DE1797084A1 - Multi-layer film - Google Patents

Description

AGFA-GEVAERT AG LEVERKUSEN

Yes at?,

Multi-layer film

The invention relates to a multilayer film made from consists of a black pigmented layer and a white pigmented layer.

The multilayer film according to the invention consists of two .. ' hydrophobic layers which are cast one after the other from dispersions in low-boiling solvents. The second Layer is already applied when the first layer still has a substantial amount of low-boiling solvent for contains the hydrophobic film-forming binder of this layer. One of these layers is a cellulose ester layer, which is a contains black pigment, while the other layer is a cellulose ester layer in which a white pigment is incorporated became.

Such a multilayer film is particularly suitable for Use as a carrier for a photographic material, in particular for a photographic material with which images can be made according to the diffusion transfer process. This photographic material can be a photosensitive one Be a material that is a very light-sensitive silver halide--

A-G 408

109830/1957

contains emulsion layer and that for exposure in a cassette of the commonly used for X-ray materials Type or in a camera used for the production of positive halftone images- The principles of the diffusion transfer process were described by E.H. Land in "Journal of the Optical Society of America" Volume 37, February 1947, Volume 2, pp.61-77.

It would be interesting if the set consisting of the photosensitive layer and the image-receiving layer were made up of the The camera or the cassette could be removed after the image-wise exposure of the sensitive layer and that both the development of the negative image and the formation of the positive image by diffusion transfer outside the camera. In this case, the structure of the exposure unit could be greatly simplified.

It is therefore advantageous, and often necessary, that the photosensitive layer should be removed until the complete end of the Processing is protected from incident light. So far none have been satisfactory in all respects for this problem Solutions proposed. A sheet of black paper with a white pigmented gelatin layer was covered as a support for the silver halide emulsion layer, there are disadvantages of high cost and cost a rough surface. The inventive light

AG 408 109830/1957

So delicate material offers a very simple as well as happy solution to this problem.

The inventive photosensitive material contains a light-sensitive silver halide emulsion layer and a hydrophobic film support consisting of two hydrophobic layers. These two hydrophobic layers were sequentially cast from dispersions in low-boiling solvents. The second shift was applied when the first shift still contained a substantial amount of low-boiling solvent for the hydrophobic film-forming binder. One of these layers is a cellulose ester layer, which has a black pigment, while the other layer is a Cellulose ester layer with white pigment is. The light sensitive The silver halide emulsion layer is on the side of the light-sensitive material where the white pigmented layer is applied.

According to a particular embodiment of the invention, J the photographic material has a photosensitive layer and, moreover, an image-receiving layer, so that in this Pail a so-called multi-layer material is created.

The invention also relates to a method for producing images according to the silver salt diffusion transfer method, according to which a photosensitive material according to the invention is exposed to an image-wise modified actinic radiation and in the presence of a treatment

109830/1957

A-G 408

liquid, a developing substance, a silver halide solvent and alkalis with an image receiving layer is brought into contact so that a negative image is developed in the silver halide emulsion layer and through Diffusion transfer a positive image in the image receiving layer arises. .

According to a preferred embodiment of this invention a light-sensitive material having a silver halide emulsion layer with camera sensitivity or with one for registering image-modified X-rays or radioactive rays suitable sensitivity contains, exposed image-wise in a light-tight camera or cassette and then in contact with a Image receiving layer protecting the front of the photosensitive Layer outside actinic ambient light brought to the camera or cassette so that the development of the silver halide emulsion layer and the further treatment as described above can take place.

Protecting the front of the photosensitive layer in front of ambient actinic light, as will be described in detail below, can be done in a number of ways. The use of an image receiving material is very interesting whose carrier is a multilayer according to the invention Film carrier is made of a black pigment containing * Cellulose ester layer and a cellulose ester layer containing a white pigment. Development seeds can

109830 / 19S7

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optionally applied to the pigmented layer are »Such an image receiving material has the advantage that there is a white background for the diffusion transfer image offers, and that it reads almost no actinic light, so that from the photosensitive material and the image receiving material set for development and image creation by diffusion transfer from the camera can be brought into actinic light immediately after putting together the said sentence, The Invention thus also applies to the image receiving material described in this paragraph and a method of making diffusion transfer images using this image receiving material optionally in combination with a light-sensitive Material containing a carrier of the same type is applied.

The hydrophobic film according to the invention exists, as already was discussed above, from two different hydrophobic cellulose ester layers, which are successively made from Dispersions were poured in low-boiling solvents. It is particularly advantageous to use the dispersion for to apply the preparation of the second layer to the first hydrophobic cellulose ester layer, namely if ^ the latter is just getting a stable form, i.e. when it

f ° is in a semi-solid state and does not change shape

sderuriqen is more subject, although it is still an essential one.

OJ the amount of low-boiling solvent for your film

Hy
bildendos contains binders, so one achieves one

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excellent adhesion between the two hydrophobic cellulose ester layers, which form the multilayer film. It is believed that this strong liability is due to fact is that the colloidal chemical state of the first layer in this particular period of its formation is that of the freshly cast second layer allows to form a strong bond with the hydrophobic cellulose ester of the first layer. However, the low-boiling solvent of the second layer cannot penetrate into the first layer to a high degree, so that the first layer is not dissolved or softened to the extent that it would be compromised.

