DE1772430A1 - Image receiving layer suitable for photographic diffusion transfer processes - Google Patents

Description

Suitable for diffusion transfer photographic processes

Image receiving layer

Priority from 26 May 1967, No. _6641670, United States

The present invention is in the field of photography, and more particularly relates to a method for Creating diffusion transfer color photographic images a as well as on products that are particularly suitable for use suitable for this process.

In U.S. Patent 2,983,606, there is a photosensitive Material described which has a dye developer and a Silver halide emulsion, which contains the exposed and in the Darkness is graded with a liquid developer compound, for example by dipping, coating, spraying, overgleaeen and the like The exposed photosensitive material becomes

00988A / 09U

placed on a sheet-shaped support before, during or after wetting, which can be used as an image receiving material. In a preferred embodiment, the liquid developer is applied to the photosensitive layer as a substantially uniform layer when the photosensitive layer comes to rest on the image-receiving layer. The liquid developer penetrates the emulsion and initiates the development of the latent image contained therein. The dye developer is immobilized or precipitated on exposed areas as a result of the development of the latent image. This rendering mobile is obviously at least partly due to a change in the solubility properties of the dye developer during oxidation and, in particular, to its solubility in alkaline solutions as a consequence of the development “In unexposed and partially exposed areas of the emulsion”, the dye developer remains unreacted and diffusible and thus, as a result of the point-by-point exposure of the silver halide emulsion, results in an imagewise distribution of the unoxidized dye developer in the liquid At least part of this imagewise distribution of the non-oxidized dye-developer is transferred to an overlying image-receiving layer during the exposure period oxidized dye

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developer is excluded. The image receiving layer is preserved diffusion of the developed emulsion of the non-oxidized dye developer, which differs according to the depths, without noticeably disturbing their image-correct distribution »so that an inverted or positive color image emerges of the developed image. The desired positive image is obtained by stripping the image receiving layer from the light-sensitive layer set free at the end of a suitable exposure period.

As mentioned above, the dye developers are »compounds, which in the same molecule both the chromophoric system of a dye and a silver halide developer function contain. Kit with the expression "a silver halide Bi *« winding function " a "group" is referred to as the exposed silver halide able to develop. A preferred silver halide developer fraction is a hydroehinonyl group «Others suitable developer functions are, for example. o-D :; hydroxyphenyl and o- and para-amino-substituted hydroxyphenyl groups. In general, the developer function is a bensoic developer function, i.e. an aromatic developer group »the when oxidizing quinoid or. Forms quinone substances.

Multicolor images can be formed using color image forming Components such as the dye developers mentioned above are obtained in diffusion transfer processes will. One possibility is to use a photosensitive silver halide layer which has at least

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two groups of selectively sensitized very small ones;., Photosensitive elements contains »which are in the form of a photosensitive »Transmission methods of this type are described in US Patents 2,968,554 and 2,983,606. In such an embodiment Every very small photosensitive element has a corresponding dye developer in or behind the silver halide emulsion assigned »Generally contain suitable light-sensitive grids, which according to the above status

^ the technology have been produced, very small red sensitive emulsion elements, very small green sensitive emulsion elements and very small blue sensitive emulsion elements, which are arranged side by side in the form of a grid and which in a corresponding manner a blue-green dye developer, a purple dye developer and a yellow dye developers are assigned ■. Another method of achieving multicolor transfer images uses dye developers in a unitary multilayer photosensitive element such as that used in the United States.

f patent 3 345 163 is described. Thereafter, at least two selectively sensitized photosensitive layers are placed on a single support and developed simultaneously without separation with a single common image-receiving layer. A suitable arrangement of this type comprises a support on which there is a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, these emulsions in

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BATH ORIGINAL

a blue-green dye developer, a purple dye developer and a yellow dye developer are assigned correspondingly. The dye developer can be used in the silver halide emulsion layer, for example in the form of particles, or it can be used as a layer behind the. corresponding silver halide emulsion layer can be used. Each group of silver halide emulsion and its associated dye Entwicklerschioht may be separated from other groups by appropriate intermediate layers, for example by a gelatin or polyvinyl alcohol layer the like. In certain cases it may be desirable to insert a yellow filter in front of the green-sensitive emulsion. Such a yellow filter can be contained in an intermediate layer.

■ ■. . ■ ·

when it is in a state that it can act as a yellow filter. In such cases a. separate yellow filter may be superfluous. .

U.S. Patent 3,362,819 and Image Receiving Layers described, the particular for use in the above Diffusion transfer methods are suitable; these Layers contain a carrier layer that has a polymeric acid layer on one of its surfaces in the following order: an inert tent or spacer layer and an image receiving layer contributes to the transfer of the diffusible dye image-forming substances to this layer results in a visible image.

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As mentioned in the above-mentioned patent specification, the polymeric acid layer contains polymers with acid groups, such as carboxylic acid and sulfonic acid groups, which react with the alkali metals, v / ie sodium, potassium and the like, or with organic bases, in particular quaternary ammonium bases such as tetramethylammonium hydroxide or potential acid-yielding groups such as anhydrides or lactones or other groups that can react with bases in order to capture or retain them, form salts. The acidic reacting groups are of course not diffusible from the acidic polymer layer Acid polymer free carboxylic acid groups and the transfer developer solution contains a high concentration of sodium and / or potassium ions. Acid polymers identified as being particularly useful contain free carboxyl groups, they are insoluble in water in the form of the free acid and they can form water-soluble sodium and / or potassium salts the. One can also use polymers "containing carboxylic anhydride groups, preferably \ least some of them have been converted before the period of exposure to the free carboxyl groups. Although the most readily available polymeric acids are derivatives of cellulose or phenyl polymers, polymeric acids from other classes of polymers can also be used. Examples of specific specified in the above-mentioned patent, polymeric acids are dibasic Säurehalbesterderivate ron cellulose, said derivatives containing free carboxyl groups, for example Gelluloeeacetat-hydrogenphthal *

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Cellulose acetate hydrogen glutarate, cellulose acetate hydrogen succinate, Ethylencellulose-hydrogen succinate, ethyl cellulose acetate-hydrogen succinate, Cellulose acetate hydrogen succinate hydrogen phthalate, ethers and ester derivatives of cellulose, the have been modified with sulfonic hydrides, e.g. with o-sulfobenzoic anhydride, Polystyrene sulfonic acid »carboxymethyl cellulose, Polyvinyl hydrogen phthalate, polyvinyl acetate hydrogen phthalate. Polyacrylic acid, acetals of polyvinyl alcohol with carboxy- or sulf ^ substituted aldehydes * e.g. o-, m- or p-Benzaldehydsilfonsäure or -carboxylic acid, partial Esters of ethylene / maleic anhydride copolymers; partial Esters of methyl vinyl ether / talic acid anhydride copolymers and the same. ·. ,

The acidic polymer layer contains at least sufficient acid groups to reduce the pH of the picture layer by one. pH of about 13-14 to a pH of at least 11 or less

A

ger after the / effective period to decrease and preferably to a pH of about 5-8 within a short exposure period · As already mentioned, the pH is the de-. Wrapping solution preferably in the area of at least 13 -

14. " ^:

■ - .. ■■■■ .. ■ '*

It is of course necessary that the action of the polymeric acid be controlled in such a way that it neither the development of the Negative, nor interferes with the image transfer of unoxidized dye developing. Because of this, the pH becomes the. Image layer held at a value of 12-14 until the

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positive dye image has formed * whereupon the pH is very high is rapidly reduced to at least about 11 and preferably 9-10 "before severing the positive transfer image and exposed to air = non-oxidized dye developer, which contain hydroehlnonyl developer groups, such as the quaternary ammonium, sodium or another alkali salt, diffuse from the negative to the positive The rate of diffusion such dye image forming components is at least in part a function of alkali concentration and it is necessary? that the pH of the image layer remains in the region of 12-14 until the transfer of the necessary amount of dye is done. The subsequent In addition to the desired effect on the image light stability, pH reduction serves to create a photographically very valuable Exercise function »by essentially preventing further dye transfer. This development technique thus effectively reducing changes in color balance resulting from prolonged exposure to multicolor transfer processes can occur using multilayer negatives.

