wide variety of other substrates, e.g. made of cellulose nitrate, glass, polyester, paper and the like, for continuous, fast processing of photographic negatives, a flexible support is preferred.

G-em according to another embodiment of the invention the permeable substrate of a porous web of material, e.g., the web may be a microporous, non-fibrous, wettable Be mat made of polyvinyl chloride · Sub is "wettable" to understand that the material is aqueous liquids absorbs and retains. The permeable substrate can be a porous sheet or a woven mat, e.g. Cellulose acetate, cellulose triacetate, polyurethane, fiberglass, paper, and the like · A microporous substrate is one in which the cavity consists of a plurality of interconnected, spaced apart There is pore openings.

The surface of the substrate according to the invention is with. Coated precipitation nuclei · Such precipitation nuclei are known

909 8 4 9/1191

and

- ΊΟ -

and consist of substances which, in the presence of suitable chemicals, cause a reduction of soluble silver halide complexes. For the implementation of the invention, the precipitating nuclei should be heavy metals or heavy metal compounds. It is advisable to use metals from groups IB, II B, IV A ₁ VI A and VIII or the reaction products of metals from groups IB, II B and IV A with sulfur or with elements from group VI A. Preferred substances which form nucleation centers are copper, Tin, lead, mercury, germanium, palladium and platinum as well as their sulphides, tellurides and selenides. Particularly preferred substances which form nucleation centers are money, silver, gold sulfide and silver sulfide. Although two or more types of precipitating nuclei can be combined, it is preferred to use only a single type for carrying out the invention.

The precipitation nucleus must be deposited on the surface of the substrate, which is preferably done by vacuum deposition he follows. For most types of F & l

“3 respiratory germs, the pressure should not exceed 10 mm Hg and in many cases a pressure of 10 mm Hg or less is preferred. It is therefore particularly preferred a vacuum deposition under a pressure of about 0.1 to about 1 χ 10 mm

the 909849 / 11-91

The precipitation nuclei are usually applied to the surface in such a way that the material is melted in a suitable container under vacuum and the substrate surface is then exposed to the molten material. At a preferred embodiment, the surface of the substrate is continuously guided over the container, so that a coating of the composition forms on the surface. Of course, a thick coating is not required and can even be disruptive. The use of a monomolecular or monoatomic layer is preferred.

The vacuum leveling can be carried out in batches or continuously. In a preferred embodiment According to the invention, the substrate is above an opening of molten material which forms precipitation nuclei in a vacuum with deposition of the desired amount of the material on the substrate · Usually is exposing the substrate to the molten nucleating material for about 0.1 to about 130 seconds.

Of course, if the silver halide emulsion gives a negative image on development, a fositive image is obtained on the substrate of the present invention, and if the silver halide emulsion gives a positive image, for example is used to make a print, one obtains

909849/1191 -

a negative image on the substrate according to the invention. One could either have a print for immediate viewing after developing the silver halide negative or receive a negative for immediate viewing after developing a positive print according to the invention " The image produced on the substrate according to the invention is called a visible reverse image in order to emphasize that the generated image has the opposite reflection or transmission properties as the image of the developed silver halide emulsion.

The development of the silver halide emulsion and the The easiest way to generate the visible reversal image on the substrate is to use the substrate a suitable single bath devolatilizer. A single bath developer contains both the reducing agents called "developers" and the "fixing agents" said silver halide solvents or silver halide solubilizing reagents. The single-bath developer can also use other common auxiliary substances, e.g. antioxidants, accelerators, a Contain solids preventing agents, hardeners and the like. Basically, however, the single-bath developer consists of a combination of an organic one Reducing agent with a solvent for silver halide

909849/1 191

To the

It is clear to the person skilled in the art that the composition of the One-bath developer according to the temperature and other conditions of use which the developer component has sufficient opportunity to reduce the exposed silver halide before the solvent removes the unexposed halide has common developers, e.g. metal, 1-phenyl-3-pyrazolidone, Hydroquinone, glycine, p-phenylenediamine, p-aminophenel, Pyrogallol, catechol, ascorbic acid and the like can be used. The solvent or fixative is usually a thiosulphate, but another solvent, e.g. a bhodanid, oyanide or the like. It is preferable to use the alkali metal or ammonium salts of the above acid radicals.