The term "low boiling solvent" means any of the known solvents for Celluloseester having a boiling point lower than 10O ⁰ C. The most important are methylene chloride, 1,2-dichloroethane, carbon tetrachloride, acetone, methanol and ethanol.

A preferred embodiment of this invention is that Cellulose ester layer with black pigment is a hydrophobic cellulose ester layer, the finely divided carbon black in one Concentration of 1-5% by weight with respect to the total amount contains solid substance in the black pigmented layer. For dispersing the soot in the black pigmented layer of the multilayer film support can be obtained, for example, from a concentrated suspension start from soot in a dilute solution of cellulose ester in (a) low-boiling solvent (s). To the

* @ 109830/1957 ^ ₀ opeiNAL

To produce this concentrated suspension, for example, a mixture of equal parts by weight of carbon black and hydrophobic cellulose ester in a certain amount of low-boiling solvent (s) for the cellulose ester is treated in a ball mill until a stable, still liquid suspension is formed. This concentrated suspension can then treated with a solution of the same · Celluloseester and the necessary amount of plasticizer in the same organic low-boiling solvent to be diluted until the desired degree of blackness M and the desired viscosity is reached. If the mass contains at least 2% by weight of carbon black with respect to the total amount of solid substance, the films cast therefrom, at least if they have a thickness of about 100 μm, are mostly sufficiently opaque for use in accordance with the invention. If the film has a thickness of less than 100 microns, the carbon black content should of course be increased so that the film is sufficiently opaque. The above figures depend on the type of carbon black used and on its degree of dispersion. The smaller the diameter of the soot particles, the smaller the required amount of soot. The optical density of the black pigmented layer must be about 8 when viewed through.

- · You can cast the white-pigmented layer ο

Proceed in a similar manner for _{O 0.} A hydrophobic cellulose

ο the ester layer becomes a well-known, finely divided white

^ l pigment such as titanium dioxide, barium sulfate, zinc oxide or lead

* j oxide added. These pigments are incorporated into the cellulose ester

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composition that contains the necessary amount of plasticizer for the cellulose ester, in a concentration of 10 to 55% by weight in relation to the weight of solids in the white pigmented layer dispersed. The concentration depends on the nature of the white pigment used and the desired degree of light reflection “When the concentration of the pigment in the hydrophobic cellulose ester layer is more than about 25% by weight, the cast layer is in spite of this added usual amounts of plasticizer for cellulose esters too brittle. However, this brittleness is also determined by the type of white pigment used. To this one The hydrophobic binder is used to remedy imperfections the white pigmented layer in this pail made of one Mixture of a hydrophobic cellulose ester and a miscible hydrophobic polymeric material, the latter as a polymeric plasticizer for the white pigmented cellulose ester layer or as an additional plasticizer if already a known plasticizer for the hydrophobic cellulose ester is used.

The bulk of white pigment and cellulose ester can also can be made using a ball mill. To this

^ Purpose is the white pigment with a certain amount

oo cellulose ester and low-boiling solvent for short-ω

^ ground early. The stable suspension obtained is

<O then intimately with a solution of the same hydrophobic cellulose

*** esters, which optionally contain a known plasticizer

contains, mixed. If necessary, a lot will be dissolved

hydrophobic polymeric material mixed with the white mass formed. The suspension is then mixed with the required amount of low-boiling solvent until it is reached diluted to the desired viscosity «

After another process, the white pigment is in dispersed a solution of the polymeric material. If necessary, a dispersant can also be added to this mass. A solution of the polymeric material and the cellulose ester and optionally a plasticizer is then added Achieving the desired proportions added.

If the casting compound contains more than 10% by weight of white pigment in relation to the total weight of the solid substance, one can hereby apply a white film to a black substrate, with the composite film at least 70% of the reflected light incident on the white side of the layer, at least if there is only a thin silver halide emulsion layer on it is shed. If the concentration of the white pigment is higher than 30% by weight, even one can be used Achieve light reflection of more than 85%. This stronger one In practice, reflection results in an increased sensitivity of the light-sensitive material. ·

oo The thickness of the cellulose ester layer with black pigment to

° is preferably 50-100 u, while the thickness of the white pigmented layer is preferably 10-50 u "^ ⁴ , so that the total thickness of the multi-layer carrier mostly fluctuates between 0 and 150 u.

Dig common hydrophobic cellulose esters e.g. cellulose triacetate, Cellulose diacetate, cellulose nitrate, cellulose proponate, cellulose butyrate, and mixed esters such as cellulose acetopropionate can expediently both for the black pigmented layer and for the white pigmented layer Layer can be used. However, it is not at all necessary that the same hydrophobic cellulose ester be both ^ for the black pigmented layer as well as for the white one pigmented layer is used.