To avoid premature pH reduction during development to prevent, for example, by undesirable reduction in the density of the positive image, it is indicated that the Acid groups should be distributed in the acid polymer layer in such a way that the speed with which they affect the alkali can be controlled, e.g., a function of the rate of swelling of the polymeric layer, wherein

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this speed in turn is in direct proportion to the Diffusion rate of the hydroxyl ions. The desired distribution of the acid groups in the acidic polymer layer may be effected by mixing the acid polymer with a compatible polymer that does not contain acid groups or has a lower concentration of acid groups, or by using only one acid polymer, that has a relatively low proportion of acid groups wearing. These embodiments are indicated in the aforementioned United States Patent 234,864 as (a) a Mixture of cellulose acetate and cellulose acetate hydrogen phthalate and (b) a cellulose acetate hydrogen phthalate polymer with a much lower percentage of phthalic groups than the first mentioned cellulose acetate hydrogen phthalate.

Ee is also indicated that the layer which the polymer Carries acid layer, a polymer that is insoluble in water may contain, preferably a cellulose ester, which effects the control and modulation of the speed with which forms the alkali salt of the polymer acid. As an accessory Games of cellulose esters suitable for this purpose are cellulose acetate, cellulose acetate butyrate, and the like. mentioned. These particular polymers and combinations of polymers used in the specified embodiments are, of course, selected to have suitable wet and dry strengths. If necessary or desired, suitable watchdogs can also be used.

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Coatings are used to make the various polymers Layers will adhere better to each other during storage and use.

You inert spacer layer of the. U.S. patent mentioned above can e.g. be a layer that contains polyvinyl alcohol or gelatin and is used to control acidity, within which the pH reduction takes place through the polymeric acid layer. This "time shift" is a! Puncture of the Speed at which the alkali diffuses through the inert spacer layer «It is stated» that the pH does not drop, until the alkali has migrated through the spacer layer, i.e. the pH is only reduced by diffusion into the The spacing layer does not decrease to any significant extent, but the pH drops quite quickly as soon as the alkali penetrates the spacer layer has diffused into the polymeric acid layer.

Examples of materials that can be used as an image-receiving layer Suitable are polymers which can be dyed in solution, such as nylons, e.g. H-methoxymethyl-polyhexamethylene adipamide; partially hydrolyzed Polyvinyl acetate; Polyvinyl alcohol with or without plasticizers; Cellulose acetate with filler, e.g. one half Cellulose acetate and one-half oleic acid; Gelatin and other materials of a similar nature. Preferred materials included Polyvinyl alcohol or gelatin, which contains a colorant ι such as poly-4-vinylpyridine (see. USA patent 3 148 061).

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- 10 -.

It is a primary object of the present invention to provide new diffusion transfer photographic color processes and a new image receiving material which is particularly useful suitable for this procedure.

Another object of the invention is "photographic Specify diffusion transfer color methods that oppose increased deodorizer temperatures are less sensitive and new image receiving materials, which are particularly suitable for this

suitable. *

Another object of the present invention is to provide novel diffusion transfer color photographic processes which with which a constant transfer image color can be achieved larger temperature range is reached and new image receiving layers, which are particularly suitable for this.

Another object of the invention is to provide color photographic diffusion transfer process, wherein the * hydrogen ion concentration is kept constant over a temperature range during the grb'sseren tibertragungsentwicklung substantially and new Bildempfangsschlchten which are particularly suitable for this purpose.

Another object of the present invention is to provide novel diffusion transfer photographic color processes, at which the hydrogen ion concentration during transfer development over a predetermined period of time

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009884/0914

177243Q '. .

independent of the temperature-dependent diffusion speed the alkaline developing solution is kept essentially constant and new image receiving materials which are particularly suitable for this.

Another object of the present invention is to provide new Specify image receiving layers that are particularly suitable for photographic Diffusion transfer paint processes are suitable, with a permeable polyvinylamide material in the composite layers t is included and to new methods of transmission that use these materials.

Another object of the invention is "new image receiving layers indicate which particular diffusion transfer color photographic processes are suitable; they contain a flexible composite structure comprising, in the following order, a carrier layer »a first polymeric acid layer, a second polymeric layer which is permeable to an alkaline solution and has special permeability properties, * where the second polymer layer contains a polyvinylamide and a third polymer layer which can be colored by a solution and new transmission methods using these structures.

Another object of the present invention is to provide an image receiving material which is particularly suitable for use in photographic diffusion transfer color

driving is suitable. This material contains several layers in

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following order: a support layer, a first polymeric alkali metal ion acceptor, a second, temperature-verses, permeable to alkali metal ions polymeric layer containing poly vinyl amide; a third polymer layer that can be colored by an alkaline solution.

Other objects of the present invention are partly self-evident, partly from the following remarks.

For a better understanding of the spirit and objects of the invention, reference is made to the following description and drawings.

Fig. 1 shows in cross section a receiving layer for use in diffusion transfer photographic processes in which a polymeric acid layer is on a support and a spacer layer which is a polymeric material having a predetermined temperature-dependent permeability, overlying the polymeric acid layer and a polymeric dyeable layer is on the spacer layer.

Pig. 2 is a graphical representation of the temperature-dependent alkali permeability of polyvinyl alcohol films of various thicknesses when they come into contact with the developer solution of Example 1. FIG.

Pig.3 iet a graphical representation of the temperature-dependent alkali permeability of films of a 40:60 interpolymer »

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13 -

made of diacetone acrylamide and acrylamide in various thicknesses » when it comes into contact with the developer solution of Example 1.

Pig.4 is a graphic representation of the temperature-dependent Alkali permeability of films made from a 50:50 copolymer of diacetone acrylamide and dimethylaminoethyl acrylamide in different thicknesses when it comes into contact with the developer solution of Example 1

Pig. 5 is a graph * of the temperature dependent Alkali permeability of films of a 90:10 interpolymer from N-Iaopropylacrylamid and Dimethylamino-äthylacrylamid with different thickness when using the 'developer solution of example 1 comes into contact «

In U.S. Patents 2,647,049, 2,661:> 93, 2,698,244, 2,698,798 and 2,802,735 are subtractive parb diffusion transfer methods describe »that employ parb coupling methods served. Here, at least in part, one or more developer substances and one or more Brought color former to react, with a positive color image on a darttberlying image receiving layer forms · In the USA patent specification 3,019,124 is the manufacture of halftone photographic elements and are shown in U.S. Patents 2,968,554 and 2,983,606 Diffusion transfer method specified, wherein a color contrastar element used to make a multicolored

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positive image on a dariib succumbing s image-receiving layer forms "In the US Patents 2,774,668, 3,345,163 and '2983606 Diffusionsubertragungsverfahren are described. which use dyes to form a positive color image on an overlying image-receiving layer.