The saturated substrate is in intimate surface contact with the emulsion layer of an exposed silver halide emulsion brought and the liquid single-bath developer contained in the substrate diffuses into the emulsion layer with simultaneous development of the exposed silver halide and removal of the unexposed silver " halides. In the hatred, in which the one-bath developer that forms a complex with silver halide Reagent the halides in the unexposed areas of the.

909849/1191

15A7858

When the emulsion dissolves, the silver complex diffuses into the surface of the substrate. The silver complex decomposes on contact with the precipitation nuclei in the presence of the alkaline developer and metallic silver hits the germs with the formation of the visible reverse image · After all of the exposed silver halide has been reduced to metallic silver, the Surfaces are separated and you get a directly visible image on the emulsion, while a visible reverse image is located on the substrate according to the invention.

The following examples illustrate preferred practical ones Embodiments of the invention without, however, being restricted to them

example 1

A Veeco 4-00 evaporation chamber is used to precipitate the precipitation nuclei on the substrate. This evaporation chamber consists of a bell jar that can be placed on an electrically heated container that contains the material that produces the precipitating nuclei; the container can be electrically heated to evaporate the material, and devices 909849/1191 are also assigned to the satchel

services to generate, maintain and measure the Vacuum in the bell jar.

A microporous polyvinyl chloride sheet is placed on top of a Cardboard peeled off and held at a height of 15 inches above a container made of tungsten foil. In the container there are spherical ears made of £ 99,999 pure silver and the bell jar is then lowered over the whole onto the base plate. The system is under a pressure of

-5 Set 10 mm Hg and the temperature of the container is set increased by electrical resistance heating to the melting point of silver, 960 ⁰ O; the attainment of this temperature is observed by eye-eye. The microporous polyvinyl chloride is then exposed to the molten silver in the vacuum for 1 minute. The current to the silver-containing tungsten shaft is then switched off, the silver is allowed to cool down and the druok in the glass globe returns to atmospheric pressure

The polyvinyl chloride carrying the precipitating nuclei is then cut into strips 16 mm wide and placed between two 16 mm wide strips of untreated polyvinyl chloride serving as controls are playful. The following Single bath developer is produced:

Components 9098A9 / 1 191

Beatand parts concentration (g / l)

Sodium sulfite 45 Hydroquinone 40 1-phenyl-3-pyr% zolidone 2 Sodium hydroxide 32 5-methylbeniotriazole 0.2 Potassium aluminum sulfate 5 Sodium thiosulfate 160 water up to 1 liter

This single bath developer is adjusted to a pH of 12.5 set.

A silver halide emulsion (DuPont 931A panchromatic Reversal film) is exposed by taking a standardized scene of f / 4 in a Bell & Howell 16 mn film camera Images / second exposed. That with silver precipitation germs Coated microporous polyvinyl chloride is saturated with the single bath developer, brought into contact with the exposed silver halide emulsion, and total 5 Hinuten treated further in the camera by means of a lane cassette. The precipitation nuclei are obtained on this The portion of the microporous polyvinyl chloride bearing a visible reverse image of the negative image on the film.

Example 2 909849/1191

Example 2

The procedure of Example 1 is then repeated with a low lunge time of 5 minutes. One receives on the vacuum coated polyvinyl chloride substrate good positive image

Example 3

The procedure of Example 2 is repeated using an aperture of f / 5.6 effective, using the substrate coated with precipitation nuclei receives a good positive image.

Example 4

The procedure of Example 1 is repeated using a conical tungsten basket in place of the tungsten foil container. A positive image is obtained on the polyvinyl chloride substrate coated with silver precipitation nuclei.

