CA1148009A - Diffusion control layers in diffusion transfer photographic products - Google Patents
Diffusion control layers in diffusion transfer photographic productsInfo
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- CA1148009A CA1148009A CA000322010A CA322010A CA1148009A CA 1148009 A CA1148009 A CA 1148009A CA 000322010 A CA000322010 A CA 000322010A CA 322010 A CA322010 A CA 322010A CA 1148009 A CA1148009 A CA 1148009A
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Abstract
ABSTRACT
A diffusion control layer comprising a polymerization product of a monomer capable of undergoing B-elimination in an alkaline environment is disclosed for use in diffusion transfer film units, as an interlayer or overcoat in photosensitive elements, or as a timing layer or overcoat in image-receiving elements.
A diffusion control layer comprising a polymerization product of a monomer capable of undergoing B-elimination in an alkaline environment is disclosed for use in diffusion transfer film units, as an interlayer or overcoat in photosensitive elements, or as a timing layer or overcoat in image-receiving elements.
Description
1J 9L8~9 Various diffusion transfer systems have been disclosed in the art. Generally speaking, a transfer image is obtained by exposing a photosensitive element or negative component comprising at least one light sensitive silver halide layer to form a developable image; thereafter developing this image by applying an aqueous alkaline processing fluid; forming, as a function of this develop-ment, an imagewise distribution of soluble and diffusible image-forming material, which may be a dye, a dye inter-mediate or a soluble silver complex; and transferring this imagewise di.stribution, at least in part, by dif-fusion to a superposed image-receiving element or posi-tive component including an image-receiving stratum to impart thereto a transfer image.
The dye image forming materials employed in such processes may generally be characterized as substances which are initially soluble or diffusible in the processing composition and then selectively rendered non-diffusible in an imagewise pattern as a function of development, or sub-stances which are initially insoluble or nondiffusible ...
1~8009 .
in the processing composition and then selectively rendered diffusible in an imagewise pattern as a function of development. Numerous examples of both types of dye image-forming materials are recited in the patent literature. A
particularly useful class of such materials are dye developers (dyes which are also silver halide developing agents) described in U. S. Patent No. 2,983,606 and many other patents.
In any of these systems, multicolor images may be obtained by employing a photosensitive element or negative component with at least two selectively sensitized silver halide layers, each having associated therewith a dye image-forming material exhibiting the desired spectral absorption ch~aracteristics. The most commonly employed elements of this type are the so called tripack structures employing a blue-, a green- and a red-sensitive silver halide layer having associated therewith, respectively, a yellow, a magenta and a cyan dye image-providing material.
The negative and positive components in such a system may be separate elements which are brought into superposition during development and thereafter retained together or separated to provide the desired transfer image ~e.g., as described in the aforementioned U. S. Patent No.
The dye image forming materials employed in such processes may generally be characterized as substances which are initially soluble or diffusible in the processing composition and then selectively rendered non-diffusible in an imagewise pattern as a function of development, or sub-stances which are initially insoluble or nondiffusible ...
1~8009 .
in the processing composition and then selectively rendered diffusible in an imagewise pattern as a function of development. Numerous examples of both types of dye image-forming materials are recited in the patent literature. A
particularly useful class of such materials are dye developers (dyes which are also silver halide developing agents) described in U. S. Patent No. 2,983,606 and many other patents.
In any of these systems, multicolor images may be obtained by employing a photosensitive element or negative component with at least two selectively sensitized silver halide layers, each having associated therewith a dye image-forming material exhibiting the desired spectral absorption ch~aracteristics. The most commonly employed elements of this type are the so called tripack structures employing a blue-, a green- and a red-sensitive silver halide layer having associated therewith, respectively, a yellow, a magenta and a cyan dye image-providing material.
The negative and positive components in such a system may be separate elements which are brought into superposition during development and thereafter retained together or separated to provide the desired transfer image ~e.g., as described in the aforementioned U. S. Patent No.
