DE1572210A1 - Methods and material for obtaining photographic images - Google Patents

Description

DR. ELISABETH 3umTUNDT7fl. "V (n.TCETrVOSSIUS PATENT Attorney _Λ τ- r-, _o λ _Λ λ

1 O / Il IU

• MÖNCHEN 23 · SIEQCSSTRASeEa * · TELEPHONE Ϊ4§Ο · 7 · TELEQHAMM-ADIIESSEi JNVENT / MONCHEN

Zl May 1967

u.Zo: C 746 (fli / Vo / KC)
Pile 900 983

MIMESOTA KIKItfG AKD MAIiUPACTUHING COMPANY Saint Paul, Hlnneeota, Y.St.A.

"Methods and material for obtaining photographic materials

Pictures"

The present invention relates to a method for obtaining photogrephiacher images, in particular method and material sur Development of negative and / or positive images on exposed sensitized photographic material.

An object of the invention is to provide a generally improved and to provide more favorable development methods both in terms of process engineering and material.

A further aim is to create development processes that are particularly suitable - although not aussohlieeslioh - does the application ira connection with the Silver Sala Di ^ fueion method.

ΘΟ0Μ1 / 07.33

Another object of the invention is to provide a development method to create in which a leaf or its path has a 3 for this Purpose of particularly suitable and inexpensive material that is also available inexpensively and in sufficient quantities, is soaked or permeated with the developer liquid.

These goals can be achieved as in the exemplary embodiment shown in the following description and the accompanying drawings of the invention, with the single figure showing a schema - represents a cross-section through a camera, which is a greatly enlarged piece of photographic material according to the before lying invention contains.

In the known photographic process, which is often referred to as the silver salt diffusion process, the photographic exposure takes place on a sensitized negative layer, which is then developed in contact with a receiver layer that is not photosensitive but has nuclei on which there are the silver can deposit. Since the principle of the diffusion process and its various variants is sufficiently well known, its basics need not be discussed here. Details can be found in many normal photographic textbooks, such as "Photography, Its Materials and Processes" by C B. Neblette, fifth Edition, published 1952, pages 234 - 244 · As described in the book mentioned and readily understandable to the person skilled in the art, the negative emulsion can be applied to one layer support and the one containing the none · receiver layer can be applied to another layer support

909881/0733.

It must be ensured that the emulsion and the recipient are not brought into contact with one another at the transfer stage of the process; another possibility is that the _f Megativschicht to the positive or receiver layer on the same substrate is coated. An application of the present invention relates particularly to such an arrangement, in which the Negativechieht is applied to the positive or receptor layer and verifiable in effective _t functional contact, although not necessarily in direct physical contact therewith is because between Negativseiiicht and positive or receptions:? - a thin separating layer is not preferably arranged, which is permeable and does not prevent the desired transfer of the silver from the negative layer into the receiving layer «

In the past, it was common to use either a To develop a liquid bath or with the help of a viscous or semi-liquid developer material in the stage of bringing together of negative layer and receiver layer was distributed between the two. The bath method is not suitable for use in a photographic career, especially not in one small, compact hand-held kaaera for the amateur. The procedure - that makes use of a viscous developer liquid, is often used in amateur karaeras but not entirely satisfactory, la it is somewhat unclean and, moreover, generally requires that the negative layer and receiver layer instead of a single layer Supports, applied to separate supports.

Ke.ch of the present invention are the development and dia άεα-iit »usamiaenuän _£ ; 2r _; the Yorggang? -i after a procedure, the BADOR.QINAL 909881/0733

completely deviates from those previously used * Hach of the invention becomes neither a liquid developer bath nor a paste-like one viscous developer material used. Instead, a hydrophilic layer or web (processing layer) interspersed or impregnated with a liquid developer and exposed with the exposed Negative face burned into contact, so that a sufficient one Amount of stored liquid developer on the iiegativschicht transferred wii'cl to the necessary development In addition, the developer-carrying hydrophilic layer is used as a means of removing or peeling off the Uegative is used by the positive layer "so that the" Positional layer presents the eye as a finished image.

In the schematic cross section of the drawing, any desired photographic support is designated by 11. Depending on its intended use it can be of any thickness and any stiffness or flexibility, so it can e.g. be a glass plate, photographic film or paper. When exposure and development in a small, compact handheld camera for the mat surge need to be done is the use of a Sch ic Ki; carrier 11 made of paper is cheapest.