The known additives such as plasticizers and, if necessary, stabilizers can be added to both layers of the multilayer Film carrier are added. As has already been explained above, it is theoretically sufficient if in the white pigmented layer as a binder only a hydrophobic cellulose ester, which is normally triphenyl phosphate as Contains plasticizer is used. When large amounts of white pigment are added to the photographic exposure To ensure a strong reflection of the incident light, one obtains with bare cellulose ester as a binder however, a layer that is too brittle. This imperfection can be remedied by adding Jj-4 parts by weight of hydrophobes - * polymeric material as described below, per part by weight

oo cellulose ester added. This is how the white pigmen- The layer is extremely flexible.

cn To form the white pigmented layer

Solution of cellulose ester a miscible solution of a

/ 8th

hydrophobic polymeric material added, especially when di ^ The concentration of the white pigment is more than 25% by weight. This polymeric material can be a low molecular weight polyester modified with an aromatic or aliphatic diisocyanate. The lower molecular weight one Polyester can be produced by reacting one to ten carbon atoms containing aliphatic diol or a mixture of such diols with a maximum ID of carbon atoms aliphatic dicarboxylic acids The term "aliphatic diol" iit to be understood in its broadest sense, i.e. he also includes aliphatic diols, the chain of which has heteroatoms, as in the case of the dialkanolamines, in particular of diethanoi amines. Very good results have been obtained with polyesters of ethylene glycol and adipic acid or of ethylene glycol, Diethanolamine and adipic acid, these polyesters having a molecular weight of about 2000-7000. These low molecular weight polyesters are mixed with aromatic and aliphatic diisocyanates, e.g. 2,4-toluene diisocyanate or hexamethylene diisocyanate modified to make hydrophobic polymeric materials with a molecular weight of about 20,000-25,000 can be obtained.

- * The composition of the white pigmented layer can be

CD _t
CD

O ₀ regulate within wide limits.

^ The best results are achieved, however, when the layer

(Xi has about 3 ^ -4 parts by weight of polymeric material per part by weight of cellulose ester. When using these products

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in a ratio within the stated wide limits, the final multilayer film, the .as support for the further layer (s), the photographic material according to the invention has a valuable flexibility.

In the production of the multilayer film which is used as a support for the photographic material according to the invention the black pigmented layer does not necessarily have to be used

Q | be poured as the first layer, after which the composition the white pigmented layer is drawn over it » In practice, the reverse order of application is actually mostly chosen. First, a dispersion is a white pigment in cellulose ester and optionally a polymer material on a rotating metal cylinder or on an endless metal belt, a film casting machine potted, after which a dispersion of a black pigment in cellulose ester with known additives such as plasticizers

P. is applied to the partially dried film. To As is known, the multilayer film is peeled off after drying and further dried. The film is now ready for Completion of the photographic material according to the invention coated with one or more layers

O become.

ο ■ Between the black pigmented layer and the - ** white pigmented layer creates a strong adhesion,

^ j because the solvent of the second layer is effective Adhesion with the still moist, first cast layer

causes.

The multilayer film base described above offers the photographic material according to the invention all sorts of advantages the diffusion of the unexposed silver halide salts in A, the image-receiving layer, enables the developing liquid and the diffusing silver halide salts to not penetrate into the support, thanks to this impermeability, so that none of them is lost.

Because the 'flexible white pigmented layer is usually is first applied to the casting machine and then the black pigmented layer is poured onto it, the surface of the white layer is particularly smooth and flat. In any case, the surface is much smoother than when conventional paper is used as a carrier, even if this is used Paper was first coated with a top layer. You can get much more even surfaces on such a smooth surface Apply layers, creating an intimate contact between the

Φ photosensitive layer and the image receiving layer during

t * i dor diffusion transfer enables «So a O

^ ₁ dense precipitation of image silver ..

** ί Such negative material is almost 1 i impermeable,

when it comes into contact with an image receiving material,

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which does not have a translucent support, due to the fact that the black pigmented layer almost completely prevents the penetration of light. Due to the presence of the white layer under a thinly cast silver halide layer, a stronger light reflection is observed during the exposure. Measurements have shown that 70 to 95 % of the light that penetrates the photographic camera is reflected, which results in a large increase in the photosensitivity of the negative material.

When preparing a photographic material for use in the silver salt diffusion transfer process, any silver halide emulsion layer capable of sufficiently rapid development of the exposed silver halide and allows a sufficiently rapid formation of silver halide silver salts can be used.

According to a preferred embodiment, the silver halide emulsion layer is rather highly sensitive, so it should be protected from the effects of ambient light. This emulsion can either be in a camera, or directly or indirectly (by means of a fluorescent screen) according to image Q modified X-rays or radioactive rays, such as oo in the published Dutch patent application 6803940

® described, be exposed.

cn To register by means of a camera one uses vorzuq vorzuq Silver halide emulsion layers with a fairly

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which gradation can be used appropriately for halftone reproductions. These emulsion layers can be of the type used in the production of black and white diffusion transfer images as well as of the type used in the production of color diffusion transfer images. Further details on this can be found in the above-mentioned EHLand article.

The photosensitive emulsion layer is over the white ^ pigmented layer of the multilayer film drawn, if necessary after only one or more suitable ones Adhesive layers and / or one or more additional layers have been applied.

The silver halide emulsion layer of the photosensitive Materials can be coated with a water-permeable layer. The latter layer can consist of a water-insoluble Metal alginate as in British Patent 998 955 or from a carboxymethyl cellulose chromium ™ salt optionally in combination with a water-soluble one Metal alginate as described in British patent specification 998 956, be composed .. Preferably

^ however, becomes an uncured or slightly cured layer

oo applied to the silver halide emulsion layer. In this co

^ Related can be found in British patents 1,054,252, ca 1 054 253 and 1 057 273.