2,983,606), or these two components may comprise a unitary structure, such as the so called integral negative-positive film units wherein the respective components are retained together prior to exposure and following image formation.
In the latter system a reflecting material such as a white pigment, e.g., titanium dioxide, is provided between the two components. This may comprise a preformed layer or one formed during development which masks the negative component 8~)09 and provides the desired background for viewing the image formed in the positive component as a reflection print.
The respecti-.~e components in such integral film units may be contained on a single dimensionally stable layer or support, , or they may be confined between a pair of such supports. Of course, any support associated with the positive component should be transparent to permit viewing of the transfer image.
As examples of such integral negative-positive film units for preparing color transfer images viewable without 1~ separation, mention may be made of those described in U. S.
Patents No. 3,415,644; 3,415,645; 3,415,646; 3,473,925;
In the latter system a reflecting material such as a white pigment, e.g., titanium dioxide, is provided between the two components. This may comprise a preformed layer or one formed during development which masks the negative component 8~)09 and provides the desired background for viewing the image formed in the positive component as a reflection print.
The respecti-.~e components in such integral film units may be contained on a single dimensionally stable layer or support, , or they may be confined between a pair of such supports. Of course, any support associated with the positive component should be transparent to permit viewing of the transfer image.
As examples of such integral negative-positive film units for preparing color transfer images viewable without 1~ separation, mention may be made of those described in U. S.
Patents No. 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.
With multicolor diffusion transfer products such as those described above employing two or more sets of silver halide emulsion layers, each layer having its own dye image-forming material associated therewith, premature migration of the color~providing material during processing can produce undesirable inter-image effects wherein the dye or other color providing material is controlled at least in part by the "wrong" silver halide layer, i.e., a silver halide layer other than the one with which it was initially associated in the film unit.
This problem may be further illustrated by reference to a conventional tripack negative employing dye developers, wherein the negative is comprised of a support carrying a 3~ red-sensitive silver halide layer having a cyan dye developer ~148~:)Q9 associated therewith, a green-sensitive silver halide layer having a magenta dye developer associated therewith and a blue-sensitive silver halide layer having a yellow dye developer associated therewith. Ideally, solubilized dye '; developer should diffuse to its associated silver halide layer, and if not bound in that layer it diffuses further to 'he image receiving element. Diffusion through the silver halide layer is generally controlled by development of the silver halide layer. If the dye developer is permitted to migrate to other silver halide layers before its associated silver halide layer has been developed, the resultant transfer image will have something less than the desired color fidelity due to dye loss and/or transfer of the wrong dye.
To illustrate further, if it is possible for the magenta dye developer to back-diffuse to the red sensitive silver halide layer before development of this layer by the cyan dye developer, some of the magenta dye developer may develop silver halide in this "wrong" layer and be tied up or rendered nondiffusible. This will produce a loss of magenta dye, or so called "magenta drop off", in the transfer image. Moreover, development of the red-sensitive silver halide layer by magenta dye developer permits some of the cyan dye developer which should have instead been o~idized to diffuse to the image-receiving element, thereby resulting in unwanted cyan transfer.
To obviate or minimize these inter-image effects, layers comprised of various materials have been inserted between the emulsions and their individual supplies of dye image-forming material to prevent premature diffusion of the 3~ latter to an unassociated silver halide emulsion. Such an 1148~5)9 interlayer is permeable to the passage of processing composition so that development can take place in the emulsions on either side of the interlayer. The interlayer is impermeable for a short time to the dye image-forming material solubilized by the processing composition so that the emulsions will be substantially developed before the dye material associated with one emulsion layer can travel through the interlayer to another emulsion layer.
Control of the diffusion of color-providing substances by deferring or retarding their ability to diffuse to the image-receiving layer until after desired development has occurred is disclosed in U. S. Patent No. 3,345,163 wherein said control is effected, e.g., by the use of a slowly hydrolyzable material as a barrier layer separating an outer emulsion and its associated color-providing substance from an inner emulsion and its associated color-providing substance.
