DE2364137A1 - LIGHT SENSITIVE PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

Priority: December 26, 1972 U.S.A. No. 318 402

Light-sensitive photographic recording material

Various diffusion transfer methods for producing color images are known. Transfer image formation becomes quite general achieved when exposing a photosensitive section or a negative section which at least one photosensitive silver halide layer associated with a dye image-forming material (which is a complete dye or a dye intermediate, e.g., a color coupler) to form a developable image; thereafter, this image is developed with an aqueous alkaline developer liquid, with one as a result An image-wise distribution of soluble and diffusible dye-image-forming material is obtained during development This image-wise distribution is at least partially due to diffusion onto an overlying image-receiving section or positive portion containing a dyeable layer to have a colored transfer image thereon, usually to evoke a positive image.

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The dye-forming materials useful in such processes are generally to (1) substances that are initially soluble in the developer solution. borrowed or diffusible, but pictorially as a consequence can be selectively made non-diffusible during development or (2) by substances ^ which are initially in the developer solution are insoluble or non-diffusible, but are made selectively diffusible image-wise as a result of development. There are numerous examples in the patent literature of the two types of image-producing materials «One in particular useful class are the dye developers (dyes that are also silver halide developing agents) and as described, for example, in U.S. Patent No. 2,983,606.

Each of these systems can be used to produce multicolored images, when using a photosensitive section or a negative section which selectively selects at least two contains sensitized silver halide layers, which in each case a dye image-forming material with the desired spectral absorption properties is assigned. The so-called Tripack uses recording materials that are a blue-sensitive, a green-sensitive and a red-sensitive silver halide layer, each of them yielding yellow, purple, and cyan dye image Material is assigned

The negative section and the positive section can initially be separated from one another, which are then placed on top of one another during development and then held together or separated again to give the desired transfer image (as described, for example, in US Pat. No. 2,983,606). They can also be present as a uniform system from the start, for example as the so-called uniform negative-positive recording material, where the corresponding sections are held together before exposure and after image formation

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will. In the latter systems, "in which the two sections are held together, a reflective layer, usually of a white pigment such as titanium dioxide, is provided between the respective components, either as a pre-formed layer or as a layer _t which is formed during development, in order to effectively cover the negative section and to give the desired background for viewing the image which has been produced in the positive section as a reflection image Of course, each support for the positive section should be transparent to enable the transfer image to be viewed «,

Examples of uniform negative-positive recording materials with which one can produce color transfer images without separation are found in US Pat. Nos. 3,415,644-3,415,645; 3,415,646; 3,473,925; 3,550,515; 3,573,042; 3,573,043; 3,573,044; 3,576,625; 3,578,540; 3,589,904; . 3,594,164; 3,594,165; 3,607,285; 3,615,421; 3,615,436; 3,615,539; 3,615,540; 3,619,192; 3,619,193; 3,621,768; _: 3,647,437; 3,652,281; 3,652,282; 3,672,890; 3,679,409; 3,689,262; 3,690,879 and others.

In photographic systems of the type described above which use an aqueous alkaline developer solution it is known to use an acidic layer (neutralizing layer) to lower the ambient pH, after substantial dye transfer has occurred Has. The use of a neutralizing layer and special materials that are suitable for this is in U.S. Patents 3,362,819 and 3,362,821 and in many of the patents mentioned above. In those systems

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who use a neutralizing layer, it is usual, an inert intermediate layer or spacer layer (in the literature sometimes also referred to as a "time layer") to be provided between the applied developer liquid and the neutralizing layer in order to reduce the pH to control, i.e. a timely control of the diffusion to the neutralizing layer and subsequent to achieve pH reduction. Suitable "time" layers are disclosed in U.S. Patent 3,362,819 and other patent publications described.

In the German patent application P 23 19 723.1 timing layers are described, which as a continuous Phase have an aqueous dispersion of a film-forming synthetic polymer, which is essentially is impermeable to the aqueous alkaline developer liquid, e.g. a latex and the discontinuous Phase comprise a material which is sometimes referred to as a "permeator" and which is permeable to the developer liquid is.