The above-mentioned objects of the invention are achieved by utilizing a diffusion transfer color photographic process of the general type described above together men with a new image receiving layer, "the more material layers in the following Eeihenfolge 'includes: a support layer, a polymeric acid layer, a permeable, polymeric spacer layer which acts as a mechanism w, & amperaturänderungen to compensate in the system and eitiv ^» rme able, from Solution dyeable polymer layer «,

In particular, the image receiving layer preferably includes a flexible composite structure including a plurality of polymer layers in the following order. exist; a carrier layer, a polymeric alkali acceptor layer, for example an alkali or quaternary ammonium ion acceptor layer, a polymeric layer with a predetermined temperature-dependent permeability and a polymeric layer which can be colored on contact with the alkaline solution containing a dye.

U.S. Patent 3,362,819, cited above, states that the presence of an inert spacer layer

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_y is effective to equalize different reaction rates over a wide temperature range »for example by preventing a premature pH decrease if the action or» development at temperatures above room temperature, z _o B "at 35 - 38 ° C (95 - 100 ⁰ P) takes place. This patent states that with an inert spacer layer, the rate at which the alkali becomes available for trapping by the polymeric acid layer becomes a puncture of the alkali diffusion rates.

In the German patent specification 1191688 is shown, the diffusion rate of an alkaline developing solution that, by a permeable inert polymeric spacer layer with increasing developer temperature increased so that, for example, at a relatively high Übercragungsentwicklungstemperatur, d "h., Transmission development temperatures above ca" 27 ⁰ C (80 ⁰ JP) an early drop in the pH of the transfer developer solution occurs, at least in part as a result of the rapid diffusion of the alkali from the dye transfer environment and its subsequent neutralization on contact with the polymeric acid layer that crosses an inert spacer layer that has optimal alkali permeability within the temperature range for optimal transfer development * Conversely, it has been shown that at temperatures below the optimal transfer developer range, e.g. Temperatures

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below about 10 ⁰ O (50 ⁰ F) the last-mentioned inert spacer layer has proven to be an effective diffusion barrier, which temporarily prevents an effective crossing of the inert spacer layer by the alkali, which shows reduced diffusion properties due to the temperature. This barrier resulted in the high pH being held in the transfer development environment for too long, so that stains could form on the transfer images, and this resulted in a deterioration in the sharpness of the positive transfer image.

In the above-mentioned patent it is also stated that when replacing an inert spacer layer in the Image receiving layer through a spacer layer which is a contains permeable polymeric layer that is independent of the ! Temperature is inversely permeable and, in particular, is a polymeric film-forming material that has decreasing permeability for alkali made soluble under increasing temperature shows the calibration of cations such as alkali metals and quaternary ammonium ions that derives the fault of a positive transfer image caused by the above-mentioned maintenance of the pH valuea too long a and / or too early pH reduction originate from, were avoided.

Examples of polymers which are described in the last-mentioned application and which show inverse temperature-dependent permeability to alkali are hydroxylpropyl polyvinyl alcohol , polyvinyl ethyl ether, polyethylene oxide,

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Polyvinyl oxazolidinone, hydroxypropyl methyl cellulose »partial Acetals of polyvinyl alcohol; such as partial polyvinyl butyral, partial polyvinyl formal, partial polyvinyl acetal, partial polyvinylpropional and the like

In particular, the spacer layer of the last-described image-receiving layer contains a permeable polymeric layer which, in the vicinity of a photographic diffusion transfer for a photographic developing solution, shows a permeability which is inversely dependent on the development temperature, compared with or measured against polymers used in the photographic field in general are known: “In general, such polymers are particularly intended for spacer layers that are relatively soluble in cold water, ie. Water at a temperature less than about 40 8O ⁰ O, the exact temperature depending on the particular polymer selected. These polymers are relatively insoluble in hot water, that is to say in water at a temperature above about 80.degree. C., the exact temperature here also depending on the polymer selected in each case. A relatively large number of such polymers are essentially insoluble in ethereal photographic developer media in the field of photographic diffusion transfer development.However, such polymers are permeable to alkaline photographic developers as a function of their swelling, which in turn is assumed to be a function of the free The energy of the decrease in solution is caused, at least in part, by the generation of heat as a result of the intermediate reaction between the polymer

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and the developer solvent and by an increase in the Entropy of the system * One nimiat that this decrease of the free energy decreases with increasing temperature of the environment will, as a result of less swelling, and that thus the permeability of the photographic developer decreases as the temperature rises.

It has now been shown, surprisingly, that if the spacer layer in the patent mentioned last is generally a polyvinylamide, preferably a polyacrylic. Λ contains amide, shows particularly good development behavior at cold temperature »eg when developing at a temperature in the range of about 10 ⁰ C (50 ⁰ F).

In a preferred embodiment, the use leads of polyvinylamides made in the manner described above are temperature inverse, contribute to a developing environment lower temperature with high transfer image maximum densities, improved photographic sensitivity, one better flexibility of the coating thickness for multicolored photographic diffusion transfer process with improved Color Isolation

When considering the present invention it becomes apparent that the polymeric spacer layer used here fall within a range of the curve of permeability - time - temperature in which the average slope of the curve can vary from slightly positive to slightly negative. One

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BATH

Tilt of 0 would indicate that 4.5 to 38 ⁰ C at about the normal ENTV / ICLK ^ ngsbereicli of (40 - 10O ⁰ F) the mechanism to reduce the pH independent of the temperature to function effectively * It must be pointed out, that the exact properties with regard to the dependence of the temperature and permeability of the spacing layer must be established as a whole according to the particular photographic system to be used and selected according to the relative dye diffusion constants as well as the development time of the system in question, which are required for the different temperatures » In this regard, the determination or selection of components of suitable polymers for use as a spacer layer in the system concerned is essentially empirical.

As explained with reference to the above-mentioned patents, the inverse temperature dependence of a polymeric film with regard to alkali permeability is not an unknown phenomenon, because the application of this property is in taking up layers for use in diffusion transfer photography The advantages relate to the use of a temperature-inverse material in a process that of the penetration of liquids at different Temperatures depends, since when the room temperature falls, the polymer tends to form hydrates and swells and thus the penetration or penetration as a function of the Degree of swelling of the polymer facilitates the swelling naturally associated with a rise in temperature

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It is also known that the rate of diffusion of a liquid, for example an alkaline liquid, increases with increasing temperature inversely to temperature obviously. The desired result would be a temperature inverse material that approximates the changes in the rate of diffusion of the permeable material with changes in temperature counteracts genes. The tempera for inverse behavior is therefore relative, because the properties desired in each case. depend on the sensitivity of the entire system to temperature changes. Extremely temperature-inverse properties are generally not particularly desirable since development of the photosensitive part of the system and dye transfer are temperature-dependent processes and should be functionally compatible with the temperature-dependent permeability of the receiving layer. An * ideal spacer layer should therefore result in a system that has the desired dye permeation temperature properties so that the dye as a result of the ent j

winding from the dome light-sensitive part of the system to the ' Recording layer can diffuse * around a positive image in of the receiving layer within a certain time, regardless of the applied developing temperature.