Several other types of photosensitive element interlayer systems have been disclosed in the art. For example, as seen in U. S. Patent No. 3,615,422 two emulsion layers may be separated by an interlayer comprised of metal-free polymeric material permeable to processing composition but impermeable to color providing substances until the polymer has become hydrated. The polymer's hydration rate is chosen so that the requisite hydration will occur subsequent to substantial development of the silver halide emulsion having the slowest development rate and prior to substantial fogging of the emulsion layer with the most rapid fogging rate. The interlayer can then retard both forward and rearward diffusion of color-~481~09 providing substances or dy~s. It retards rearward diffusion of dye associated with the next outer silver halide emulsion layer and forward diffusion of dye associated with the next inner silver halide emulsion layer. A variety of polymeric material found especially useful in this type of system is disclosed in U. S. Patent No. 3,421,892 which relates to the use of polyvinyl amide interlayers. These interlayers function like molecular sieves whose interstices become so enlarged by hydration of the polymer that a molecule of dye or other color-providing substance can pass through.
The interlayer material disclosed in U. S. Patent No. 3,384,483 is comprised of an alkali permeable, water insoluble polyvalent metal salt of a film forming, alkali permeable and water soluble polymer with free carboxyllc acid groups. It appears that this polymeric salt, which is less permeable to dye developer in aqueous alkaline solution than the polymeric carboxylic acid used to prepare it, retards diffusion of dye developer to an unassociated emulsion layer during development via a cross-link mechanism, i.e., polyvalent metal moieties form the requisite alkali permeable, water insoluble salts by cross-linking with carboxylic acid moieties of the polymeric carboxylic acid. When this salt becomes hydrated during processing, it swells enough to permit diffusion of unoxidized dye developer through its interstices to the image receiving element.
Rather than employing an interlayer consisting essentially of only a single phase of material, an interlayer comprised of an admixture of materials may be utilized.
Such a system is disclosed in U. S. Patent No. 3,625,685, where silver halide strata are separated by interlayers ~L~4~9 containing two phases which are intimately admixed, the dye permeation-inducing component or discontinuous phase (comprised of processing composition permeable material) and a coalesced latex or continuous phase (comprised of the ~j coalesced essence of an aqueous film-forming synthetic polymeric dispersion). In this system tne dye permeation-inducing material, which may be permeable or impermeable to the processing composition and is impermeable to dye image forming material, forms a lattice structure with the coalesced latex which is permeable to processing composition. Upon contact with processing composition, the dye permeation-inducing material, which is preferably a polymer, becomes permeable to solubilized dye material, thereby making it possible for dye to pass through the lS interlayer.
In a preferred embodiment of the above described system, the interlayer is rendered permeable by hydration of the discontinuous phase. This phase expands when hydrated to create interstices in the interlayer's lattice structure of sufficient size to permit the passage of solubilized dye therethrough. The rate of hydration and swelling is usually chosen so as to block migration of the dye image forming material until development of all emulsion layers in the photosensitive element is substantially completed, although it can also be chosen so as to achieve layerwise development of the emulsions and diffusion of the dye image forming material. In the latter type of system, an interlayer between two emulsion layers would preferably prevent such dye diffusion until there had been substantial development of the outer (closer to the image-receiving ~148009 element) emulsion layer.
As can be seen from the discussion above, polymers rendered permeable to the passage of solubilized dye image forming material by hydration may be used alone or in a mixture with other materials to form a barrier interlayer between two emulsions. It is believed that such an interlayer system can act as a selective barrier because of the large size of the dye (or dye precursor) molecules. While many of the molecules of processing composition e.g., water, alkali, etc., are small enough to slip through interstices in the interlayer lattice, those of the solubilized dye image forming material are too large to do so in the time span contemplated for photographic processing unless these interstices are expanded by hydration of the barrier polymer.