Preferred latices are, for example, a 60-38-2 interpolymer of Methyl methacrylate, butyl acrylate and acrylic acid; a 60-30-4-6 interpolymer of butyl acrylate, diaeetone acrylamide, styrene and methacrylic acid; a 60-30-4-6-1.5-0.5 copolymer of butyl acrylate, Diaeetonacrylamide, styrene, methacrylic acid, 2-sulfoethyl methacrylate and divinylbenzene; refer to all weights on a dry weight basis. Other useful latices are those made from polyvinyl chloride, yinyl chloride-yinylacetate mixed polymers, Acrylic polymers and interpolymers, e.g. a terpolymer of butyl acrylate, Methyl methacrylate and small amounts of acrylic acid or methacrylic acid and numerous other latices that match the Are readily known to those skilled in the art. An extensive list of suitable latices useful for this purpose can be found in U.S. Patent 2,795,564.

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Suitable permeators are, for example, isopropyl cellulose, preferably one which contains about 1.3 isopropyl groups per cellulose monomer unit, hydroxypropyl cellulose, acrylonitrile-acrylic acid copolymers, methacrylate-acrylic acid copolymers, preferably those containing about 3% by weight of acrylic acid contain, poly-F-ethyl acrylamide, polyacrylamide, polyethylene oxide, terpolymer of K ^- ethyl acrylamide, methyl acrylamide. and acrylamide, copolymers of N-ethyl acrylamide and 2-vinyl pyridine, copolymers of DT-isopropyl acrylamide and N-vinyl pyrrolidone, copolymers of N-isopropyl acrylamide and dimethylaminoethyl acrylate, and the like. Other useful permeators are graft copolymers such as those described in U.S. Patent 3,575, which are given as materials for useful time shifts.

Subject of this "publication is the collapsed latex section the "time shift referred to as the" continuous phase ", while the permeator component is referred to as the "discontinuous phase". With this phraseology a mixture of the two components is called in which the former component is in a greater concentration as the latter is present, optionally in the form of continuous channels and the like through the coalesced latex may be present. The ratio of latex to the permeator can; depending on the desired degree of Diffusibility in the photographic system vary, in to which it is applied. It is easy to see that as the concentration of the permeator increases, so does the permeability the layer also increases. A typical latex / permeator time layer of the mentioned invention may have a ratio of Latex to permeator on the order of about 19 s 1 to about 99ί1, with a typical ratio in the Of the order of about 40: 1. In any case, the selection of the proportions of the constituents required in each case is important for a given recording material is obvious to the person skilled in the art, so that the above-mentioned ratios only are to be regarded as examples.

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In general, the time layers have according to the invention, a -solche total thickness that the film would be only from the coalesced latex "exist, would be impervious to the _alkaline% developer liquid. The thickness can" for example in the order of 2.5 to 177 8 µ (0.1 to 0.7 mil) thick and contain approximately 300 to 1700 mg solids / 0.09 m surface. When used in systems where the photosensitive layer must be exposed and / or the resulting image must be viewed through that layer, it is desirable that the layer be similar to other layers through which the exposure is to be made and / or through that the picture is viewed is as thin as possible. In these cases, of course, the time layer according to the invention should also be as clear and transparent to visible light as possible. To achieve this clarity, it is important that the latex and permeator be compatible, since incompatibility would result in a film that is not as permeable or clear as desired and that would not be macroscopically homogeneous. With different latex / permeator mixtures it is obvious that different degrees of compatibility can be achieved. An indication of such compatibility is the clarity that is ultimately achieved in the recording material, with light scattering being the undesirable result of a more or less greater incompatibility between the latex and the permeator, while a further indication of this is the degree of macromolecular inhomogeneity. It can therefore be seen that the discontinuities between the coalesced latex film, caused by the permeator, should in such cases be sufficiently small to avoid scattering of incident light. The layer can be regarded as homogeneous if the coalesced latex contains a permeator which is tolerably distributed through the coalesced latex film so that it does not cause any scattering of incident light. Viewed microscopically, this means that the layer generally in

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essential from the confluent latex with numerous small localized areas "containing the permeator."