(Xl ■

To carry out the inventive method, the in combination with the above photosensitive

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Material to be used for the image receiving layer is part of a well known separate image receiving material. Such a receiving material contains a suitable support for example a paper support or a hydrophobic film support, and the image receiving layer, which is usually (a) Has substance (s) for the formation of an imagewise silver precipitate from the diffusing silver halide salts, i. E. the so-called physical and / or chemical development

t germs in a colloid or in an inert environment.

Silica are dispersed.

According to a particular embodiment of the invention the image-receiving layer containing development nuclei on the hydrophobic multilayer film support, on which the photosensitive layer was also cast, applied, see above that a multilayer material is formed. However, the image receiving layer and then the photosensitive layer can be applied. Most of the time, however, there is one between the two layers suitable separating layer provided. More details on multilayer materials and their treatment can be found are found in British Patents 1,060,292 and 1,027,742. ° However, the multilayer material can also be used one after the other

cj support, the photosensitive layer and the image receiving

^ * ■ layer included. A thin layer in which the diffusion:

P ₁ transmission image is present, although this is not inaner

-4 ■■ ■;.:

is necessary to be transferred to another sheet « AG 408

To produce a diffusion transfer according to the invention. ^c : Image, the photographic light-sensitive material is imagewise exposed and kept in contact with an image-receiving layer in the presence of a processing liquid, a developing substance, a silver halide solvent and alkalis. After the image has been formed, in most cases at least a thin layer of the image receiving layer containing the diffusion transfer image is peeled away from the photosensitive layer.

The photosensitive layer and the image receiving layer must not necessarily brought into contact with each other after exposure. Sometimes e.g. when a multi-layer material is used, the image-receiving layer will in fact be in contact with the silver halide emulsion layer earlier brought.

The term "touch between" does not necessarily mean direct contact, but also the ™ Contact with at least one water-permeable intermediate layer that allows the transfer of the treatment liquid, the required for image production by diffusion transfer

Tf borrowed ingredients and the silver halide salts from one CO

Co layer to allow another.

_{im / k} The image-receiving layer is the layer containing the development germ

tfl in or on which the diffusion transfer image is formed

will. When separating the photosensitive layer from the Image receiving layer is at least one thin film

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Layer of the latter from the silver halide emulsion layer deducted.

According to a particular embodiment, the development - · germs instead of being incorporated into the image-receiving layer during its manufacture, the image-receiving layer during its manufacture the treatment, for example, made available with a treatment liquid containing developmental germs. Details about this embodiment can be found in the British Patents 1,001,558 and 1,052,022.

The image receiving material includes all of the material with the Image receiving layer, possibly including that on it transferred thin layer containing the diffusion transfer image.

When carrying out the method according to the invention the aqueous treatment liquid on the photosensitive Material and / or the image receiving material, preferably on the photosensitive material alone or on both materials attached «The treatment liquid can be applied in various ways, e.g. by submerging the material to be moistened

_ »In the treatment liquid, by means of a roller

o,

Ό Contact of the material with an _{object soaked in treatment liquid o} by spraying on or by

- * spread of a treatment liquid that is viscous or not, to

encapsulated in a container, for example.

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The ones used to carry out the diffusion transfer process required ingredients ie. the developing substances, the silver halide solvents and the alkalis may be incorporated into the treatment liquid. One or however, several of these ingredients can be used in the Photographic materials incorporated «More information about the incorporation of the developing substances into the materials can be found in the niedgr land i see patent specification 107 251 and in British patents 1,012,476, 1,042,477, 1 054 253, 1 057 273, 1 086 510 and 1 093 177. If all developing substances are entered in the materials used

the treatment liquid can be reduced to a merely alkaline one Solution that optionally contains a silver halide solvent may contain, returned. When the alkalis and If the silver halide solvent is also incorporated into the materials, even water alone can be used as the treatment liquid. In this context can See British Patent 1,013,343. For the production of colored images in the image receiving layer the necessary compounds must be present in the materials used and / or in the treatment liquid

~ »Be. The others more common in the diffusion transfer process

* £ wisely applied ingredients are allowed in the used O materials and / or incorporated in the treatment liquid - * leads to be. Such ingredients are e.g. stabilizers,

^ ₁ Hardeners, preservatives for developing substances, compounds that prevent yellowing, image tinting agents, sludge preservatives, pigments and latexes.

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All of the treatment liquid or those used Ingredients incorporated into materials are used in the usual concentrations generally known from the specialist literature. .

According to a preferred embodiment of the inventive The method becomes a photosensitive as described above Material protected from ambient light in one Imaged according to the camera or in a cassette.

