JPS633300B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF APPLICATION OF THE INVENTION The present invention relates to photography. More particularly, the present invention utilizes a stripping layer having a plurality of adjacent hydrophilic layers, one of which contains a certain amount of particulate material, to cleanly separate the image-receiving layer from the rest of the assembly after processing. Regarding black and white and color diffusion transfer photography. In a preferred embodiment,
The separated image-receiving layer has substantially no stripping layer attached thereto. PRIOR ART Various configurations of color integral transfer elements are described in the literature, such as U.S. Pat. No. 3,415,644;
3415645, 3415646, 3647437, 3635707, 3756815 and Canadian Patent No.
It is described in the specifications of No. 928559 and No. 674082. In these forms, the image-receiving layer with the photographic image for observation remains permanently bonded and integrated with the imaging and auxiliary layers present in the structure (the transparent support is used for observation of the assembly). (when used on the side). The image is formed by the dyes produced in the imaging layer and, after diffusing through each layer of the structure, reaches the dye image-receiving layer. After exposure of the assemblage, an alkaline processing composition penetrates the various layers and initiates development of the exposed light-sensitive silver halide emulsion layers. The emulsion layers are developed in proportion to the extent of each exposure and the image dyes formed or released in the respective imaging layers begin to diffuse through the structure. At least a portion of the imagewise distributed diffusible dye diffuses into the dye image-receiving layer, thus forming an image of the original object. There is no need for the user to time this process. The monolithic assembly described above has one problem.
That is, the silver halide and other imaging layers, the used pot that originally contained the processing solution, and the trap holding excess processing solution all remain with the print after processing. As a result of this, the resulting prints are bulky and pose some difficulty in storing and organizing in albums. Peel-away configurations for color diffusion transfer assemblies are also prior art, e.g., U.S. Pat. No. 2,983,606;
It is described in the specifications of the same No. 3362819 and the same No. 3362821. In these configurations, the image-receiving element must be separated from the photosensitive element after a certain amount of time, typically about one minute. This means that
This means that the user has to time the process, which is a disadvantage if a clock is not at hand. Additionally, some of the assemblies to be disposed of are wet with caustic processing solutions and must be handled with care. U.S. Pat. No. 3,730,718 relates to a diffusion transfer assembly that uses a stripping layer to allow the image-receiving layer to be separated from the photosensitive element during development. Examples in this patent use stripping layers between layers that both contain particulate material. However, assemblages in which particulate matter is present in layers on both sides of the stripping layer cause the stripping layer to fracture unevenly during separation, exhibiting the following drawbacks. Further, U.S. Pat. No. 4,359,518 relates to a diffusion transfer assembly that uses a stripping sheet with a release layer to strip the photosensitive layer from the film unit after processing. Particulate materials such as silica particles are used in the timing layer of the stripping sheet to prevent blocking and act as an antistatic agent. Example A of this patent uses a release layer between the silver halide emulsion layer and a "protective layer" (the composition of which appears to be unknown). However, this patent does not disclose the use of a hydrophilic layer between the stripping layer and the silver halide emulsion layer and containing particulate material as described herein. Problem to be Solved by the Invention The use of stripping layers in assemblies such as those described above has one problem. Although it would be highly desirable to remove the stripping layer as a uniform piece and retain it in a section to be separated and discarded, it has been found that in practice the stripping layer itself fractures. The result is parts of the stripping layer that adhere irregularly to two separate surfaces. The back of the image-receiving layer separated in this way has a highly speckled appearance, which is undesirable for commercial products. This speckled appearance is particularly noticeable in the Dmin region with a form of transparency. Structure of the Invention The present invention comprises (a) a photosensitive element comprising a silver halide emulsion layer, (b) an image receiving layer, and (c) a stripping layer between said silver halide emulsion layer and said image receiving layer. , both sides of said stripping layer have directly adjacent thereto hydrophilic layers different from the photosensitive silver halide emulsion layer or the image receiving layer, provided that one of said hydrophilic layers is substantially non-photosensitive. The above problem is solved by providing a photographic assemblage comprising particulate material in an amount of 5 to 75% by volume of the hydrophilic material-particulate material mixture in its layer, which when separated:
Substantially all of the stripping layer is retained in the portion of the assembly having the hydrophilic layer containing the particulate material. In a preferred embodiment of the invention, a hydrophilic layer containing particulate material is present between the stripping layer and the silver halide emulsion layer such that, when separated, substantially all of the stripping layer contains the halogenated silver halide emulsion layer of the assemblage. It is retained in the area containing the silver emulsion layer. To form a black and white image, the exposed photosensitive element is developed. As a result of this development, in the unexposed area,
The silver halide complexing agent contained therein dissolves the silver halide and transfers the dissolved silver halide to the image receiving layer. Next, the silver precipitate-forming nuclei contained in the image-receiving layer cause reduction of the previously transferred silver halide complex, converting it into silver. In this way, an image pattern corresponding to the original is formed. Process details are well known to those skilled in the art, as described, for example, in US Pat. No. 3,220,835 and US Pat. No. 3,820,999. In a preferred embodiment of the invention, the silver halide emulsion layer has a dye image-providing material associated therewith. In the present invention, any material can be used as the stripping layer as long as it has the necessary properties. Such materials are disclosed, for example, in U.S. Pat. A preferred embodiment of the invention uses hydroxyethyl cellulose. The stripping layer materials used in this invention can be used in any amount effective for the intended purpose. Good results are obtained when the concentration is between 5 and 2000 mg per m ² of element. This specific usage is
Variations will, of course, depend on the particular stripping layer material used and the particular diffusion transfer element selected. The materials used in the hydrophilic layer on each side of the stripping layer in the present invention may be any of the well-known materials commonly used for such applications in the photographic field. These materials include, for example, gelatin, polysaccharides, acrylamide polymers and other polymeric materials, such as
Research Disclosure, December 1978, Volume 176, Page 26
Contains polymeric substances listed in Section 17643.
A preferred form of the invention uses gelatin. The coverage of the hydrophilic layer can vary within wide limits as desired. 0.1~ per ^1m2
Good results are obtained with a coating layer of 2.0 g. The particulate material used in the hydrophilic layer of the present invention described above may be any material that produces the desired result in intimately bonding the layer to the adjacent stripping layer. Such materials should not be photosensitive as they may interfere with image formation in the photosensitive portions of the photosensitive element. Cabot Regal 400 carbon black with an average particle size of 0.07μm and CITGO (Colombia) with an average particle size of 0.07μm
Carbon black like Carbon Raven 410;
Gulf and Western with an average particle size of 0.25μm
Good results were obtained using titanium dioxide such as Horsehead Rutile; colloidal silica such as Dupont Ludox AM with an average particle size of 0.012 μm; and poly(methyl methacrylate) beads with an average particle size of 0.5 μm. In a preferred embodiment, carbon black is used. The particle size of the particulate material used in the present invention can vary over a wide range as indicated in the particle size ranges above. Generally, the particle size ranges from 0.01 μm to 0.5 μm. The amount of particulate material to be coated can also vary widely, as long as the volume percentage of particulate material in the mixture of hydrophilic material and particulate material in that layer is between 5 and 75%. less than 5% or
If more than 75% particulate material is used, the desired improvement in layer separation will not be achieved. This percentage is commonly referred to in the art as PVC percentage (pigment volume content). The preferred PVC percentage for this invention is 10-50%
It is. The amount of particulate material to be coated in the hydrophilic layer is a function of its density. Particulate materials have been used in photographic elements for a number of reasons. For example, the above-mentioned US Pat. No. 4,259,518 discloses in column 4 that silica particles in the outermost layer prevent blocking when the stripping layer is wound. Such materials are known in the art as "antiblocking" agents. Therefore, the presence of such a material in one layer would be expected to reduce the adhesion of that layer to adjacent layers. However, it has surprisingly been found that exactly the opposite occurs according to the present invention. It has been found that the hydrophilic layer adjacent to the stripping layer containing particulate material bonds to the stripping layer more strongly than the hydrophilic layer on the other side. Delamination occurs at the weakest interfacial bonds, allowing the stripping layer to be retained in the part of the assembly to be discarded after separation (usually the part containing the silver halide emulsion layer). The image-receiving layer then peeled off will therefore have a clean appearance on its back side. The use of particulate material in one of the hydrophilic layers adjacent to the stripping layer in the assemblies described herein is a means by which the bond between these two layers can be strengthened. This allows stripping to occur on the opposite side of the stripping layer. The hydrophilic layer opposite the stripping layer is