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The tenperatiirinversen properties of members of the Class of polymers that are suitable for the purpose of the present invention are partly due to the present; aaa predetermined balance of hydrophobic and hydrophilic groups in the polymer molecule. The likely mechanism by which temperature inversion occurs is the formation of hydrogen bonds between the hydrophilic part of the polymer and the hydrogen of the solvent at low temperature, the hydrogen bond will dissolved when the temperature of the material rises due to thermal degradation. The system then takes the form of one less hydrate, less swollen and therefore less permeable polymer as a function of increasing temperature at. It can thus be said that the preferred polymers which are suitable for the purposes of the invention are those which contain hydrophilic groups as a result of solvation these groups in a given solvent Cause swelling and which also contain hydrophobic groups, which modulate the swelling in such a way that with a defined ratio of hydrophilic to hydrophobic groups

the resulting connection has temperature-inverse properties. It can also be concluded from this that the intermediate reactions that are responsible for the temperature inversion, forces such as hydrogen bonds and bonds between hydrophobic vxia. are hydrophobic components.

It has now been shown, surprisingly, that a class of polymers, based on Polyvinylaraiägruppen der

009884/0914 bad original

Formula Jt

CH ₂ - OH

where E is a carboxamido or carbamyl group gives far better results when considering the criteria mentioned above than other polymer groups which have heretofore been used for the purpose in question _β

Preferred polymers in the context of the present invention contain Polyvinylamides of the general formulas

GH -] - - £. CH ₂ - GH 4-

I!

and in particular polyacrylamides of the last-mentioned formula, where RJ and R _{2 are} hydrogen, alkyl or aryl groups. It should be pointed out that in the context of the present invention the groups R * and Rp are to be regarded as equivalents and consequently, depending on the desired results, may contain substituted or unsubstituted alkyl and aryl groups and the like. In general, R ₁ and R _{2 can be} any group which functionally contributes to the desired hydrophilic or hydrophobic character of the polymer. Polymers which are suitable for the purposes of the invention can be prepared by predetermined in each polymer molecule

009 * 81/0914

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Incorporates quantities of hyalopilic and hydrophobic groups so that a suitable equilibrium is reached. _s that leads to the desired permeability at the intended temperature and thickness. These polymers include graft polymers as well as random interpolymers. In the former case, the product could be achieved, for example, by grafting vinyl amide groups onto a polyvinyl alcohol backbone. Homopolymers are also suitable for the present invention, it being possible for various derivatives to be present in the monomer in order to give it varying degrees of hydrophilic and hydrophobic behavior.

Interesting monomers eur production of copolymers or terpolymers with the necessary hydrophilic and hydrophobic balance are BB H-methylmetbacrylamide, ethyl acrylate, ff-ethyl acrylamide, K-methylolacrylamide, H, N-dimethylacrylamide, Ν, Ν-dimethyl methacrylamide, N- (n-propyl) ( Dimethylamino) ethyO / methacrylamide, 2- / 2 * - (acrylamido) ethoxy / ethanol, N- / 5'-methoxypropyl / aorylamide, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride »Z-acrylamido-S-methylbutyramide, acrylamidoacetamide» methacrylamido acetamide, 2- / 2'-methacrylaraido-3 * -methylbutyramido / acetamide , N-vinylpyrrolidone, diacetone acrylamide, dimethylamino-ethyl methacrylate, dimethylamino-ethyl acrylate, vinyl acetate and the like.

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Polymers, which are suitable for the purposes of the present invention:

(1) Poly-H-methacrylamide: - + CH ₉ CH-I-

* "I ^J χ CO

NHCH ₃

(2) Poly-H-methyl methacrylamide: -pβH ₂ -C

(3) Poly-K-ethyl acrylamide: - [o

CO

(4) 31 si si terpolamer of H-ethyl acrylamide: H-methylol acrylamide: acrylamide

χ - Ί

00

CO

HHOH ₂ CH ₃ HHCH ₂ OH 'HH ₂

(5) Poly-F-ethyl methacrylamide:

• ir

HHOH ₂ OH, (6). 9ι1 Mieohpolymer of H-Ätbylaorylamid ι 2 vinylpyridine

Lh ₂ OH,

(7) Poly-H, U-dimethylacrylamia: —PcH ₉ OH-I-

• Ί

CO Η—

(8) Poly-U, H-dimethyl methacrylamide:

CH,

CO

(9) Poly-H- (n-propyl) acrylamide: -f-CH _o CH-l ·

CO

UHCH ₂ CH ₂ CH ₃

(10) Poly-H-isopropyl acrylamide: —WH ₂ CEi—

Ix

CO

₃ ) ₂

(11) 9: 1 copolymer of N-isopropyl acrylamide: acrylamide:

! 0

CO

C HHCH-fCH ₃ ) ₂ MH ₂

(12) 3: 1 copolymer of N-Ieopropylacrylamid! Methacrylamidι

CH,

CO

IiHCH- (ΟΗ ₃ ) ₂

00986A / Q91A

(13) 9: 1 copolymer of ΪΓ-isopropyl aeryl amide: methyl acrylate

CO CO

NHCH-4CH,) 2 OCH,

(14) 1: 1 interpolymer of N-isopropyl acrylamide: N-ethyl acrylamide · -IcH ₂ O ^CH 2

f ^z I -

00

Il

HHOH- (OH ₃ ) ₂ HHOHgOHj

(15) 3: 1 copolymer of N-isopropylacrylamide: N-methylol-

acrylamide: —EcH ₀ CH-I— HCH ₉ CH -? -

CO CO

NHCH-fCH,) _o NHCH ₀ OH

(16) 3s2 mixed polymer of N-isopropyl acrylamide t N, N-dimethylacrylamide —-WHgCH-J

CHl · JcHj.C J ^J 3x ^{L 2} |

00 CO

4) ₂ N-fC

(17) 19: 1 copolymer of N-isopropyl acrylamide: acrylic acid

CO COOH

-

009884/0914

(18) 3: 1 copolymer of N-isopropyl acrylamide: N- (β-hydroxyethyl) acrylamide

3x - I χ Ό CO

NHOH ₂ OH ₂ OE

(19), 9 * 1 mixed polymer of N-isopropyl acrylamide: N- / B- (dim thylamino) ethyl / acrylamide fco

9x

00

MHOH-fO

(20) 9ϊ1 copolymer of N-isopropyl acrylamide Dimethylamino-ethyl acrylate

OH3Ε ^Η 2?

I 9x I

00 CO

NHOH-f CH ₅ ) ₂ OCH ₂ CH ₂ If- ^ CH ₅ ) ₂

(21) 9: 1 copolymer of N-isopropyl acrylamide: dimethylaminoethyl methacrylate

00 CO

NHCH ^ - ^ ORj) ₂ 00H ₂ OH ₂ N-4OHj)

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(22) Poly-N-isopropyl methacrylamide

■ fc

30th
NHGH-fCI

(23)

Poly-II, IT-diethylacrylamide | cH ₂ OH-J-,

30th

Η— £ CH ₂ CH ₅ )

(24) Poly-N-ethyl-H-methy! Acrylamide - [? ^H 2?