In order to achieve the treatment which leads to the formation of a diffusion transfer image performs at least for the most part in actinic To be able to carry out light, whereby the treatment device ζ.Bo the camera itself can be considerably simplified, must also be the front of the exposed silver halide material protected from actinic light before removing this material from the camera, cassette or treatment device, which protects the superhalide material from ambient actinic light. Protecting against Actinic ambient light can also be used with an image receiving material, one or more layers of which do not allow light to pass through (e.g. a material with one of the light-sensitive Material similar multilayer film base) or

_{ω of} which the back with a separate opaque oo

to foil can be realized by the ο

_ ^ Image receiving material against the light-sensitive material

cn is pressed before the sentence thus formed is exposed to the light is exposed. The separate opaque film can be removed afterwards if necessary. In the event of

Wall of a multilayer material comprising a photosensitive silver halide emulsion layer and an image-receiving layer, a separate opaque film can be brought into intimate contact with the multilayer material before the whole is exposed to the actinic ambient light. This separate foil may also dienen- as an auxiliary layer for separating the photosensitive layer of the image receiving layer after image formation by diffusion transfer this auxiliary layer (a) compound (s) GT, which is needed for the manufacture of Diffusionsubertragungsbildes (are), as described in the American Patent 1,027,742.

The treatment liquid can, as described above, straight be applied before the light-sensitive material and the image receiving material or auxiliary layer are brought together » The sentence is then passed directly into the light, so that the development of the silver halide emulsion layer and diffusion transfer image formation ^ can take place. During these treatments, the photosensitive layer is protected from actinic light » Instead of applying the treatment liquid, you can

to the latter also be encapsulated in a container, with

this container forms part of the said set.

^ ₄ By compressing this sentence brought into the light Ή the liquid can be spread out so that the development - • 4

can begin.

A Π 4 ΛΟ

SAD

- 22 The following examples illustrate the invention.

At game 1

By polycondensation of adipic acid with a mixture of ethylene glycol and diethanolamine, a polyester with a Molecular weight from 5000 to 7000 formed, according to which by reaction of this polyester with 2,4-toluene diisocyanate a polymeric material with a molecular weight of about 25,000 results.

A mixture that consists of 400 g of titanium dioxide and 60 g of cellulose triacetate in 880 ml of a mixture of 90 parts by volume Methylene chloride and 10 parts by volume of ethanol is treated in a ball mill for 48 hours. So educated white paste is a solution of 60 g of cellulose triacetate in 1000 ml of said mixture of solvents admitted. A solution of 400 g of the polymeric material obtained in 8OO ml of 1,2-dichloroethane is with the obtained suspension mixed.

The white pigment composition is applied to an endless belt of a film casting machine in such a way that the Film after drying has a thickness of about 30 u.

_o This film contains 43.4% by weight of titanium dioxide, 43.4% by weight of CO

polymeric material and 13.0 wt.% cellulose triacetate. ο

_ »Before the white pigment film is completely dry and

as soon as it becomes stable, there will be a black on the latter Pigment composition attached with the following ingredients:

A. Mixture that consists of 1760 g of cellulose triacetate, 265 g of tri: r.-nyIphosphat, 2600 g of carbon black and 47.5 l mixture of 90 parts by volume Methylene chloride consists of 10 parts by volume of ethanol, ..Ij el 2 '': Treated for hours in a ball mill * A lot of 100 ml of a paste formed in this way contains 3.5% by weight of cellulose triacetate, 0.5% by weight of triphenyl phosphate and 5.2% by weight

1.2 1 of this black paste becomes 10 1 of a solution of

2200 g triacetate and 330 g triphenyl phosphate in a mixture ι

of 90 parts by volume of methylene chloride and 10 parts by volume of ethanol added. The black pigment composition becomes such on the still flexible white layer that the multilayer film has a thickness of about 110 u after drying. The black layer contains about 2.4% by weight of carbon black.

The multilayer film is then off the caster removed and on its white side successively with a gelatin adhesive layer and a highly sensitive gelatin silver halide emulsion layer coated with soft gradation "

A lightning protection layer is then applied to the back.

"~ * brings.
ο

to the photosensitive material thus formed can expediently

__j sig, for the production of halftone images gemass

cn be used in the silver salt diffusion transfer process »

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The black pigmented layer lets almost no light through, while the white pigmented layer is a very strong one light reflective ability and a very smooth surface possesses, so that the light-sensitive applied to it Layer is also very flat, which results in a more even ... and closer contact with the image receiving material possible will.

_2

Ethylene glycol is polycondensed with adipic acid to form a polyester with a molecular weight of about 2000. This Polyester becomes a polymer with 2,4-toluene diisocyanate Modified material with a molecular weight of about 20,000.

According to the method described in Example 1 is then prepared a white paste containing 60.78% by weight of 1,2-dichloroethane, Contains 32.80 wt.% Titanium dioxide and 5.76 wt.% Of the polymeric material described above. Afterward 0.66% by weight photographic inert dispersant is added. This white paste is then used to make a series of casting compositions, all of which contain 40% by weight of titanium dioxide, prepared by mixing the white paste with a

_o Solution of 22.5% by weight of cellulose triacetate and 30% by weight of the to

oo polymeric material in a mixture of 90 parts by volume co

^ Methylene chloride and 10 parts by volume of ethanol mixed. The (O added amounts are chosen such that in the under - "" * different casting compositions I ₁ 1.5, 2, 3.2 or 6.6 parts by weight of polymeric material per part by weight of cellulose

triac (Ei; at ^{: 1} <are present.