Preferably, it is free or substantially free of particulate matter. This is because the presence of a significant amount of particulate matter in that layer tends to undesirably strengthen the bond between that layer and the stripping layer. The present invention can be used in diffusion transfer assemblies where it is desirable to obtain reflective prints without the bulk of silver halide and other layers, spent pots and traps. In other words, the assemblage of the present invention combines the feel and archival properties of conventional photography with the convenience and advantages of instant photography. Transparency can also be obtained in a similar manner. Additionally, by using a transparent support and utilizing the image carried in the element, and subsequently removing the residual image dye, silver halide and opacifying layer,
Transparency elements can be obtained according to the invention. In that embodiment, the portion of the assembly that includes the dye image-receiving layer is the portion that is to be discarded, so it is desirable to have the stripping layer in that portion. In that case, the particulate material is present in the hydrophilic layer between the stripping layer and the dye image-receiving layer. In this case, there will be a clean separation on the other side of the stripping layer, if desired. Removing the layers of silver halide and dye image-providing materials from the assemblage also creates the option of recovering these expensive materials from the waste portion of the assemblage (if it is economical to do so). (if possible). The method of forming photographic images in color according to the present invention includes the following steps: () a support and at least one light-sensitive silver halide emulsion layer on the support in which a dye image-providing material is associated; () treating said element with an alkaline processing composition in the presence of a silver halide developer, thus developing each exposed silver halide emulsion layer;
Thus: (a) the imagewise distributed dye image-providing material is formed as a function of development of the silver halide emulsion layer, and (b) at least a portion of the imagewise distributed dye image-providing material is formed in the dye image-receiving layer. () separating the dye image-receiving layer from the remainder of said light-sensitive element using a stripping layer as described above and an adjacent hydrophilic layer, wherein substantially all of said stripping layer is in the form of particulate particles as described above; the hydrophilic layer comprising the substance retained in the element portion. In the methods described above, the photographic element can be treated with an alkaline processing composition to effect or initiate development in any manner. One preferred method for applying the treatment composition is the use of a breakable container or pot containing the composition. In a preferred embodiment of the invention, the photographic assembly comprises the following elements: (a) a support and at least one light-sensitive silver halide emulsion layer on the support in which a dye image-providing material is associated; (b) a transparent cover sheet located on the outermost layer of the photosensitive element; (c) a dye located either in the photosensitive element or on the transparent cover sheet; an image-receiving layer; and (d) an alkaline processing composition and means for containing and discharging said composition between said photosensitive element and a transparent cover sheet, and the assembly comprises a stripping layer and as described above. Contains an adjacent hydrophilic layer. In one preferred embodiment of the invention, the means containing the alkaline treatment composition is a breakable container or pot. The container or pot is such that the contents of the container are released into the photographic assembly by compressive force applied to the container by a pressure member, such as found in cameras designed for in-camera processing. It is made to be in such a position that during the processing of the assembly. The dye image-providing materials useful in this invention are either positive-working or negative-working and are initially mobile or immobile in the photographic element during processing with the alkaline composition. . The present invention is useful in a configuration for integral photographic elements having a negative-working image receiving element, which configuration is disclosed in Canadian Patent No. 928,559. In this embodiment, the support of the photographic element is transparent and includes an image-receiving layer, a substantially opaque light-reflecting layer, said stripping layer and an adjacent hydrophilic layer, and said photosensitive layer(s). is coated. A