Applied to the substrate 11 is a receiving layer 13 "which is any check a conventional receiver layer composition, v / IE in £ iffusionsverfahren known ₅ act canoe containing 'lie required germs,

About the Er.pi'än _i -: er.TChio ..- t 13, is a peel previous year of. likewise ^ .- .. '^ "". ar kind of encouragement or relief

909881/0733

the separation of the receiver layer 13 from the overlying one Negative layer 17. All layers from 11 to 17 are made of conventional material, the details of which are for the purposes of the present Invention are insignificant and can be varied according to the available possibilities «

All of the layers 11, 13, 15 and 17 represent according to the invention the photographic material that is placed in the camera for exposure purposes and exposed in the focal plane of the camera with the light falling on the negative sheet 17 · After the In accordance with the invention, the material is then conveyed by suitable transport means of a conventional type, such as transport rollers or similar elements transported forward out of the focal plane and at the time of what is left the focal plane or at any other> later point in time, as long as it is still in the dark, with the hydrophilic rail 21 (processing layer) in contact brought, which was previously soaked or interspersed with developer fluid. The hydrophilic layer is created by any suitable means printed firmly against the front of the hegative layer 17, z, B « by a guide roller 23 around which the layer 21 runs when it meets the negative layer, the pressure on the opposite side of the composite material opposite to the collector 23 by a fixed surface or a rotatable one Role 25 is exercised.

The Andrueliraittel press the layer 21 so firmly against the layers of the total material that is contained in the layer 21 Liquid in sufficient quantity on the kegativschic / it

BAD ORIGINAL _QnöOQ .- _{/ n} «*«

17 passes over _e to the ENTV / i-sfctung this negative film to make, in the manner known in Ciffusioneverfahren, the undeveloped silver diffused into the negative layer 17 then by the intervening release layer 15 to the Empfangerschient 13, which contains the nuclei which promote the transfer of silver so that a silver image arises in the receiver layer 13, which is the counterpart to the latent image in the negative layer 17.

After the transfer of the silver salts from the negativschichi; 17 in the receiver layer 13, the negative layer 17 is to be peeled off from the receiver rail 13 so that the finished positive image on the layer 13 is released for viewing.This is done by using a material as the processing layer 21 whose affinity or adhesion to the negative layer 17 is greater than that of the negative layer to the receiver layer 13 * When the processing layer 21 is peeled off from the substrate 11 and the Em · "pfängerschicht 13 _f thus remains the Hegativsehichi; 17 lie on the processing layer 21 and is removed with it from the receiver layer 13, which Separation from the receiver layer is facilitated by the arrangement of the release layer 15 between the layers 17 and 13. The removal of the layers 21 and 17 from the receiver layer 13 is shown on the left in the figure »For example, the entire compound Material consisting of layers 11 to 21 is pulled or otherwise transported beyond the pressure means 23, 25 and then left in contact with one another for the required time (which varies between a few seconds and a minute or more), before that part of the combined sngssstaten

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j'aterial3 _f at which the development is completed, from the remaining "eil of the material ^ b ^ erissen and layer 21 together with layer 17 can be removed from the layers 11 and 15 °. The intermediate peeling layer 15 is so thin in any case, that it is irrelevant whether it is peeled off with layer 17 or remains stuck to layer 13 or whether it remains partly on positive layer 13 and partly on negative layer 17 'if both are separated from one another.

The ability of the hydrophilic layer 21 to adhere to the negative layer 17 j to adhere and the negative layer with it from the positive layer Subtracting 13 is important to the proper functioning of the development process of the present invention. If negative layer and the receiver or positive layer are applied to separate substrates or materials, both can After development has ended, the support can be peeled off from one another in order to separate the negative layer from the positive layer. It is obvious, however, that this is not possible if the Negative layer according to the method of this invention on a hearty one Layer support is applied over the positive layer. If ' '' Negativτ and PoBititcschicht are on a single layer support, one way of removing the negative layer would be to pass the composite material through a liquid bath, which dissolves the negative layer without the to damage the Pösltivschicnt underneath. However, while theoretically possible, it is for use in a small, compact handheld camera unsuitable for amateur use. The present invention solves this problem by using the particular Processing hole 21, which serves the dual purpose of