In the photographic systems in which the positive, section is a separate section (as opposed to uniform negative-positive recording materials), containing a neutralizing layer, this section or image receiving section generally has a suitable one Support, which can be opaque or transparent, e.g. a paper support with the desired neutralizing layer, e.g. an acid layer as described in U.S. Patent 3,362,819, a time layer, which comprises a latex of the type described above (see US Ser. No. 246,779) with polyvinyl alcohol as the permeator and a dyeable layer such as that described in U.S. Patent 3,148,061 and polyvinyl alcohol and poly-4-vinyl pyridine contains. Other reagents such as stabilizers, development retardants, UV light absorbers and the like can also be used be present, but do not in themselves constitute part of the present invention.

A typical image receiving section as described above contains, for example, a paper support on which there is in the following order: An approximately 20.3 μ (0.8 mil) thick layer which contains the partial butyl ester of a polyethylene / maleic anhydride mixed polymer, which according to example 10 of U.S. Patent 3,362,819; a time layer about 7.6 µ (0.3 mil) thick comprising about a 40: 1 ratio of a 60-30-4-6 interpolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid, and polyvinyl alcohol, e.g., one with high viscosity and $ 100> contains hydrolyzed polyvinyl alcohol; a 10.2 µ (0.4 mil) thick dyeable or image receiving layer containing a 2: 1 mixture (parts by weight) of polyvinyl alcohol and poly-4-vinyl pyridine.

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Instead of the neutralizing and time layers that Associated with the positive section, as in the previous example, they can also be arranged in the negative section (see U.S. Patent 3,562,821) or in both sections.

The preferred uniform negative-positive recording materials according to the invention are those described in US Pat. No. 3,415,644. According to this, the essential layers of the negative and positive section are enclosed between two layer carriers, one of which is opaque and is assigned to the negative section, while the other is transparent and is assigned to the positive section. The recording material is exposed through the latter and the resulting color image is then viewed through reflecting light. Essentially, such a recording material for the production of color images contains in the following order a transparent support, a neutralizing layer, a time layer according to the invention, a dyeable layer, a blue-sensitive silver halide emulsion layer, to which a yellow dye image-forming material is assigned in the same or an adjacent layer is, a green-sensitive silver halide emulsion layer to which a purple dye image-forming material is assigned in the same or an adjacent layer, a red-sensitive silver halide emulsion layer to which a cyan dye image-forming material is assigned in the same or an adjacent layer and a opaque substrate. Preferably, an interlayer or spacer layer between each set of silver halide and its associated dye image _r built-forming material such as an intermediate layer is as described in US-PS-3,625,685 and includes a latex and a permeator, in accordance with the present invention the permeator used in these negative interlayers will be polyvinyl alcohol,

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as in the journals according to this invention. The negative and positive components are preferably pre-laminated as described in U.S. Patents 3,652,281 or 3,652,282. The pre-lamination is then carried out in such a way that delamination takes place at this intermediate point after the application of an aqueous developer solution in order to enable development and formation of the transfer image, with re-lamination taking place due to the presence of a viscous substance in the developer fluid, with which the cohesion of the finished image is accomplished. In addition to these essential photographic reagents, the developer liquid also contains a reflective agent, e.g. a dispersion of titanium dioxide, so that when applied to this layer it effectively covers the negative portion (including developed silver and any associated dye image-forming material) and the necessary background for viewing the Color transfer image made possible by reflected light through the transparent support without separation. The developer solution preferably also contains an additional opacifying agent which, in conjunction with the opaque layer support, results in a "light-tight envelope" in which the negative section is sandwiched so that the recording material can be developed in the light. This last-mentioned embodiment is described in many of the patents described above, with a preferred system being illustrated in U.S. Patent 3,647,437. Thereafter, the developer solution contains one or more optical filter substances (sometimes also called "indicator dyes ¹¹ ), which are strongly colored at the alkaline pH of the developer liquid, but which are" lightened "or made essentially transparent at the lower pH of the subsequent neutralization, see above that they do not interfere with viewing the broadcast image.