CO

N — CHoCH,

JLi WJU r \ \

CH,

(25)

Poly-Nt-butylaerylamide --CcH ₉ CH-I-

CO

(26) 1: 2 mixed polymer of N-t-butylacrylamide: N-Btethylamino) ätbyl7aoTyXanid

CO

30th

• 29 -

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(27) Poly ~ N- / i- (dimethylamino) ethyl / acrylamide - fcH

I ₂ CH ₂ ] J- (CH ₃ ) ₂

(28) 3ϊ1 copolymer of methyl acrylate: N- / 5- (dimethylamino ) ethyl 7 acrylamide

| ^ 3x ^ ² | CO CO

OCH »NHCH ₉ CHoN- (CH,) ₉

(29) Poly-N- / β- (dimethylamino) ethyl / methacrylamide

CO

MHCH ₂ CH ₂ N- (30) poly-N-Z3- (diethylamino) ethyl7acrylamide

NHGH ₂ N- (CH ₂ CH ₃ ) ₂

(31 ) Poly-2- ^ 2 "- (acrylamido) ethoxy / ethanol, CI

T

HHCH ₂ Oh ₂ OCH ₂ OH ₂ OH

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Ii "! UfS ¹ IS» I!. "SHi

(52) 3? Oly ~ lI- / 3 '-methoxypropyl7acry! Amido

GO

IiHGH ₂ OH ₂ CH ₂ OOH ₅

(33) polydiacetone acrylamide

Ί ^x

GO

M-- · G ———- CH ₂ -CO GH ₃ %

CH, ·

(34) '2: 3 copolymer of diacetone acrylamide and acrylamide

3H ₉ CH ^ -

J ^J 2x ^{L 2} J ^J 3x

CO CH, CO

II ⁵ I

1ΪΗ — C — CH ₀ —00 — CH * BH ₉

• 2 3

CH

(35) 6: 3: 1 terpolymer of diacetone acrylamide: acrylamide: dimethylaminoethyl methacrylate _CH

2. _yJii -, ι OH / jCH ¹ I ¹ ■ ■ J OHq * "* 'I

j 6x J ^J 3x * - j ^J χ

PO CH ₃ CO CO

M-

! -CH ₂ COCH ₃

CH ₃

~ 31 -

009884 / 09U

(35a) 6; 2; 2 polyesters of diacetone acarylöfflid; Acrylamide: Difliethylaminoethyl acrylate

(36) 5: 3: 12 terpolymer of biacetone acrylamide, ethyl acrylate; Acrylamide

5x ** ^c \. * 3x ^{L c} \ ' 12x

CO OH * CO CO

HH-H

3-0H _n OOOH, OCHoCH ₇ HH

CH,

(37) 1: 1 mixed polymer of Diacetonacrylsniidl and. Dimethylaminoethyl methacrylate

Β,

J ^x '

CO OH CO

II ³ i

NH C-CH ₂ COCH ₇

CH,

(38) 7: 3 Miecopolymer of diacetone acrylamide and Dimethylaminoethyl aorylate

7x CO OH ₃

H,

NH- - 0 - OHoCOCH,

009884 / 09U

BATH ORIGINAL

39) 3t2 liiscbpolymär of biaeetone acrylamide ίΓ- ^ β- (BJLfflethylaiaino) äthyl7acrylaffiid

MCH ₂ OH ₂ II.

20 CH,

(40) t: 1 misoh polymer of diacetone acrylamide and 2-Hydro3cy-5-metiiaoryloyloxy-propyltrimethylainmoniumclalorid

CO CH, HH-

70

-CH ₂ COCE ₅

JH,

OCHgCHCH ^ - ^ - föH »), OH Cl ^

(4t) Poly ^ I-acrylamido-J-methylbutyrainldJ

CO

GH-CO-IfH

CH

t ti Kiecbpölymer of acrylamide and 2 ^ & crylaiü ± do-5-methylbutyramide

fcH

1 00

(43) 1st copolymer of 2-acrylamido ~ 3-methylbutyraiaid and acrylamidoacetaraide

« Q&A —— fcH _o CH-J—

L,

CH

(44) 1: 1 copolymer of 2-AcD ^ lamido ~ 3- ~ methyltmtyramid and methaorylamidoacetamide

CH ₅

_o 4—

_o - C
2

CO CO

I- I-

NHCHCOKHo UHCH ₉ OOIiHp

2 2

(45) Poly-IT-Cpyridyl-4-methyl); 2-acrylamido-3-methylbutyramide

009884 / 09U

- 54 -

!! '". ■!'! ■". ■■■! Ϊ́ίϊ "Ι *" '

(46)

~ lf- ~ / ß- (dimetfaylaia3.no) -

ethylT-btatyramide

GO

JH

(M ₃ )

(47)

butyramide

JO

ί ",

(48) Poly-2- £ 2 '-metliacrylaiaido ~ 3 "-metliylbutyramido / acetamide

GH,

CO

- CH - CO - HH - GH ₂ - CO -

and

(49) - 3: 1 mixed polymer of N-IsopropylacrylEiinide and N-vinyl pyrrolidone

GO

Cf

009884/091

In general it can be said that a completely hydrophilic material is not temperature inverse »When the hydrophobic content decreases _? the solubility, which is directly related to the swelling capacity of the polymer, will decrease until the polymer is soluble or swellable, which, for example, can only be the pail in cold water. If the hydrophobic content is increased further; the polymer becomes insoluble, but coatings of such a material "if they are applied from a solvent other than water" can show a temperature-inverse permeability for water,

As expected, the thickness of the layer teaiperaturinversen somewhat critical, since by the Hydratiaierungsmeehanistius the layer actually holes formed in the film by the _T flows through the developer solution. In order to obtain an even development time *, the thickness of the individual polymer layers should be determined so that an even penetration time is achieved during the working temperature »In Hegel, a thickness of 1.7 to 20 * 32 microns (0.05-0 , 8 mil) the area in which the desired development time for penetration of the developer solution is achieved, for example with Polaroid 108 pilm packs.

Many compounds useful for the purposes of the present invention are insoluble in neutral or basic Medium and must therefore be coated with an acid system. Note in particular the following Examples II, IV, V and VI. When the polymer layer is applied as a coating from an acidic solution, it is actually in

00988A / 09U - 36 -

Acid salt form. As soon as it comes into contact with the strongly basic developer solution used for processes of the present invention, the polymer is rendered insoluble and results in a thin alkali-permeable layer.

As already mentioned, is used, the polymeric acid layer, which is used in a Diffusionsübertragtingsaufnahmeschieht, in addition to the hydrogen ion concentration to reduce the developer solution and at the same time as a waste λ coffer (sink) for Salsrüekstände to diener. ,, which is in the uppermost layer the image-receiving layer during the development process form "If! temperature is high, and no temperature inverse layer is used as a" time control "is bad dye densities and other errors (" gappiness ") result in the photograph * These phenomena should probably too early Neutralizing the developer. If the temperature is too low and a temperature inverse time layer is not used, the neutralization of the developer will be too slow and result in the unwanted salts being kept in the topmost layer of the photographic image. It is clear that this leads to cloudy, dirty colors and, in some cases, the developer reagents sticking to the surface of the image so that they are not selectively stripped off with the photosensitive layer.