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- 25 -

A white paste is also prepared as a comparison material, which only contains cellulose triacetate as a binder.

Before venting and applying, the viscosity becomes all Casting compositions by adding methylene chloride 25oOOO cPs regulated.

These become on the endless belt of the film casting machine white casting compositions cast films which, after drying, have a thickness of 30 u. Immediately after ™ After the application of the white layer, a black layer is poured over it in such a way that the multilayer Film has a thickness of about 110 u after drying - The black coating composition consists of 22.5% by weight Cellulose triacetate, 3.3% by weight triphenyl phosphate and 0.75% by weight carbon black in a mixture of 90 parts by volume of methylene chloride and 10 parts by volume of ethanol. The dried black pigmented layer contains 2.8% by weight of carbon black Relation to the total weight of solid material in this layer '

The mechanical properties of the multilayer films are presented in the table below

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Table 1

Total thickness in μ

Tensile strength in kg / mm2

Elongation at break in%

Fold strength, number of double folds at 50% relative humidity

at 30% relative humidity

Light reflection in %

CeI lulosetriace tat / polymer ratio ;; j Material in the white layer:

1/0

Comparative material

110
8.7

11.0
22nd

64.3

1/1

105 9.5

15.3 90 86 92

1 / 1.5

105 8.8

14.0 64 68 92

1/2

105 8.7

12.8 76 66 92.5

1 / 3.2

100 8.9

11.1 95 80 91.5

i / 6, G j

125 7.3

13.5 89 73 93

The tensile strength and elongation at break are included on the Devices on the market e.g. "Instron Tester" measured » The folding endurance is measured using the MIT Folding Endurance Tester, which is described in "American Standard Method for Determining the Brittleness of photographic film "(PH 1.31-1965).

The figures included in the table show that the brittleness of the reference material is too strong, because the number of double folds made with this material can be made is very low. However, a noticeable improvement in the number of folds is achieved if

the cellulose triacetate of the white layer composition , .olynercs material is added. After adding 6.6 weight; - tcriien polymers! Material per part by weight of cellulose triacetate the material does indeed become pliable »although its surface still aIbu is sticky and the material in this way is still useless «, if the white pigmented layer of these materials is successively covered with a conventional gelatin adhesive layer and a gelatin silver halide emulsion layer is coated, photosensitive materials are obtained expediently in silver salt diffusion transfer processes can be used.

1500 kg of white paste, which consists of 475.5 kg of titanium dioxide and 83.5 kg of polymeric material consists of 1,2-dichloroethane (see Example 2), a solution of 200 kg of low-viscosity cellulose triacetate and 300 kg is added with stirring polymeric material (see Example 2) in 1900 1 of a mixture of 90 parts by volume of methylene chloride and 10 parts by volume of methanol added «After thorough mixing, the viscosity of the white composition is increased by adding a mixture of 90 parts by volume of methylene chloride and 10 parts by volume

^ Ethanol regulated to around 20,000 cP, _WO according to the composition

co is completely vented at negative pressure. Then ^{ω is} made from this casting composition in a casting machine

_ * a film is cast which, after drying, has a thickness of about ω

Oi has 30 u = the white layer consists of 45% by weight «J Γ

Titanium dioxide and 55% by weight binder mixture (1 part cellulose triacetate per 1.9 parts of polymeric material) «Before the

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When the layer is completely dry, it becomes a rind Layer applied in such a way that the total thickness of the dried multilayer film obtained is about 140 µ = Die The coating composition of this black layer is prepared by adding a mixture of 52 kg of carbon black, 32 kg of cellulose triacetate,

4.8 kg triphenyl phosphate, 828 l methylene chloride and 92 l ethanol treated in a ball mill for 20 hours Part by weight of this black paste is 10 parts by weight of a solution of 2 parts by weight of cellulose triacetate and 0.3 parts by weight of triphenyl phosphate in a mixture of 10 parts by volume of methylene chloride and 10 parts by volume of ethanol mixed «The formed composition is diluted with the same mixture of methylene chloride and ethanol, until a viscosity of 25,000 cP is measured.

It turns out that the very flexible black and white carrier formed does not allow sunlight to pass through and 94% of the reflected light. If you apply a gelatin adhesive layer one after the other on the white pigmented layer

and applying a silver halide emulsion layer is obtained

a photosensitive material which is conveniently in used a silver salt diffusion transfer process

_ω can be, being that of the photosensitive material

ω and the image receiving material existing sentence outside the ο

^ The camera is guided into the daylight to see the development of the

cn, photosensitive material and image production by

Allow diffusion transfer to take place.