BAD ORIGINAL 809881/0731

Firstly, to serve as a means of applying the developer fluid to the negative layer and, secondly, to separate the lying layer from the poeitive layer after development is complete - the requirements that must be placed on a special processing layer to fulfill these two functions are still very much a must adhere well enough to the gelatin (emulsion) in the negative layer 17 to be able to take the negative layer with it when the processing layer is peeled off the positive layer. In other words, the attraction between the hydrophilic processing layer and the photosensitive negative layer must be greater than the attraction between the photosensitive negative layer and the positive receiving layer, at least after the hydrophilic processing layer has been in contact with the photosensitive negative layer long enough to allow the negative image to develop complete and transfer the fositive image to the recipient layer. In addition, the hydrophilic treatment layer must have sufficient absorption capacity and be able to absorb a sufficient amount of developer solution to achieve the desired result. Furthermore, the processing layer must not have any adverse photographic effect. This means that nothing in the particular processing layer must react adversely with the negative photosensitive layer or any other part or element of the composite photographic material or the camera in which it is used. In addition, the processing layer must be stable to the alkaline nutrient liquids or solutions that are to be used. After all, it would be of great advantage if this special processing was in the form of an inexpensive and easily available,

S09M1 / 0733 _BAD

self-supporting film would be available »

Quite unexpectedly, it was found that the film of regenerated cellulose (regenerated cellulose), all of these desirable properties combined in to _$ and it is the use of regenerated Csllulosefc-lie for this purpose, which one of the v represents esentlichen points of this invention üie using normal regenerated is preferable to the so-called moisture-resistant regenerated cellulose, normal regenerated cellulose is well known and is dealt with in visual technical publications. See, for example, the article "Cellophane" beginning on page 280, BairL 3 "of the 1949" Encyclopedia of Chemical Technology (edited by Raymond E. Klrk and Donald F. Othraer, edited by Intersaionce _{c Hew York City),}

Pur purposes of the present invention, commercially available Regeneratcellalosefolle proved normal quality _(e n h ₀ are not moisture resistant) with a thickness of about 0.05 mm as well geeignet-, she takes with ease about 5 milliliters developer;? -

solution per 929 cm on _o "This amount is sufficient to achieve a completely sufficient development of the negative and transfer of the image to the positive. In addition, this film material has sufficient stability in an alkaline developer solution with a ρ" - fourth of over 11.0 ο

The microporous structure of the film material is also an advantage / since it allows the diffusion of water to the back of the film sum Ajcaats des there; allows evaporating water and thus contributes to the i'röckxiunt ;, des_ 3es «hiohteten material, ^BAD 90988 1/07 33

The excellent adhesion between the foil material and the Gelatine on the photosensitive coating layer is a special one unexpected property, and it is this liability that is essentially responsible for the success of this invention by it opens up the possibility of a single .working layer (hence the regenerated cellulose film) for the dual purpose of Application of the developing liquid to the composite photographic material and the separation of the developed Jiega ™ tive layer of this material to be used.

The discovery of the excellent bonding properties between the film of regenerated cellulose and the gelatin of a photographic emulsion also makes it possible, in another application example of the invention, to use the film for removing the gelatin from photographic material, where these are due to different circumstances and not necessarily is desired in connection with the diffusion method, the invention may in sinem = application example used such a! film _F üb. In connection with one of the well-known methods for the production of photographic gelatine = tanning reliefs to be applied to unwashed gelatine and peeled off, see page 422 and the following in the obsn’t mentioned book by Neblette .;

Means for receiving a supply of ausamraengesetaten pho'so-graphic Matsrials punch a supply of with SNTV / ioiclerf3 üa assured by continued iOlie are preferably "dingt ιώβ-but not in the camera" built Thus, the Kaisieragehäuse 31? as indicated in the table, means for receiving a gate roll, 53 of the assembled photographic material with the layers

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11r 13 »15 and 17 as well as means for receiving a supply roll 35 of the iOlienmaterials 21 interspersed with the liquid. Means are provided for transporting the required quantities of photographic material from the supply roll 33 to the recording position designated 41, where the material is exposed to the light falling through the lens 43 into the camera when controlled by a suitable shutter (not shown) of known construction can. Means are also provided for transporting the exposed material from the pick-up position 41 to that position which can be referred to as the development or processing position 47, as well as for the simultaneous transport of the desired amount of film 21 from the supply 35 to the front-to-front pressure the exposed material and in particular on its negative layer 17 during the development period and while the negative EC layer is in the development division 47. It is assumed that the processing layer or the liquid carrier layer 21 of the regenerated cellulose film remains motionless on the negative layer with which it is in contact for the period of development. On .rinde the development period dae developed material is torn away from the remaining material and the layer 21 drawn off from the substrate 11, the layer 21, the! "Egativschicht entrains 17 and _t are as above, already explained, the positive layer leaves on the substrate 11 13 .