BATH ORIGINAL

- 37 -

004884/0914

The present invention is illustrated in detail by means of the following examples, which, however, are not intended to be limiting serve the invention «

.Example I

An image receiving layer was made by using a Cellulose nitrate coated baryta paper with the partial butyl ester of polyethylene / aleic acid anhydride copolymer was coated. This was made by taking 14 hours long 300 g DX-840-31-H (trade name of Monsanto Chemical * Co, St.Louisj Missouri »for a high-viscosity polyethylene / Maleic anhydride), HO g of n-butyl alcohol and 1 ml of 85 # phosphoric acid were heated to reflux. A polymeric acid layer approximately 17.8 microns (0.7 mil) thick was formed from the reaction product; The outer surface of the acid layer was coated with a solution of 40:60 copolymers of diacetone acrylamide and acrylamide to form a polymeric spacer layer approximately 13.97 microns (0.35 nil) thick. The outer surface of the spacer layer was then applied with a 2: 1 mixture (parts by weight) of polyvinyl alcohol and poly-4-vinylpyridine at a coverage of approximately 600 mg / 0.09 m (600 mg / ft) to form a seal polymeric image receiving layer approximately 7 * 62 microns (0.30 mil) thick. The 80 image pickup Each layer was prepared then. Maintained for C (180 °?) For 30 min at 82 ⁰ and echliesslich allowed to cool them.

The 40:60 mixed polymer of diacetone acrylamide and acrylamide

.38- 009884/0914

was prepared as follows: 155 g of diacetone acrylamide and 86 g of acrylamide were dissolved in 2.0 l of distilled water. 20 ml of isopropanol were added. The solution was vented for 1 hour under nitrogen and then 3.2 g (SK ^) ^ 2 ⁰ Q ' and 1.6 g NapSO ^ were added at the same time. The solution was stirred overhead under nitrogen and then applied as a coating.

A multi-color photosensitive multilayer film was prepared in a manner similar to that set forth in U.S. Patent 3,345,163 mentioned above and described in more detail below. A green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are located behind the emulsions, dispersed in water-immiscible organic solvents, in separate gelatin polymer layers, a blue-green dye developer, a purple dye developer and a yellow dye developer off developer and the green-sensitive emulsion layer and also between the purple dye developer layer and the red-sensitive emulsion layer Sensitive layers, for example, use 1 *, 4-bis- (α-methyl-β-hydrochinoyl-ethylamino) -5 · 8-dihydroxyanthraquinone (a blue-green dye developer); 2- (p- ^ 2 ' _v 5 ^f -Dihydroxyphenäthyl7-phenylazo) -4-isopropoiy-1-naphthol (a

" ⁵⁹ - 009.884 / 09U ·.

purple dye developer) and 1-phenyl-3-n-hexyl-earbamyl-4- (p- ^ BydroquinonyläthylZ-phenylazo) -5-pyrazolone (a yellow dye developer). The yellow ones mentioned last and purple dye developers are in the United States patent 3,134,764 and the cyan dye developer in U.S. Patent 3 135 606. A multicolor photosensitive material with Iripack type dye developers can also be obtained from Polaroid Corporation, Cambridge, Massachusetts; this material contains the negative component of photographic film made by that company under the trade name Polacolor Film, 3? Yp 108 is distributed.

The photosensitive layer was then exposed to light and developed at various temperatures by spreading thereon an aqueous liquid developer at a pH of not less than about 12; it contained:
water
Potassium hydroxide

Hydrocythyl cellulose (high viscosity) (Commercially available from Hercules Powder Co., Wilmington, Delaware, under the tradename Hatrasol 250) Potassium thiosulfate
Benzotriazole

N-benzyl-ff-picolinium bromide Lithium hydroxide

The developer was distributed between the image-receiving layer and the exposed multicolor layer when they were in a

100 3 nl G 11.2 G G 4.03 g G 0.5 G 3.5 2.3 0.3

- 40 ~

009884/0914

"1772A30

Polaroid Land camera Pack came to rest on one another * After an exposure period of 60 or "135 sec., The tests at 24 and 38 ⁰ O (75 and 100 ⁰ F) or at 4.5 and 1O ⁰ O (40 and 50 ⁰ P) were carried out, the pH of the developer had reached a value below about 8 and the image-receiving layer was then separated from the best of the pilm pack.

For comparison, a picture was taken using the above method? but made with the exception that the spacer layer contained a polyvinyl alcohol layer 7.62 microns (0.30 mil) thick and was coated from a solution containing 1 <$> polyvinyl alcohol in water. This last-described image receiving layer was then developed at various temperatures, as mentioned above.

Examination of the resulting images showed the following differential maximums containing the difference between the maximum and minimum densities recorded for the various Pmrbwi of the Pil " alt " in "* Quantalog MaoBeth Densitometer · ',

■ repair AD _08x ^ max \

⁰ O ( ⁰ V) 40:60 mixed polymer of polyvinyl alcohol

¹ \ Diacetona ylamide and comparative abtande- Acrylnpwjd Abstanflsohlcht 'layer

red green blue red 'green blue 4.5 (40) 1.73
10.0 '"(50) 1.75
U (75) 1.3
Jt (100) 1.7 ■

1.70 1 , 85 1.13 1.25 1 , 28 1.73 1 , 79 1.15 1.33 i .94 1.25 1 , 86 1.36 1.30 1 .44 1.66 1 »77 1.06 1.65 ·. * OOtMt / etU BAD ORIGiNAU.

In addition to far better differential half-space transmission densities » Especially in the cold, it has been shown that slightly glossier images can be achieved if the spacer layer is used used according to the invention than in the usual Standard polyvinyl alcohol spacer,

The optimum thickness with the compound in question was found to be 13.97 and 14 microns (0.55 mils), respectively. Thinner coatings of 11.4; 7.62 and 5 _f 1 microns (0.45; 0.3 and 0 _r 2 mil) cause either a blotchy appearance at high temperatures or surface sticking of the reagents at low temperatures. A good pH drop was also observed in the Developer composition observed., In the same way, the compound was found to be quite immobile and it adhered well to the multilayer film.

Example II

The procedure of Example I was repeated using a receiving layer with a spacer layer, which in turn contained 9: 1 H-Ieopropylaorylamid and B ^ ß- (D im ethylamino) äthyl7acrylamid instead of the 40:60 polymer of diacetone acrylamide and acrylamide. An oversug with a thickness of 4.45 microns (0.175 mils) is applied as an oversug. The 9: 1 N-Isopropylacrylamid and N- ^ ß ~ (Dimethylamine) -äthyl7acrylamld was prepared as follows: 250 ς H-Isopropylacrylamid and 34.9 g H- ^ I- (Dimethylamine) -Uthyl7aorylamid were distilled in 2.56 l Water dissolved.

^-42 ~ 009884/0914

BATH ORIGINAL

5 ml of isopropanol were added to the solution under nitrogen 1 hour "deaerated · The solution was brought to a pH" of 6.4 was adjusted with concentrated nitric acid and then 0.30 g of sodium bisulfite and 0.30 g of potassium persulfate at the same time admitted. The solution was under nitrogen Stirred overnight and then against running water for 24 hours dialyzed for a long time.