Example 5

A continuous transport system is used in the Veeco 400 evaporation chamber, so that the substrate

90 9 849/1191 _fc ^ _{4 4} ...

continually

can be continuously sucked over · The transport system is connected via a flexible cable of an I / 4 PS Motor, which rotates at 1725 o / ain and is equipped with a speed controller, driven · The transport system can thus be used to drive the substrate at a constant speed and vacuum conditions can be set in the bell jar during one pass The amount of the precipitating nuclei that is to be precipitated is regulated by a variable opening over which the web runs. It has been found that such a transport system enables germs to be killed more uniformly on the substrate results. The Wolframsohiffohen used for the evaporation of the Niedersohlagskeime is with a Chromel-Alumel thermocouple equipped by the Thermocouple by point welding with the boat connected so that temperature readings can be taken during a run

In the shuttle metallic silver is added, one erseugt in the bell jar, a vacuum of 10 mm Hg, the silver is heated to 980 ⁰ O, and supplies the microporous Polyvinylohloridsubstrat across the opening at a rate such that it is subjected to 10 seconds to the silver vapor · Naoh the substrate is made of the

Glass globe 909849/1191

The bell jar was pulled out and used to treat a Kodak Spe * ialluftbiläfilra with great image sharpness and a silver halide emulsion type SO-243, which film was subjected to a centakt exposure with a dissolution test image in an Edgerton, Germeshausen, and Grier Model VI sensitometer for 1/100 seconds, with the test image exposure from a Reutraldiohtefiltration τοη 2.3 to 3.8 in steps tone each of a f-number varied (log S » 0.3) · The substrate saturated with single bath Eatwiokier is then 5 minutes at 70 °? brought into contact with the exposed silver halide emulsion to develop the emulsion. A positive image with a resolution of 22.7 lines / mm is obtained on the substrate.

Example 6

The procedure of Example 5 is repeated using a nucleation time of 15 seconds · Das The image obtained on the substrate has a resolution of 25.6 lines / mm.

Example 7

The procedure of Example 5 is followed using a Depression time of 50 seconds repeated «You get

9 0 9 8 4 9/1191

on

a positive image on the substrate with a resolution of 25 * 6 lines / mm.

Example 8

The procedure of Example 5 is repeated using a lapse of 130 seconds. Man receives a fositive image on the substrate with a resolution of 16.0 lines / mm

Example 9

Bas procedure of Example 5 is repeated with a Niedersohlagungsdauer of 7.5 seconds and a SiIbertemperatur of 1080 G ^0. A fositive image with a resolution of 16.0 lines / mm is obtained on the substrate.

Example 10

The procedure of Example 5 is repeated using gold as iällungskeime forming material, wherein the UOID is deposited from a Wolframschiffohen at a temperature of 1075 ⁰ O under conditions such that the Niederβohlagungsdauer is 5.4 seconds. With an exposure of 1/100 seconds at 1.8 to 3.5 leutraldiohtefiltration on the sensitometer, a fositive image bit with a resolution of 28.5 lines / mm is obtained.

909849/1 191

Example 11 Example 11

The procedure of Example 10 is followed with a deposition period repeated for 13 seconds. A positive image with a resolution is obtained on the polyvinyl chloride substrate of 22.7 lines / mm.

Example 12

The procedure of Example 10 is repeated using a Mederschlagungsdauer of 30 seconds and a temperature of 1170 ⁰ C. A positive image is obtained on the polyvinyl chloride substrate with a resolution ₁ of 28.5 lines / mm «

The above examples illustrate the use of a porous web for processing. Of course, this web can either be saturated with the single bath developer or the single bath developer can be passed through the web from a reservoir in which the web and halide emulsion are immersed kick hindu.

According to another embodiment of the invention , as mentioned above, a hydrophilic layer, for example gelatin, is applied to a support. This · hydrophilic

.'909849 / 1191 Sohioht

So he did so many developers in a reasonable amount of time can hold back and release again, as required for processing the exposed silver halide emulsion is. It is therefore preferred that the hydrophilic layer can release at least 7 g / puss of the single-bath developer In addition, the hydrophilic layer should be retained as such stay and separate easily from the halide emulsion let · The hydrophilic layer must withstand a strong drying out, because the precipitation germs in the vacuum to be applied to their surface.

Example 13

An aerial photographic film is made by processing with a halide solvent from the emulsified one Silver halide freed. The clear film is then as in Example 1 with silver precipitation nuclei deposited in vacuo provided, but the deposition time is 30 seconds.