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An example of a uniform negative-positive recording material can, for example, according to the above information. by being prepared by applying a layer coated with a gelatin, 101.6 p. (4 mil) thick opaque polyethylene terephthalate support coated with the following layers ι

1. A layer of blue-green developing dye,

dispersed in gelatin; about 75 mg of dye and about 80 mg

2
Gelatin per 0.09 m;

2. a red-sensitive gelatin silver iodobromide emulsion;

ρ about 140 mg silver and about 70 mg gelatin per 0.09 m;

3. a layer of a 60-30-4-6 mixed polymer of butyl acrylate, Diacetone acrylamide, styrene and methacrylic acid together with polyacrylamide; about 150 mg of interpolymer and about

2
5 mg polyacrylamide per 0.09 m;

4 "a layer of a purple dye developer, dispersed in gelatin; about 79 mg of dye and about 67 mg of gelatin per 0.09 m;

5 · a green sensitive gelatin silver iodobromide emulsion;

2 about 80 mg of silver and about 40 mg of gelatin per 0.09 m; ^:

6. a layer of the mixed polymer described in layer 3, together with polyacrylamide; about 100 mg mixed poly

2 mer and about 12 mg polyacrylamide per 0.09 m;

7. a layer of "yellow dye developer" dispersed in gelatin; about 83 mg of dye and about 65 mg

2 -

Gelatin per 0.09 m;

8. a blue-sensitive gelatin silver iodobromine demulsion with an auxiliary developer substance, namely. 4'-methylphenylhydroquinone; about 120 mg of silver, about 60 mg of gelatin and about

30 mg of auxiliary developer substance per 0.09 m and

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9. a gelatin layer; about 50 mg gelatin per 0.09 m ² .

The three developer dyes mentioned above have the following Formulas

a cyan dye developer;

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HO-CH ₂ -CH ₂ HO-CH ₂ -CH ₂ '

N-SOo- '

OH

, -C-CH ₂ -CH ₂ -

OH

a purple dye developer; and

NO,

C ₃ H ₇ O

.CH =

Cr H ₂ O

-0

CH ₂ -CH ₂

a yellow dye developer.

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Then put on a clear 101.6 u (4 mil) thick Polyethylene terephthalate layer base applied the following layers in the order given:

1. As the polymeric acid layer, the partial butyl ester of polyethylene / maleic anhydride mixed polymer; he was, by adding 300 g of highly viscous poly (ethylene / maleic anhydride), 140 g of n-butyl alcohol and 1 ml of 85% phosphoric acid for 14 hours refluxed for a long time; about 2500 mg mixed

2
polymer per 0.09. m »

2nd time layer made of a 60-30-4-6 copolymer of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid as well as with polyvinyl alcohol in a ratio of 40: 1; cover

2
about 500 mg per 0.09 m and

3. polymeric image-receiving layer made from a 2: 1 mixture

(Parts by weight) of polyvinyl alcohol and poly-4-vinvl-

2 pyridine; Coverage about 400 mg per 0.09 m.

The two sections were then combined into a laminate, which represented the desired uniform recording material.

At the lead edge of each of the laminates can then be a tearable Container attached with an outer layer made of lead foil and an inner lining made of polyvinyl chloride with an aqueous alkaline developer solution in the container. The "fastening" can be done with a pressure-sensitive tape, the container and the laminate are joined together so that after Applying compressive force to the container's edge seal tears open and seJtn content between the dyeable (layer 3 of the positive section) and the gelatin layer (Layer 9 of the negative section) is distributed.