The means mentioned for transporting the composite photo graphic material as well as the means of transporting the layer need be nothing more than a manual pull on the material to overcome the frictional resistance and to pull through between

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the rollers 23 and 25 ο Of course, motor-driven Transport rollers of known type are used. The same goes for

for the means mentioned for separating or peeling off the layer 21 from the layer carrier 11, which also only needs to be a manual pull, the layer carrier 11 with one hand and the layer 21 is taken with the other and both are separated from each other by pulling.

At various points in the explanation and in the claims the fact is mentioned that a layer is "in contact." with “or“ on ”another layer. It should be noted that this formulation is only functional in one aspect Sense is used and not to identify the exact physical construction or relationship that can be varied. For example, in the preferred exemplary embodiment, the negative layer 17 can be referred to as "on" the substrate 11, although the layers 13 and 15 between layer 17 and substrate 11 are »Likewise, the negative layer 17 can be described as" in contact with "the positive layer 13, since it is used to transfer the image from the negative layer 17 into the positive layer 13 is in effective functional contact therewith, although the thin release liner 15 is physically between the two. The negative layer 17 can also be said to be "in contact with" the layer 21 made of Hegenerat cellulose, although it may at times be desirable to have some known form of coating over the Use negative emulsion, provided that it is a permeable coating that allows the transfer of developer fluid from the layer 21 to the negative layer 17 does not hinder nor the ^ strii & aoxite adhesion of the layer 21

909881/0733 iAD oricknal

impaired on the negative layer.

As mentioned above, one of the essential ingredients is the Invention in the use of a film made from regenerated cellulose both as a carrier of the developer liquid and as a means of application this liquid on the negative layer as well as for Achievement of adhesion on the negative layer that enables peel off the negative layer quickly and easily from the positive layer «, The exact details of the negative layer, the positive or receiver layer, the release layer (if one is used is) and the developer liquid used are therefore of no importance in the overall framework of the invention and can be used the available options can be varied as desired. To name a specific example of the invention, however, can be said that the following construction has proven itself:

As a support 11 paper of the type of photographic paper, for. B. baryta paper, with a thickness of about 0.25 mm can be used. The positive receiver layer 13 preferably contains the seeds for promoting the image transfer from the negative layer. These germs can be made of colloidal particles of silver, gold "or consist of platinum, or from the sulfides, selenides or tellurides of Silberp GoID _n platinum or other heavy metals; or Mer- = captanen or Metallsalaen of mercaptans" You can in gelatin or other colloids or Embedded in polymers, and they can be bound to colloidal silica or other inert, water-soluble substances which tend to combine the nuclei into suitable aggregates. Suitable receptor layers are known and are described in US Pat

8Q8881 / 0733 BAD original

No. 2,352,014, 2,698,236, 2,698,237 and 2 _β 698,245 as well as French patent specification Mr. 879 »995 and many others.

The photosensitive liegativaohicht 17 preferably contains one Halogen-silver-gelatin emulsion of the conventional type with one sufficient for taking pictures in a popular camera Speedβ An emulsion with a speed of 100 up to 200 ASA is considered sufficient.

To make it easier to peel off the light-sensitive negative layer 17 from the image-receiving layer (positive layer f receiver & sees) 13, an intermediate or peeling layer 15 can be provided, as already mentioned. This layer is only necessary or particularly desirable; when the negative layer 17 would normally have a greater affinity for the receptor layer 13 as compared with the machining processing layer 21 * This would be _o the case if the receiver layer 13 contains a high gelatin content as film-forming Kolloild "Suitable release liners are known in the photographic art and can be composed of one or more of the following substances: gum arabic, acetyl cellulose, polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, sodium alginate "pectin, polymethacrylic acid and other VS.SSQT" or allialil-soluble polymers. In addition, mixtures of the above substances can also be used with water-soluble, non-polymeric substances can be used. These layers are preferably very thin · Thicknesses between one and three microns have all proven to be suitable »

»09881/0733" * BAD ORIGINAL

~ 15 -

A separate peel layer is not necessary if the affinity falls

of the photosensitive layer 17 for the receiver layer 13 in when wet is much lower than for machining layer 21. -This is the case «if that is the receiving layer 13 forming colloid consists of a material that has only limited compatibility with gelatin, such as polyvinyl alcohol, by adding e.g. dirnethyl urea or aromatic Polyhydroxy compounds can be cured or crosslinked.

The following composition can be used for the nutritional fluids be chosen:

Sodium sulfate (anhydrous) 40 g Hydroquinone 25 g

1-phenyl-3-pyras! olidone 5 g

Sodium hydroxide 12.5 g Sodium thiosulfate. 20 g

1-phenyl-5-mercaptotetrazole 0.23 g

fill up with water to 1 liter

Clay of such a solution will be about five milliliters per 929 om incorporated into the poly for the processing layer 21.