The seed-coated substrate is used to treat a Kodak special high-resolution aerial image film, type SO-243, which was exposed in the Bell Se Howell camera at 16 frames / second and f / 2.8. After two minutes of treatment, the negative is completely developed and a translucent positive image has formed on the substrate coated with germs.

909849/1191

Example 14 Example U

The procedure of Example 13 is repeated using gold as the precipitating nucleating material at a temperature of 1080 C to produce the substrate. The type SO-243 film in the model VI Sensito- ■ eter at 1/100 seconds is exposed to a neutral density filtration 0.8 to 2.3 and coated in the Eontakt ■ it precipitation nuclei clarified film for 5 minutes at 70 ⁰ F developed. A legative image is obtained on the aerial image file and a positive image is obtained on the substrate coated with precipitation germs.

Example 15

The procedure of Example 14 is referred to as silver sulfide minucleating material repeated. You get a negative image on the halide aulelon and a positive image on the substrate coated with precipitation nuclei.

Example 16

The process of Example 13 is repeated to produce a hydrophilic surface layer containing silver as precipitation nuclei. If the material to a fünfainutigen treatment at 70 ⁰ F of type SO-243 air

909849/1191

picture file »

Bildfilme is used, you get a Poeitivbild with a resolution of 64 lines / mm · A standard « Material but use in the diffusion transfer process, in which the precipitation nuclei through the whole hydrophilic layer, resulted in a resolution of only 40 lines / mm under the same exposure «- and Treatment conditions

Example 17

The device described in Example 5 is used for the deposition of silver precipitation nuclei on a cleared film. The silver is deposited on a pressed wool frame for 30 seconds. After the deposition, the coated substrate is used for the treatment of a silver halide emulsion which was exposed for one hundredth of a second in the model YI Sensitoaeter with a neutral density filtration in steps of 2.3 to 3.8. Is obtained during the development of Halogenidenulsion for 5 minutes at 7O ⁰ F a good Fositivbild on the substrate.

Example 18

The procedure of Example 17 is repeated with a germ depletion time of 60 seconds. You get

9 0 9 8 k 9/1 1 9 1 during

a good one during the development of the halide emulsion Positive image.

Pat entanaprüohe

909849/1191

Claims (12)

"26 - Pat entana preexe 1) A surface bearing precipitating germs Contact this surface with an exposed silver halide emulsion and a single bath developer A visible reverse image producing substrate, characterized in that the substrate for single bath developer is permeable. 2) substrate according to claim 1, characterized in that that the substrate consists of a hydrophilic material. 3) substrate according to claim 2, characterized daduroh, that the hydrophilic material is a coating of gelatin, polyvinyl alcohol, gum arabic or polyethylene oxides is. 4-) substrate according to claim 1, characterized in, daae the substrate is made of a microporous polyvinyl chloride consists. 5) substrate naoh claim 1, characterized in that it is a porous web or mat. 6) substrate according to claim 5, characterized in that the porous web or mat made of cellulose acetate, 909849 / 119t "., _ _ Cellulose triacetate Cellulose triacetate, polyurethane, fiberglass or paper ordered 7) substrate naoh one of claims 1 to 6, characterized in that the precipitation nuclei metals of groups IB ₁ II B, 17 A or TIII ₁ sulfides, selenides and tellurides of these metals or metals of group YI A are. 8) substrate naoh one of claims 1 to 6, characterized ■ marked that the precipitation nuclei silver, gold, mercury, tin or lead or the sulfides of these Metals are. 9} substrate according to one of claims 1 to 6, characterized marked that the precipitation nuclei UoId or silver are. 10) Method of manufacturing a substrate like one of the previous claims, characterized in that the coagulation germs are deposited in a vacuum will· 11) The method according to claim 10, characterized in that the bottom lowering takes place at a pressure of not more than about 10 ~ ⁵ mm Hg 909849/1191 12) Method of producing a visible reversal image on the surface of a substrate according to one of claims 1 to 9ι characterized in that nan an exposed silver halide emulsion with the surface and at the same time with single-bath developer in Touch holds. 909849/1 191