breakable container containing an alkaline processing composition including a developer and an opacifying agent is located intermediate the top layer and the transparent cover sheet, and the cover sheet also has a neutralizing layer and a clear cover sheet above it, in order. It has a timing layer. The film unit is housed in a camera, exposed through a transparent cover sheet, and then passed between a pair of pressure members in the camera and withdrawn therefrom. A pressure member ruptures the container and disperses the processing composition and opacifying agent therein onto the negative portion of the film unit to desensitize the negative portion. The processing composition develops each silver halide layer and the dye image formed as a result of development diffuses into the image-receiving layer;
Thus, a correct positive image is provided. This image can be viewed through a transparent support on an opaque reflective layer background. Yet another useful integral configuration with which the present invention can be used is U.S. Pat. No. 3,415,644;
It is described in the specifications of No. 3415645, No. 3415646, No. 3647437, and No. 3635707. The assemblies of the present invention can be used to form monochrome or multicolor positive images. In a trichroic system, each of the silver halide emulsion layers of the film assembly has a dye image-providing material associated therewith, and the dye image-providing material includes a portion of the visible spectrum to which the silver halide emulsion is sensitive. It will have the main spectral absorption in the region where it has. The dye image-providing materials associated with each silver halide emulsion layer are contained within the silver halide emulsion layer itself or are otherwise contained in a layer adjacent to the silver halide emulsion layer. A variety of silver halide developers are useful in the present invention. Specific examples of developer or electron transfer agents (ETA) useful in the present invention include hydroquinone,
Catechol, and 3-pyrazolidinone compounds. Combinations of different ETAs can also be used. If neutralizing substances are used in the described assemblies, the stability of the transferred image can be increased. This neutralizing substance increases the PH value of the image layer from about 13-14 to at least 11.
up to 5 to 8, preferably 5 to 8, within a short time after imbibition. Suitable substances and their functions can be found, for example, in Research Disclosure
July 1974 edition, pages 22-23, and Research
Disclosure, July 1975 edition, pages 35-37. A timing layer or an inert spacer layer can be used over the neutralization layer. This layer allows you to "time" the decrease in PH value as a function of the rate at which the alkali diffuses through the inert spacer layer.
Or you can control it. Examples of such timing layers and their functionality can be found in the literature cited in the above paragraph regarding neutralization layers:
Disclosed in Research Disclosure. The term "non-diffusible" as used herein has the meaning commonly accepted as a photographic term and, for all practical purposes, in an alkaline medium and preferably at PH=11 or Refers to a material that does not migrate or float through an organic colloid layer, such as gelatin, in a photographic assemblage when processed in a further medium. The word "immobility" can also be given the same meaning as above. The term "diffusive" has the opposite meaning when applied to the materials of this invention and has the property of diffusing effectively through the colloidal layer of a photographic element in an alkaline medium. Refers to matter. “Mobility” has the same meaning as “diffusion.” The term "in combination with" as used herein has the meaning that two or more materials may be present in either the same layer or different layers, as long as the materials are accessible to each other. is intended. Aspects of the Invention The following examples are intended to further illustrate the invention. Example 1 (A) Comparative integrated image receiver (IIR) by coating the following layers in the order listed on a transparent poly(ethylene terephthalate) film support:
Manufactured elements. Amounts are given in parentheses in g/m ² unless otherwise stated. (1) Poly(styrene-co-N-benzyl-N,
N-dimethyl-N-vinylbenzylammonium chloride-co-divinylbenzene) (molar ratio 49:49:2) (1.1) and gelatin (1.2)
image-receiving layer, (2) poly(styrene-co-1-vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride) (50:40:10 molar ratio)
(1.6) and gelatin (0.75) image receiving layer, (3) titanium dioxide (17) and gelatin (2.6)
(4) Opaque layer of carbon black (0.95) and gelatin (0.65); (5) Gelatin interlayer (0.54); (6) Stripping layer of Natrosol GXR-250 hydroxyethyl cellulose (0.81); (7) Gelatin interlayer (0.64), (8) cyan dye Releaser B of U.S. Pat. No. 4,356,250 (0.37) and gelatin (0.54), and (9) gelatin overcoat (0.43). Layers 8 and 9 are the top and bottom layers of the finished IIR as described in Example 1 of US Pat. No. 4,356,250. For the purposes of this test, it was not necessary to have a complete photosensitive element. (B) Same as (A) except that layer 7 further contains poly(methyl methacrylate) beads (0.56) with an average particle size of 0.5 μm at 47% PVC (pigment volume content).