Although such polymers have proven to be useful in delaying the diffusion of dye image-forming material, it has been found that they sometimes permit premature diffusion. This is because polymer hydration and the resultant interlayer expansion generally begin as soon as the polymer is contacted with processing composition. Thus, some dye diffusion could occur before substantial development of the silver halide emulsion protected by the interlayer. Further-more, these polymers tend to produce rather slow interlayer expansion. Instead of switching quickly from a very impermeable condition to a highly permeable one as would often be desired, interlayer permeability usually occurs more gradually, sometimes beginning too soon and taking too long.
U. S. Patent No. 3,362,819 discloses image-receiving elements, particularly adapted for employment in the preceding diffusion transfer processes, which comprise a 8~09 support layer possessing on one surface thereof, in sequence, a polymeric acid layer, preferably an inert timing or spacer layer, and an image-receiving layer adapted to provide a visible image upon transfer to said layer of diffusible dye image-forming substance.
~8~g The acid polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 12 to 14 to a pH
of at least 11, and preferably to a pH of about 5 to 8 after a predetermined period.
It is, of course, necessary that the action of the polymeric acid be so controlled as not to interfere with either development of the negative or transfer of image dye formers. For this reason, the pH of the image layer is kept at a level of pH 12 to 14 until the positive dye image has been formed, after which the pH is reduced very rapidly to the desired final pH.
1~48C~9 The inert spacer layer of the aforementioned patent, for example, an inert spacer layer comprising polyvinyl alcohol or gelatin, acts to "time" control the pH reduction by the polymeric acid layer. This timing is disclosed to be a ~unction of the rate at which the alkali diffuses through the inert spacer layer.
1148~09 The use of diffusion control layers in silver trans-fer processes, such as timing layers to control a neutralizing layer, is known in the art; see, for example, United States Patent 3,772,025, issued November 23, 1973 to Edwin H. Land.
The present invention seeks to provide novel diffusion control layers for use in photographic diffusion transfer prod-ucts and processes, said diffusion control layers controlling the diffusion transfer of a reagent to or through a layer of a photosensitive component or a positive component of a diffusion transfer film unit.
Thus additionally the present invention seeks to provide products for use in photographic diffusion transfer color processes which include a photosensitive element interlayer which substantially prevents diffusion of solubilized dye-form-ing material through said interlayer until after a predetermined period.
Alternatively this invention seeks to provide such an interlayer which rapidly switches from a condition of substan-tial impermeability to solubilized dye image-forming material to one of substantial permeability to such material.
In another aspect this invention seeks to provide such an interlayer of a polymer which is initially impermeable to solubilized dye image-forming material, which interlayer becomes permeable to such solubilized dye image-forming material following a predetermined, short time period after said inter-layer has been contacted with an alkaline processing composition, which composition solubilizes and transports said dye image-forming material through the interlayer.
A still further alternative aspect of the present invention is to seek to provide products for use in photo-graphic diffusion transfer processes which include a neutraliz-ing system for lowering the pH of an aqueous alkaline process-, - 12 -~"
114~ 9 ing fluid, said neutralizing system including a neutralizing layer and a timing layer so disposed with respect to the neutral-izing layer that said processing fluid must first diffuse through the timing layer before contacting said neutralizing layer, said timing layer being capable of rapidly switching from a condition of substantial impermeability to alkali to a condi-tion of substantial permeability thereto.
In a still further alternative aspect this invention seeks to provide a polymeric overcoat for an image-receiving element which rapidly switches from a condition of substantial impermeability to processing fluid to one of substantial permea-bility to such material.