A-G 408

A photosensitive material is made by a white-black multi-layer film base (see Example 1) on its white pigmented layer one after the other with a gelatin adhesive layer, a highly sensitive one

blue sensitized pelatin silver halide emulsion layer (27 ° DIN) with very weak gradation (equivalent amount of silver nitrate: 2.5g per m2) and a gelatin top layer

coated in a ratio of 0.5 g per m2. _

An image receiving material is prepared by making the Baryta side of a baryta paper, which lets almost no visible light through, has a high-gloss finish. The baryta paper is then provided with a layer containing development germs by the following composition is applied in a ratio of 1 1 per 10 m2:

Water 825 ml

Gelatin 41 g

0.2% by weight dispersion of nickel *

sulfite germs in a 10 wt.% igen

aqueous solution of gelatin 41 ml

1% strength by weight solution of bis (dimethylthiocarbamoyl) sulfide in ethanol 82 ml

12.5% strength by weight aqueous solution of saponin 4 ml

"f 20% aqueous solution of formaldehyde 2 ml

W The following developer solution is used:

_(piA distilled water 1000 ml

tn l-phenyl-3-pyrazolidinone 1 q

anhydrous sodium sulfite 75 g

Sodium hydroxide 25 g

Hydroquinone 16 g

p-monomethylaminophenol sulfate 5g

Potassium bromide lg

anhydrous sodium thiosulfate 8.2 g

Ammonium thiosulfate 24.5 g

Sodium metabisulfite 7.3 g

The pH of this developer solution is 11.5.

The light-sensitive material becomes image-wise in a camera exposed according to a halftone original and then moistened with the developer solution on the emulsion side alone = The material is then brought into contact with an image receiving material. Immediately afterwards it will the one from the light-sensitive one pressed against one another Material and image receiving material existing set outside the camera in the daylight. Then the Photosensitive material development and image formation carried out by diffusion transfer for about 60 seconds, after which both materials are separated from each other. The image receiving material shows a positive halftone print, good quality from the original. There will not be a single mistake due to exposure to daylight during the treatment noticed.

10 9830/1957

8ADORiSfNAL

' c.'. Score 5

"IC, '-. MO -.j Titanium dioxide and 1640 g of cellulose triacetate are ■■' .- · ^: uriia in 27.35 1 mixture of 90 VolI toi lon methylene chloride and 10 parts by volume of ethanol in a ball mill L ^ h- A solution of cellulose triacetate and 9 kq diphenyl phosphate in a mixture of 90 parts by volume of methylene chloride and 10 parts by volume of ethanol is then added

The thoroughly mixed white figment composition that 13.5% by weight of titanium dioxide in relation to the solids present <nl holds, v. is cast using a film casting machine in such a way that d: ss after drying a film with a thickness of about 30 microns is formed.

Before the white pigmented layer is completely dry and as soon as the layer becomes stable, it becomes a black one pigmented layer (see Example 1) applied so that

the total thickness of the multilayer film is about 90 µ λ

amounts to",

The following table lists the mechanical properties of the multilayer film with those of a completely transparent cellulose triacetate film with the same Thickness comparedο

109830/1957

Table 2

Layered
Movie Light through
casual filrr Tensile strength in kg / mm2 10.6 10, G Elongation at break in % 15.6 20.3 Fold strength, number
of double folds
50 % relative humidity 60 65 Light reflection in% 75 -

These mechanical particles are measured according to the method described in Example 2.

The multilayer film is then cast off the casting machine removed »The white pigmented layer has a light-reflecting capacity of 75%.

The white side of the multilayer film is then sequential with a gelatin subbing layer and a highly sensitive silver halide emulsion layer with soft gradation coated «.

The photosensitive material thus formed can be expediently for the production of Hälijfeontildern according to employ the silver salt diffusion transfer process.

108830 / 1SS?

A-G 408

Claims (1)