Manufactured IIR. (C) Layer 7 further contains poly(methyl methacrylate) beads (0.18) with an average particle size of 0.5 μm, PVC22%
An IIR similar to (A) was produced except that it contained . (D) Layer 7 is also Dupont with an average grain size of 0.012 μm.
Ludox AM Colloidal Silica (0.95)
An IIR similar to (A) was produced except that it contained 47% PVC. (E) Layer 7 is further made of Dupont with an average grain size of 0.012 μm.
Ludox AM Colloidal Silica (0.32)
An IIR similar to (A) was produced except that it contained 23% PVC. (F) Layer 7 is Cabot with an average grain size of 0.07 μm.
Regal 400 Carbon Black (0.95) PVC50
IIR was prepared similar to (A) except that it was contained in %. (G) Layer 7 is Cabot with an average grain size of 0.07 μm.
Regal 400 Carbon Black (0.32) PVC25
IIR was prepared similar to (A) except that it was contained in %. (H) Layer 7 further contains Gulf and
Western Horsehead Rutile Same as (A) except containing titanium dioxide (1.8) in 48% PVC.
Manufactured IIR. (I) Layer 7 further contains Gulf and
Western Horsehead Rutile Same as (A) except containing titanium dioxide (0.59) in 24% PVC.
Manufactured IIR. The coatings described above were prepared using particulate materials with approximately constant PVC percentages. Therefore, the actual coating weight will vary. Each material was coated at IX and 3X levels. I conducted a "tape test" on the above IIR. This test has a high correlation with actual stripping performance in actual photographic coatings. This test is based on 3M's Layer 9 on top of the IIR to be tested.
It consists of firmly pressing a small section of Scotch 810 Magic transparent tape and pulling it rapidly over the tape. IIR's B-I thus tested were debonded at a point between layers 6 and 5, showing the weakest bond in that element. In control IIR A, irregular discontinuous stripping occurred. A second tape test was then performed on the remaining elements above layer 6 to determine weak bonding. If layer 6 was not removed by this second test, the bond between layers 7 and 6 is considered strong. If layer 6 is removed in the second tape test, the bond is weaker (but still layers 6 and 5
is considered to be stronger than the bond between The following results were obtained:

【table】

[Table] The above results show that in all examples, the use of particulate material in the hydrophilic layer adjacent to the stripping layer improves the adhesion between these two layers, thus increasing the Indicates that it causes peeling. In IIR elements B, D, F and H, strong bonding between layers 6 and 7 was achieved due to the use of high concentrations of particulate material. Example 2 (A) Example 1, except using the following layers after layer 7:
An IIR similar to (A) in was prepared with: (8) cyan redox dye-providing layer, (9) gelatin interlayer, (10) red-sensitive silver halide emulsion layer, (11) gelatin interlayer, (12) a magenta redox dye-providing layer, (13) a green-sensitive silver halide emulsion layer, (14) a gelatin interlayer, (15) a yellow redox dye-providing layer, (16) a blue-sensitive silver halide emulsion layer, and (17) Gelatin overcoat layer. Layers 8-17 are similar to those described in Example 1 of Irani et al., US Pat. No. 4,356,250. (B) Layer 7 is also Dupont with an average grain size of 0.012 μm.
PVC9 Ludox AM Colloidal Silica (0.11)
An IIR similar to (A) was produced except that it contained . (C) Layer 7 is further made of Dupont with an average grain size of 0.012 μm.