Thus in a first embodiment the invention provides a photographic diffusion transfer film unit comprising:
a. a photosensitive element comprising at least one photosensitive silver halide emulsion layer having associated therewith a processing composition soluble and diffusible image-forming materials;
b. an image-receiving element;
c. means for discharging an alkaline processing composition within said film unit; and d. a diffusion control layer in at least one of said photosensitive element or said image-receiving element;
said diffusion control layer including a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula f~
~8~g -- R~-C=O
A - C - E
D - l - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E, or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a second embodiment the invention provides a photo-sensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment;
said polymerization product comprising recurring units of the formula ~ 8~1g)9 ---R" -C = O
o A - C - E
D - C - H
y wherein R" ~s the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a third embodiment the invention provides a photo-sensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least one photosensitive silver halide emulsion layer coated upon said support, said emulsion layer having associated therewith a processing composition soluble and diffusible dye image~-forming material; and a diffusion control layer positioned as an overcoat including a polymerization product of a monomer capable of under-going ~-elimination in an alkaline environment; said polymeriza-tion product comprising recurring units of the formula R~ -C = O
f A - C - E
D - f H
y - 14a -~8~09 wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a fourth embodiment the invention provides a photo-sensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer comprises a mixture of polymers, at least one of which polymers includes a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula R"
C=o o A - C - E
D - C - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of r~
- 14b -~8~ 9 hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a fifth embodiment the invention provides a photo-graphic film unit comprising in combination a photosensitive element and a diffusion transfer image-receiving element, said combination comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula - R~
C = O
o A - C - E
D - C - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
~ - 14c -11~8~;)9 In a sixth embodiment the invention provides a photo-graphic film unit comprising in combination a photosensitive element and a difEusion transfer image-receiving element, said combination comprising:
a support layer;
at least two selectively sensitiziod silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which polymers comprises a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula R~ -l = O
A - f E
D - f H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D
may be methyl or phenyl, and Y is an activating group for said ~-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
In a seventh embodiment the invention provides an ele-ment for use in diffusion transfer photographic processes com-prising:
` ` - 14d -1~8~)9 a support layer, a polymeric acid layer, and a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going ~-elimination in an alkaline environment, said polymerizat-ion product including recurring units of the formula R"
C = O
D - C - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E and D
may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In an eighth embodiment the invention provides an image-receiving element for use in diffusion transfer photograph-ic processing comprising:
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a mixture of polymers, at least one of which polymers comprises a polymerization product of a monomer capable of under-going 3-elimination in an alkaline environment, said polymerizat-ion product comprising recurring units of the formula ~ - 14e -1~8~9 - R~ -C = O
o A - C - E
D - f H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, meth-yl, and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination; and an alkali permeable and dyeable image-receiving layer.
In a ninth embodiment the invention provides a photo-graphic film unit comprising in combination a silver halide photosensitive element and a diffusion transfer image-receiving element, said image-receiving element comprising:
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going ~-elimination in an alkaline environment, said polymeriza-tion product comprising recurring units of the formula R"
C = O
A - C - E
E - C - H
y wherein - - 14f -1~48009 R" is the addition polymerization product of an ethylenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl, provided that no more than one of A, E or D
may be methyl or phenyl; and Y is an activating group for said ~-elimination; and an alkali permeable and dyeable image-receiving layer.
FIGURE 1 is a cross-sectional view of a photographic film unit including diffusion control layers of this invention;
FIGURE 2 is a cross-sectional view of an image-receiv-ing element including a diffusion control timing layer of this invention;
FIGURE 3 illustrates a model arrangement for measuring the "hold-time" of the interlayers of this invention; and FIGURE 4 is a graphical depiction of dye density as a function of time in a system including an interlayer of the present invention.
- 14g --8~3~)9 It has been found that polymerization products of monomers capable of undergoing ~-elimination in an alkaline environment are useful for providing timed diffusion control in diffusion trans~fer photographic film units. Diffusion 5 control layers of these polymerization products may be formulated for use as diffusion control interlayers or overcoats in photosensitive elements, and as diffusion control, e.g., timing layers or overcoats in image-receiving elements. These polymeric materials must undergo 3-elimination before substantial swelling occurs, ~-elimination and swelling being a prerequisite to permeation by selected materials soluble in or solubilized by an aqueous alkaline processing fluid.