Ί797Ό84- Claims 1. Multi-layer film, which consists of two hydrophobic layers, which are successively made up of dispersions in low-boiling Solvents are poured, of which the second layer is already applied when the first Layer still a substantial amount of low-boiling point Has solvent for the hydrophobic film-forming binder of this layer, and one of the two layers is a cellulose ester layer containing a black pigment while the other layer is a cellulose ester layer is in which a white pigment is incorporated Multi-layer film according to Claim I _1, characterized in that the cellulose ester layer contains finely divided carbon black with black pigment as the black pigment. 3ο multilayer film according to claim 2, characterized in that that the carbon black is in a concentration of 1 to 5% by weight in relation to the weight of the solid material in the black pigmented layer is present. 4. Multi-layer film according to claims 2 and 3, characterized in that that the cellulose ester of the black pigmented layer is cellulose triacetate. 109830/1957 AG 4 08 Multi-layer film according to Claims 1 to 4, characterized in that that the white pigmented layer contains finely divided titanium dioxide as pigment., Multi-layer film according to claim 5, characterized in that that the white pigment in a concentration of 10 to 55% by weight in relation to the weight of the solid substance in the white pigmented layer is present. ^ 7 »Multi-layer film according to claims 5 or 6, thereby indicated that the cellulose ester of the white pigmented layer is cellulose triacetate « Β »Multi-layer film according to claims 1 to 7, thereby characterized in that the white pigmented layer also has a polymeric material, which by modification with a diisocyanate of an aromatic or aliphatic low molecular weight polyester of (A) an aliphatic diol with 2 to 10 carbon atoms or W ' a mixture of such diols and (B) an aliphatic dicarboxylic acid with a maximum of 10 carbon atoms is formed. 9 = multi-layer film according to claims 5 to 8, characterized in that that per part by weight of cellulose ester in the white pigmented layer, half a weight to four weight parts of polymer material is (are) present. 109830 / 1-95 * 0 _{A. G} 408 BAD ORWiNAL 10. Multi-layer film according to claims 5 to 9, characterized in that that the polymeric material is a low molecular weight polyester of ethylene glycol and adipic acid is, this polyester with 2,4-toluene diisocyanate has been modified. 11. Multi-layer film according to claims 5 to 9, characterized in that the polymeric material is a low molecular weight polyester of ethylene glycol, diethanolamine M and adipic acid, this polyester having been modified with 2,4-toluene diisocyanate. 12ο Multi-layer film according to claims 1 to 11, characterized in that that the black pigmented layer has a thickness of 50 to 100 microns. 13. Multi-layer film according to claims 1 to 12, characterized in that the white pigmented layer has a thickness of 10 to 50 u. M. 14ο Photographic light-sensitive material that has a multilayer film base according to claims 1 to 13, characterized in that the white pigmented Layer of this film support covered with a photosensitive silver halide emulsion layer is. 10 08 30/195 7 A-G 408 and 15. A photographic light-sensitive material according to claim 14, characterized in that this material in one Silver salt diffusion transfer process is used. Ib ο i; A hotographic photosensitive material according to claim 15, characterized in that the photosensitive ^) Emulsion layer (s) used in the production of colored images according to the silver salt diffusion transfer ^ drive common type belongs to (belong to). 17 “Photographic light-sensitive material according to Claims 14 to 16, characterized in that in this photosensitive material at least one Ent- winding substance in effective contact with the silver halide emulsion layer is available. IC. Photographic light-sensitive material according to Claims 14 to 17, characterized in that a Fe water-permeable layer on the silver halide emulsion layer is applied. 19o photographic light-sensitive material according to claim 18, characterized in that the water-permeable cover layer is an uncured layer. 20. Photographic light-sensitive material according to Claims 15 to 19, characterized in that the photosensitive material is a multilayer material, that is a photosensitive silver halide emulsion layer 109830/1957 and has developed an image-receiving layer containing - * "" * 9m ORieiNAL 21, if hotographic photosensitive material, n: .ch claims 14 to 20, characterized in that the light-sensitive emulsion layer has a high sensitivity. Silver halide emulsion layer with camera receiver inulichk- ..; or modified when registering image-wise,.! · X-rays or radioactive rays usually · .. used type is. 22ο Photographic image receiving material for use ^ j in the silver salt diffusion transfer process, thereby characterized that this material is a multilayer Film base according to claims 1 to 13 contains. 23 "Photographic image receiving material according to claim 22, characterized in that development nuclei are applied to the pigmented layer » Fusion transfer method 24 "method for producing images according to the Silbersalzdif after which a photo- M photographic light-sensitive material according to claims 15 to 21 picture modified according to actinic rays is suspended and ^ ing into the presence of a Behändlungsflü, a Entwickelsubstanz, a Silberhaloqenldlösungnmittel and alkalis in contact with an image receiving layer in order to develop a negative image in the silver halide emulsion layer and then to allow image formation to take place by diffusion transfer Ln of the image receiving layer. 109830/195 7 25, / according to claim 24, characterized in that at least one thin layer of the Bi LK mpi mqsschi.c'n i., Which contains the diffusion transfer image, is drawn from the silver halide emulsion layer and another Material is transferred » "Ancestors according to claims 24 and 25, characterized in that the image-receiving layer Entwicklur g · -iccj.r- ... ^r ht the diffusing silver halide salts nithait = 27. The method according to claim 26, characterized in that q .kon ^r i? E_'jt ~ net, dciss the development nuclei through, φ, ν «. B <bnSncilungsi lu ^ £% can be made available * t ^x " 28. The method according to claims 24 to 2 7, dadurcH, njefceiiöeftachnfct that a photographiscnc s li.q ^ jtieirifpf5i "ndiicljeS M | ^ <jrikSt ^v according to claim 21 in ei-n ^ r '" ³ Karfiera Qd ^ t *. §Irter Kasset-te ^ 4A-ut9i_es-es material before akti'niäc'h ^ m UmgcbjurH ^ sl ^ 'ch't schützC ^ i (JpAIdcjemass is exposed and' anS- ^ hU "^ e'rid in Beru ^^ up ^ with an image receiving layer und.qr 'ffehtrtz. 'isette, so that the development, de' -. i ^: -; alogenidomulsion layer and the further Bchf · ;.;, i;.: j .. ~ v ^J '· ndcn can, 109830/1957 , .. rf .hi ^ n η '"- I Ar.Socht 2 ?, characterized, ^r hs:: ■.: .- .. '" it. ι ..; u £ d <_rr photosensitive H ;. t> .. ri -. 1 una '.i'.i ti ■ • .r. - · -: -:.: C: iichfc}; :; teht_ _: r "_;'i-_ Sentence ausrjcrh- .:] b d -._ r K r; .. j. r, - ; i "-: ht v;.!.] d, _i; .s l-chut ^^ r. / er ·". kti ri c: ch ._: ri Unv.; i_Lu: "ig .. ..! ■ .: ii - ^. ■ ..!: ^Λ . ■■ _ ■>: ', \ ndur.q Lines BiIdempf ~ ncjsm ^ t ^ rials after ". .r: .. j" ^: .Jc! n -.:, 2 ^ or.:r 23 realized v / ird- 109830/1957 BATH