The comparison was made with a control, as in Example I. Examination of the resulting images showed the following differential maximum diphts:

temperature

9 * 1 N-Igopropylacrylamide polyvinyl alcohol

C (F) and Ng # M Dimethylamine) - Comparative Distance-

ethyl acrylamide layer

_mmmmm Spacer layer

red green blue red green blue

10.0 (50) 1.79 1.63 1.63 1.40 "1.48 1.45

24 (75) 1.43 1.64 1.59 1.59 1.65 1.66

38 (100) 1.77 1.70 1.65 0.98 1.24 1.43

The optimal thickness of the spacer layer described here Compound was found to be 4 »45 microns (0.175 mil) and it showed an excellent temperature-dependent permeability. Thicker coatings, such as made 7.62 microns (0.3 mil) a dirty picture at high temperatures. The adhesion was not as good as some other joints.

BAD ORiOlNAL - 43 - 009884 / 09U

Example III

Ϊ772430

The procedure of Example I was repeated, using a recording layer having a _{Abstandsschiclrt%} in turn, a 3: containing 60 ~ of Misehpolymers Diaeetonacrylamid and acrylamide;: 1-copolymer of U-Isopropylacrylaraid and N-methylol acrylamide in place of 40 it was applied as a coating to a thickness of 2.54 microns (0.1 mil). The 3 ^ copolymer of N-isopropylaerylamide and N-methylolacrylamide was prepared as follows:

25.0 g of H-isopropyl acrylamide and 7.8 g of N-methylol acrylamide were dissolved in 300 ml of distilled water and ^{cooled to 5 °} C. in an ice bath. The solution was deaerated for 1 hour under nitrogen and 0.026 g of Na ₂ SO ₅ and 0.034 g of NaBrO were added at the same time.

The solution was stirred under nitrogen for 3 hours and. then an additional 0.026 g of Na ₂ SO ₅ and 0.034 g of NaBrO _{5 were} added. The solution was stirred under nitrogen overnight and then dialyzed against running water for 48 hours »

A comparison was made with the control batch according to Example I. The examination of the resulting images showed the the following differential maximum densities:

temperature
⁰ C ( ⁰ F) (50) Max
3: 1 mixed polymer of
N-isopropyl acrylamide
and N-methylol acrylamide
Spacer layer AD
Max
Polyvinyl alcohol
Comparison distance
layer blue BATH ORIGINAL , 42 (75) red OTÜn blue red jR? ün 1 , 72 10.0 (100) 1.71 1.66 1.66 1.34 1.44 1 , 45 24 1.45 1.66 1.68 1.44 1.62 1 38 1.60 1.64 '* 1.60 0.74 1.20
009884 / 09U

The optimal thickness for the compound described herein, for the "intended purpose" herein, was found to be 2> 54 microns (0.1 mil). A more satiated reproduction was obtained at room temperature and at 1O ₃ O ⁰ O (50 ⁰ P). At 38 ⁰ C (100 ⁰ P) however some salt formation was observed when the layer thickness was increased to 5.1 to 7.6 microns (0.2-0 * 3 mils) «,

Example IV

The process of Example I was repeated with a receiving layer which, as a spacer layer, contained a 6:;>: 1 ~ 3rpolymer of diacetone acrylamide / acrylamide and H ^ / dimethylamino) ethyl7 ~ methacrylate instead of the 40:60 high polymer of diacetone acrylamide Layer was applied as a coating to a thickness of 8.25 microns (0.325 mils). The 6: 3: 1! Derpolymer of diacetone acrylamide? Acrylamide and dimethylamino) äthyl7methacrylat were prepared as follows: 30.5 g of diacetone acrylamide, 4.71 g of N- / 5- (dirnethyiaaino) ethyl / methacrylate and 6.4 g of acrylamide were dissolved in 300 ml of distilled water. 1 ml of isopropanol was added and the solution was adjusted to pH 6.4 with concentrated nitric acid. The solution was deaerated with nitrogen for 1 hour and then 0.05 g of K ₂ S ₂ O ₈ and 0.05 g of NaHSO _{5 were added} at the same time. The solution was stirred under nitrogen overnight and then dialyzed against running water for 24 hours.

The comparison was made with the control batch according to Example I.

_A , 009084/0914

- 45 -

, BAD ORIGtNAt

The examination of the resulting images showed the following differential maximum densities:

! Temperature AD

Max

6: 3: 1 terpolymer of (F) diaeetonacrylamide,

Acrylamide and tf- / B ~ _ (dimethylamine) ethyl / methacrylate
Spacer layer

Polyvinyl alcohol

Comparative distance

Red

green

(40) 1.96 1.78

(50) 1.71 1.60

(75) 1.44 1.73

(100) 1.72 1.72

blue

1.157 1.78 1.66

Red

1.13.
1.15
1.36
1.06

green

1.22

■ 1.33 1.65 1.30

blue

1.28 1.34 1.79 1.44

The optimum thickness was found to be 8.25 microns (0.325 mil). The compound tested here showed excellent temperature-dependent permeability. Layers thinner than 5.1 Microns (0.2 mils) caused some gappiness at high temperature.

Example V

The procedure of Beiapiela I was repeated with a receiving layer, the abatandsachicht a 50: 50 ~ mixed polymer of diacetone acrylamide and N- ^ B ~ (dimethylamino) ethyl / acrylate instead of the 40:60 mixed polymer of diacetone acrylamide and acrylamide contained; she became "in a thickness

- 46 -

009884709U

BATH ORIGINAL

of 12.7 microns (0.5 mil) introduced »The SO-.SO from diacetone acrylamide and dirnethylaminoäthylaerylat was manufactured as follows:

50:74 g of diacetone acrylamide and 42.9 g of N- ^ δ- (dimethylamine) ethyO / acrylate were dissolved in 1.0 l of distilled water. 2 ml of isopropanol were added and the solution was adjusted to a pH of 6.4 with concentrated nitric acid. The solution was under nitrogen for 1 hour d. long vented and then mixed with 0.10 g NaHSO ₅ and 0.10 g KgS ₂ O ₈ at the same time. The solution was stirred under nitrogen overnight and then dia3, ysized against running water for 18 hours.

A comparison was made with the cloning approach, Example I. Examination of the images obtained revealed the

temperature
V / \ * / (50.) 50:50 mixed polymer of
Diacetone acrylamide and
N- / B- (dimethylamino) -
ethyl / acrylate
Spacer layer green Blue ^A1} max
Polyvinyl alcohol
Comparison distance
layer green blue (75) Red 1.62 1.58 Red 1.61 1.62 10.0 (100) 1.81 1.59 1.63 1.14 1.68 1.74 24 1.35 1.56 1.54 1.50 1.57 1.69 38 1.65 1.61

The optimum thickness was found to be 12.7 microns (0.5 mil). Good inversion behavior could be noticed with the exception of a certain turbidity at very high or very low levels

■■ -. 47 - 009884 / 09U '· "BAD ORIGINAL

1 7 7 2 / ι 3 O

Temperatures _c Thinner overhangs, z _a B ,. 7.6 Hikron (o, 3 mil) caused at 10 ° ö (5O ⁰ P) a significant salt formation.

Example VI

The procedure of Example I was repeated with a receiving layer, which is a 3 ^ copolymer as a spacer layer from diacetone acrylamide and F- ^ B- (dirnethylamino) ethyl / acrylamide instead of the 40:60 mix polymer of diacetone acrylamide and

^ Contained acrylamide. It was made at a thickness of 8.9 microns (0.35 mil) is applied. The 3s2 copolymer made from diacetone acrylamide and Bf- ^ ß- (dimethylamino) ethyl / acrylamide was like is made as follows:

In a 5 l 3-neck round bottom flask with a stirrer and nitrogen supply was provided, 3 l of distilled water, 204.6 g of diacetone acrylamide and 170.4 g of N- ^ B- (dimethylamino) ethyl7acrylamide given. The solution was made by adding concentrated nitric acid to pH set from 6.4; in addition, 10 ml of isopropanol, 0.5 g

r E ₂ S ₂ O ₈ and 0.5 g NaHSO were added. The solution was stirred under nitrogen overnight and then dialyzed against running water for 18 hours.