The ~-elimination step which the polymeric materials of the diffusion control~layers of this invention undergo ensures that there is a delay in permeability after contact of the diffusion control layer with the processing composition, and provides a "hold" of the alkali or soluble or solubilized material followed by a rapid "release" or opening to permit the soluble or solubilized material to pass. The polymeric materials may be thought of as "hold-release"
polymers which delay diffusion therethrough of alkali or material soluble in or solubilized by processing fluid by a predetermined time, e.g., from less than five seconds to more several hundred seconds.
- The diffusion control layers of this invention may be used as interlayers between silver halide emulsion layers sensitized to different regions of the spectrum, each emulsion having an associated dye image-forming material.
They may be utilized, e.g., in the manner described in aforementioned ~. S. Patent Nos. 3,615,422 and 3,421,892, substituting the hold-release polymers of this invention for the interlayer polymer compositions disclosed therein.
1~8~09 The time for ~-elimination to occur subseguent to contact with processing compositioncnd for subsequent hydration should be sufficient to maintain the interlayer substantially impermeable to solubilized dye image-forming material until there has been at least substantial development of the emulsions bètween the interlayer and the image-receiving layer but before there has been substantial fogging of the emulsion layer with the most rapid fogging rate.
The diffusion control layers of this invention may be used as timing or spacer layers empIoyed between the alkaline processing composition introduced into the film unit and a neutralizing layer, e.g., a polymeric acid layer, to control the initiation of pH reduction by acting as a substantially impermeable barrier to the alkaline processing composition until ~-elimination occurs.
The diffusion control layers of the invention can also be utilized as an overcoat layer, such as overcoat layer 19 shown in Fig. 1. The employment of such an overcoat layer can be utilized to control, for example, desired dye transfer by conversion of a substantially dye-impermeable layer to a substantially dye-permeable layer.
The introduction of double bonds into a molecule containing single bonds involves the elimination of atoms or groups from adjacent atoms. When elimination reactions involve ~-substituted esters, acids, ketones, aldehydes and nitro compounds,they are called ~-eliminations. According to Hendrickson, Cram and Hamrnond, Organic Chemistry (3rd Edition, McGraw-Hill Book Company, 1970), the electron-withdrawin~ qroups have stronq acid-strenqthening effects on the ~ roton which is removod by base during th~ reaction.
This 1,2-elimination under ~asic conditions i9 very familiar as shown by Fiqure 14-3 from Hendrickson, Cram and Hammond which follow~.
` :1148C~09 I I :B
-------C------C N02 ~ I 1 2 \ NO
> \ ,, 2 where L is a leaving group, B is a base and -N02 a typical activating group. In general terms this might be written:
H
l -BH
> ~ = C\ +L (~
where Y is an activating group.
Substituents which activate ~-elimination under basic conditions are known. The nature of the activation in ~-eliminations was studied by J. Crosby and C.J.M.
Stirling in J. Chem. Soc. (B) 1970 page 671. It was concluded that resonance stabilization of a carbanionic species was an important component of activation.
It has been discovered that such a ~-substituted compound may be incorporated into a polymer to provide a polymer which is substantially impermeable to alkali or certain materials which are soluble in or solubilized by alkaline processing fluid until after ~-elimination breaks bonds liberating groups capable of absorbing water, swel-ling and causing the polymer to become permeable to these soluble or solubilized materials and that such polymer may be used as a diffusion control layer, the resulting pre-determined time delay preventing premature diffusion of the alkali or soluble or solubilized materials. By controlling the mole proportion or ratio of such ~-elimination moieties in the polymer, as well as the thickness of the polymeric layer, one may provide a predetermined permeability time desired for the particular diffusion transfer system.
With reference to the above general formulation for ~-elimination, the leaving group, L, is the polymeric structure from which a ~-substituted material is eliminated or such a polymer additionally containing grafted moieties as disclosed and claimed in Canadian application Serial No. 322,011*, in the names of Bedell, Sullivan and Taylor and filed concurrently herewith.