As can be seen from the above explanation, Zweok and The aim of the invention is fully met. However, it is specifically pointed out pointed out that the above description of an application example is only intended to explain the method and not as a $ ftechlimitation is to be understood and that the details are without being taken from the Deviation from the invention can be varied within the scope of the following patent claims

909881/0733

Claims (1)

■ - 16 claims I ο / 2 2 Ί Ο 1 «A photograph! High development pack consisting of one Layer support (11), a positive receiver layer (13) on this Layer carrier which is not suitable for receiving a fositive image from a negative layer (17) by diffusion from the negative layer (17), a negative layer (17) over the receiver layer (13), a peel-off layer (15) inserted between the negative layer (17) and the receiver layer (13), a transfer layer (21) superimposed on the negative layer (17) and a transfer layer (21) in developer liquid stored in the transfer layer, characterized in that the transfer layer (21) consists of regenerated cellulose and a larger, Has affinity for the negative layer (17) than the negative layer (17) for the receiving layer (13), so that after the development of the negative layer (17) has been completed, the developer liquid contained in the transfer layer (21) removes the transfer layer (21) from the support (11) can be pulled off and thereby taking the negative sheet (17) with it, whereby the fositive receiver sheet (13) remains on the layer support (11). 2 · Combine a gelatin-based photographic emulsion with a layer Regenerated cellulose, which is directly superimposed on the emulsion mentioned and has a strong affinity for the gelatin of the emulsion, so that when the regenerated cellulose is peeled off from the Layer support the gelatin of the emulsion has a tendency to adhere to the regenerated cellulose layer and to move with it 909881/0733 To solve the support. 3. Containing a photographic apparatus a) Means for receiving a supply of a pack photograph! aohm Materials, one part 1) a support (11) and 2) a receiver layer (13) on the layer support (11) » 3) a photosensitive emulsion layer (17) and 4) a peel-off layer (15) embedded between the receiver layer (13) and the light-sensitive layer (17) » b) Means for transporting said pack from a storage position to a receiving position »so that it can be exposed to light falling on the light-sensitive layer (17)» c) Means for receiving a supply of film (21) made of regenerated cellulose with an impregnated developer liquid, d) Means for transporting said part of the pack out of the Exposure position in a development position and, at the same time, transport of part of the polio (21) from its storage division to a development position and direct front-to-front contact between the film (21) and the light-sensitive one Layer (17) of the pack mentioned, so that both adhere to one another and the developer liquid soaked in the film (21) forms is transferred to the photosensitive layer (17) and its Development as well as the diffusion transfer of a positive image onto the receiver layer (13), as well as BATH ORIGINAL 909881/0733 e) Means for separating the film 21 and the photosensitive layer (17) adhering thereon from the support (11) and the remaining receiver layer (13). 4 «Sin photographic apparatus containing: a) Gown for taking a stock of a pack of photograph! - see materials, including 1) a support (11) and 2) a receiver layer (13) on the layer support (11), 3) a photosensitive layer (17) and 4) a peel-off layer (15) embedded between the receiver layer (13) and the light-sensitive layer (17) » b) Means for transporting said Fackung from a storage position in a receiving position, so that it can be through to the light-sensitive layer (17) falling light can be exposed » c) Means for receiving a supply of τοη film (21) made of rain cellulose with soaked developer liquid, d) Means for transporting said part of the pack from the exposure position to a development position and to simultaneous transport of part of said film (21) from its storage position into a development 909881/07 33 ^v bad original position and direct front-to-front contact between the Film (21) and the photosensitive layer (17) of said pack, so that both adhere to one another and the in the film (21) Soaked developer liquid is transferred to the photosensitive layer (17), and its development as well as the diffusion transfer of a positive image to the receiver layer (13) causes e) said film (21) having a greater affinity for the photosensitive layer (17) than between the photosensitive layer (17) and the receiver layer below (13), so that the film (21) when peeling off the support (11) takes the photosensitive layer (17) and the Enpfängerschlcht (13) leaves behind on the substrate (11). 5. The process of developing a photographic material, characterized in that a layer support (11) and a light-sensitive gelatin layer (17) located thereon are also included a developer containing processing layer (21) from Rege- neratcellulose whose affinity for at least a part of the Qelatineschloht is greater than the affinity between this part of the Qelatineso layer (17) - and the layer support (11), if necessary with an interposed peel layer (15) in front-to-front contact brings and, after development, the layer (21) is removed from the layer support (11). BATH ORIGINAL 909881/0733 Lee Fie ite