The comparison was carried out with the control batch from Example I. Examination of the resulting images showed the following differential shark dimensions:

- 48 -

009884 / 09U

BAD OBJQiNAL

Temperature

10.0

_ο
(P)

3: 2 Mach polymer of Diaoetonacrylamid and! WßCDithli)

ethyl / acrylanide spacer layer

Max
Polyvinyl alcohol

Verglexcbsabatandsschicht

Red

green

(50) 1.61 1.60
(75) 1.47 1.69
(100) 1.67 1.66

blue

Red

1.70 1.76 1.65

1.45
1.35
1.12

green

1.55 1.71 1.38

blue

1.53 1.77 1.56

The optimum thickness of the connection described here proved is 8.9 microns (0.35 mil). Excellent temperature-dependent permeability and flexibility were noted « The adhesion of the spacer layer and the polymer top layer was good.

Although the preferred image receiving layer is a mixture of polyvinyl alcohol and poly-4- vinylpyridine, the invention is not limited thereto. Other BiI receiving layers known per se can likewise be used. Furthermore, although a preferred embodiment has been described on the basis of the presence of a quaternary ammonium compound (see US Pat. No. 3,173,786) and in particular a quaternary ammonium compound which can form an active methylene base in alkali, the invention is not limited thereto, although the advantages Particularly noticeable is the use of a quaternary ammonium salt that forms a fully active methylene.

- 49-

009884/0914

BATH ORIGINAL

SO · ''

Both of the mentioned carrier layers can be the usual rigid or flexible carriers, e.g. glass, paper, metal, polymeric films of synthetic _{or natural origin.} Examples of suitable materials are paper, aluminum; Polymethacrylic acid, methyl and ethyl esters, vinyl chloride polymers, polyvinyl acetal, polyamides such as lylon, polyesters such as polymeric films derived from ethylene glycol terephthalic acid and cellulose derivatives such as cellulose acetate, triacetate nitrate, propionate, butyrate, acetate, propionate, or acetate.

If desired, the support may be used for the image receiving layer be transparent or opaque. Suitable opacifiers can be incorporated into the negative and / or into the positive so that the action can be carried out outside the camera, i.e. in an environment in which the arctic is exposed Light acts on the silver halide emulsion layer.

The new image receiving layers according to the invention make it possible to use a wider range of room temperatures the pH-sensitive image dyes and especially the Allow use of dye developers that have a lower pH isolation than the final pH of the image layer and which can thus be controlled more precisely and reproducibly.

The development is preferably carried out in the presence of a silver halide auxiliary or accelerator substance, which essentially

009884/0914

- 50 -

BATH ORIGINAL

1 7 7 JL *?

form. Be

1 7 7

is colorless , at least in the non-oxidized form, substituted hydroquinones such as phenyl hydroquinone, 4 * -methylphenyl hydroquinone, xoluo hydroquinone, tertiary butyl hydroquinone and 2,5-triptycene diol are particularly useful. These hydroquinones can be ver apply as a component of the developing solution or may be incorporated in one or more layers of Hegativs. Particularly useful results are achieved when 4'-methylpheny! Hydroquinone is dispersed in one or more gelatine intermediate layers and / or in a gelatine layer which is located as a coating on the blue-sensitive emulsion layer »

As already mentioned, the present invention is intended to reduce the pH of the positive image to a value which essentially excludes air oxidation of the developer substances. It is also within the scope of the invention to use antioxidants such as arbutin before the image is exposed to air to provide additional protection against oxidation. As the reduction -

the pH continues for at least a short time after-. After the positive image has been separated from the negative , the use of such an antioxidant enables the positive to be separated at a slightly higher pH than would otherwise be desired.

It is also possible to use other aids, e.g. U.T. absorbers that are effective to light stability or to improve other properties of the positive image. A

- 51 -

009884/0914

"" ^: J772430

Such a UV absorber can be contained in the developer solution his 12th image is seen during the exposure period may be deposited or it may become a thin coating on the image receiving layer prior to exposure are located*

With all preferred. Embodiments of the invention is the polymeric acid layer is preferably thicker than the image receiving layer and has a considerably higher milligram coverage per 0.09 a (ft). The image receiving layer is P preferably about 6.35 to 10.2 microns. (0.25-0.4 mil) thick, the polymeric acid layer is preferably 7.6 to 38.1 microns (0.3-1.5 mils) thick and the aforementioned spacer layer is preferably about 1.3 to 20.3 lukron (0.05-0.8 mils) thick.

Although the invention has been explained in the context of dye developer », is? and the invention is particularly applicable to color developers because of their susceptibility to air oxide tablet at high pH, so the image receiving. Layers, which according to the invention are also used in other diffusion transfer processes, as already described, are * in which a pH reduction is achieved and in particular transfer images with great optical clarity and luminosity in a larger area. Eaumtempöraturen zu ersleleat »

live the one described. publicly they can

also one or more other schiohten

or coatings contain »which in turn contain one or more

-. 008 * 84/0914

- 52 -

1772Λ30

5. Image recording layer according to claims 1-3 _f, characterized in that the polymer layer contains a mixed polymer of N-isopropylacrylaald and M Cβ {diuethylaeino) -ätiiyl] acrylamide.

6. The image receiving layer according to claims 1-3 · characterized in that the polymer layer contains a high-quality polymer of H-propyl acrylamide and 1-methylol acrylamide.

* ■ ■

7. Image recording layer according to claims 1-3, characterized in that the polymer layer is a mixed polymer of diacetone acrylate and bimetylaminoethyl acrylate.

8. Image receiving layer according to claims 1-3, characterized in that the polymer layer is a terpolymer of diacetone acrylamide, acrylic acid and I-methylaminoethyl acrylate is.

9 * Image recording layer according to Claims 1 -8, characterized in that it is polyvinylamide in one

8Iureealzee is available. -

BATH

009884 / 09U

Claims (4)

PATENT CLAIMS 1. An image receiving layer suitable for photographic diffusion transfer processes, containing a support polymeric acid layer as well as a polymer layer and a polymer layer which is permeable to alkali and can be dyed, thereby characterized in that the polymer layer between the polymeric acid layer and the alkali-permeable layer p polymer layer contains a polyvinylamide. . 2. Image receiving layer according to claim 1, characterized in that indicates that the polyvinylamide is a polyacrylic amide 1st. 3. Image receiving layer according to claim 1 or 2, characterized in that the polyvinylamide is hydrophilic ?; and contains hydrophobic groups in such amounts that the Polymc layer shows a lower permeability for alkaline drainage solutions with increasing temperature. 4. Bildaufnahmeeohicht according to claims 1-3, characterized in that the polymer rail contains a mixed polymer of diacetone acrylamide and acrylamide · 0Q988.4 / 09U BATH ORIGINAL Additives such as leveling agents or other intermediate layers may contain, for example, to improve the adhesion « Claims ~ ⁵³ ~ 009884 / 09U