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For example, the tearable container can contain a developer solution contain the following composition:

water 100 ml Potassium hydroxide 11.2 G Hydroxyethy cellulose (high -
viscous); in trade from the
Hercules Powder Co., Wilmington,
Delaware under the designation
Natrasol 250 3.4 S. LT-phenethyl- pico liniumbroinid 2.7 G Benzotriazole 1.15 G Titanium dioxide 50.0 G

2.08 g

~ 12 ^H 25 "°

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0.52 g

OH

1.18 g

OH

C-CH ₃

OH

-CH,

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The recording material can then be exposed in a known manner become., whereby a developable image is obtained; the recording material reported in this way can then pass through Applying a compressive force to the rupturable container is developed, thereby removing the aqueous alkaline developer solution and thus a multicolored transfer image formed by the transparent polyethyleneterephthalate layer support as a positive R-efl.exi.ons image can be viewed.

The use of polyvinyl alcohol as a permeator instead iron the permeator. like polyacrylamide used in German Patent application P ..,.,. are described, results in certain Gate parts, the most important of which is the manufacture of the gate parts from a commercial point of view.

The layers according to the invention can easily be produced thereby be able to get the polyvinyl alcohol, latex and other solids in the desired amounts in a single Mixing containers together. In contrast to this simple process, permeators such as polyacrylamide cannot do so easily be mixed together, because polyacrylamide must first be brought into solution. This takes about 24 hours and requires storage containers for subsequent use, in technical hat.

To the poor solving power and the storage problems with such bermeators, fluctuations in the amount of permeator solids in these containers with the permeator solution Do not avoid so that it is difficult to use permeator latex layers to obtain in which the exact ratio of permeator to latex is adhered to, so that the photographic Use of the recording material at a constant rate and produces reproducible results. This latter problem is -naturally not insurmountable, but requires a quality control, analysis and testing from the standpoint

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large-scale production are highly undesirable. All of these problems become simple and effective through application dissolved by polyvinyl alcohol.

In addition, the use of polyvinyl alcohol has been surprising led to improved photographic results. So you could have better behavior while developing at low temperatures notice while the same behavior was maintained at room temperature and higher. Thus, polyvinyl alcohol gives better performance over the temperature range from hot to cold in terms of timing the alkali diffusion and the subsequent pH decrease within the prescribed time sequence during the development stage.

For the person skilled in the art it is self-evident that the permeator and the latex which form the layer are interrelated in the sense should be compatible that they do not interact with each other in such a way that light is absorbed and / or reflected. It has been found that this is how polyvinyl alcohol behaves when alkali is added to adjust the pH, e.g. pH 7 to cause fogging. In systems such as the standard one described as an example Negative-positive recording material viewed through this layer is of course undesirable and the neutralization stage described above should therefore be observed. For example, the layer is without neutralization, e.g. completely clear at a pH of 4.5 and fulfills its desired function in the prescribed manner.

The fogging resulting from the neutralization is of course not a problem in systems in which the Time and neutralization layers are arranged in the product, e.g. in the negative section, so that they do not overlap to be in the path of the light with which one is contemplated. It seems

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also that there is no problem with the systems with which the scb.icht.en thus arranged in the image receiving section which is separated after the image is formed. Although the' The actual causes are not yet fully understood, the fogging problem appears to be a surface phenomenon that should be considered with these systems.

So if contained in the spacer layer according to the invention alkali or if it comes into contact with it in order to adjust the pH, it goes without saying that this measure should be avoided if the pH adjustment "becomes undesirable Haze formation leads. In any case, lead the invention Spacer layers to the advantages mentioned above.

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Claims (1)

Claim light-sensitive photographic recording material, containing a photosensitive portion with at least a photosensitive silver halide emulsion layer, the one dye developer, one! color coupler or another color former known for diffusion transfer processes is assigned, as well as an image receiving section which is a dyeable layer contains, on which a color image can form and where a neutralizing layer in the image receiving section and a spacer layer is included through which initially Diffuse an aqueous alkaline developer solution .must., before it reaches the neutralizing layer, after Building patent application P 23 19 723 «1, whereby the distance— sehicht in ϊΌπη a dispersion is present., whose continuous Phase consists of an aqueous film-forming synthetic polymer that is used for the developer liquid is essentially impermeable and its discontinuous phase consists of one for the developer solution permeable material, characterized by g e k e η 21, that the discontinuous phase consists essentially of polyvinyl alcohol. 8th! 6/091) 6