Ludox AM Colloidal Silica (0.32)
IIR similar to (A) was produced except that PVC23 was included. (D) Layer 7 is also Dupont with an average grain size of 0.012 μm.
Ludox AM Colloidal Silica (0.65)
IIR similar to (A) was manufactured except that PVC38 was included. (E) Layer 7 is further made of Dupont with an average grain size of 0.012 μm.
Ludox AM Colloidal Silica (0.95)
IIR similar to (A) was manufactured except that PVC48 was included. (F) Same as (A) except layer 7 further includes CITGO (Columbia) Carbon Raven 410 carbon black (0.11) with an average particle size of 0.07 μm in PVC10.
Manufactured IIR. (G) Same as (A) except layer 7 further includes CITGO (Columbia) Carbon Raven 410 carbon black (0.32) with an average particle size of 0.07 μm in PVC25.
Manufactured IIR. (H) Same as (A) except that layer 7 further includes CITGO Carbon Raven 410 carbon black (0.65) with an average particle size of 0.07 μm in PVC40.
Manufactured IIR. (I) Same as (A) except that layer 7 further includes CITGO (Columbia) Carbon Raven 410 carbon black (0.95) with an average particle size of 0.07 μm in PVC52.
Manufactured IIR. U.S. patent for cover sheet and treatment pot
These were prepared similarly to those in Example 1 of the '4356250 specification and laminated into a film assembly. The film assembly described above was exposed to a graded density color test object (to demonstrate that the stripping layer and adjacent hydrophilic layer had no sensitometric effect). The assembly was treated by spreading the contents of the treatment pot between the cover sheet and the IIR using a pair of juxtaposed rollers. The laminated film assembly was stored at room temperature for 1 week, at room temperature for 3 weeks,
It was left standing at 32°C/15%RH for 3 weeks. Each assemblage was then manually peeled to separate the receiver from the overlying silver halide emulsion layer. Ideally, separation should occur between layers 5 and 6 (denoted as position 1). Separation sometimes occurred between layers 6 and 7 (marked as position 2). In this case, macroscopically visible, irregularly shaped areas of the stripping layer disadvantageously remain on the back side of the stripped receiver. In other cases, separation occurred at various locations above layer 8 (labeled location 3). This is the least preferred separation point because the emulsion layer and dye-providing layer are retained on the image-bearing element and can cause smear problems in addition to being visually undesirable. The data below shows the stripping properties for various particulate materials in layer 7 coated adjacent to stripping layer 6. The % separation area is shown in the table by position 1/2/3. Therefore, the ideal separation would be 100/0/0. 100% separation area relates between layers 5 and 6 for both the wet area (center) and the dry area (edges). 30/60/10
, a very unsatisfactory separation covers 1/3 of the area
Approximately 2/3 of the stripping layer was retained on the back side of the separated receiver, indicating that a significant portion of the emulsion layer was fractured. Separation begins in the dry outer mask area of the assembly and continues through the initially wet central image area. It is therefore desirable to have clean separation in both the dry and wet regions of the assembly, as well as at interfaces. The following results were obtained.

[Table] The above results show that when adding particulate matter to layer 7,
This shows that both wet and dry stripping have been improved. In most cases, as the amount of silica or carbon black increases, layer 5
The separation between and 6 was improved. however,
Very high concentrations should be avoided since problems arise with layers lacking integrity (spontaneous separation) and being brittle.

Claims (1)

[Scope of Claims] 1. A photosensitive element comprising (a) a silver halide emulsion layer, (b) an image-receiving layer, and (c) a stripping layer between the silver halide emulsion layer and the image-receiving layer. , both sides of said stripping layer have directly adjacent thereto hydrophilic layers different from the light-sensitive silver halide emulsion layer or image-receiving layer, and only one said hydrophilic layer is a substantially non-light-sensitive layer. The particulate material is added to the hydrophilic material in the layer at 5 to 75% by volume of the particulate material mixture.
Photographic collection containing in the amount of.