The ~-elimination reaction can then be written either *See also United States Patent 4,297,431.
,: ' ' ' .009 H-h~H
i H-C-H + CH2=cH-Y
where L is ~H l ' 1 L H ~ ~ and R' is hydrogen or methyl and Y is selected from the group O O
consisting of _SO2WJ -C-T, -S-GJ and -CN where W is 6 5 3J CH3J OC2HsJ -C6H5J -NR2 -n(CH2C6H5)2; T
is -OC2H5J -CH3J -HJ -NH2J -NR2; G is phenylJ methyl or ethyl and R is alkyl J e.g. J methyl or ethyl; or CH2 IC ~ 2 Cl ~:H2 1~ ECH2 H~ H
H--Cl--H
B + CH2=cH-Y
~8~0g where L is t CH2 ~ R' CH--f ~
C=O
1~
and R'and Y are as defined above.
More generally, the reaction is:
~R"~ n C=O C=O +n A-C=c-y O ~ O ~ E D
A ~ C - E
D - C H
y wherein R" is the addition polymerizatiorl unit of an ethylenically unsaturated alkyl group of from two to five carbon atoms, including a graft of such an ethylenically unsaturated alkyl group onto a polymeric organic backbone, A, E and D are selected from the group consisting of hydrogen, methyl and phenyl provlded that no more than one of A, E or D may be methyl or phenyl, Y is an activating group as defined above. Typical monomers which have demonstrated that they provide to their polymerization product a ~-elimination activating group include 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, and 2-carbethoxy-ethyl methacrylate.
Other monomers which should provide the same functionality to their polymerization products include, for example, 2-p-toluenesulfonyl-ethyl acrylate and 2-methane sulfonyl-ethyl acrylate.
The reaction usin~ the polymerization product of 2-cyanoethyl acrylate can be visualized thusly;
~1~8~109 ll l l l H H
----C--C -- ----C--C----El C--O > I H C=O
H- C-H + CH2=CHC.--N
C -N
The diffusion control layers of the invention can comprise homopolymers or copolymers, including graft copolymers as mentioned hereinbefore. Mixtures of polymers can also be employed. Suitable copolymers for use as diffusion control layers will include, in addition to the ~-eliminating component, units from comonomeric materials which provide the polymers with certain desired properties. Such materials may, for example, modulate coalescence or viscosity, improve film integrity and coatability, or provide for more even fluid permeation and ion penetration~ For exampIe, butyl acrylate is useful in providing hydrophobic balance and control to the dye permeation rate.
Comonomers which are non-hydrolyzable or cross-linking may be used. Acrylic acid, methacrylic acid, 2-sulfoethyl methacrylate and 2-acrylamido-2-methylpropane sulfonic acid have been found useful comonomers in assuring that all parts of the diffusion control layer allow processing composition to pass through at essentially the same time and rate so as to promote uniform ~-elimination and hydration of the permeation-inducing component. Ethylene glycol dimethacrylate, a cross-linking monomer, for example, is useful in the diffusion control layer 1~48~0g used as an interlayer to modulate dye transfer rate after the initial hold.
As shown in Figure 1, the diffusion control layers of this invention may be employed in a photographic film unit having a photosensitlve element 26 and an image-receiving element 27. Interlayers 13 and 16 are positioned between red- and green-, and blue- and green- sensitive silver halide emulsions, respectively, in the photosensitive element. These interlayers and the emulsions with their associated dye image-forming material, e.g., dye developer, are preferably arranged on a support 10 in the following order from that support: cyan dye developer layer 11, red-sensitive silver halide emulsion layer 12, interlayer 13, magenta dye developer layer 14, green-sensitive silver halide emulsion 15, lS interlayer 16, yellow dye developer layer 17 and blue-sensitive silver halide emulsion layer 18. An overcoat layer 19 may be coated on top of the blue-sensitive silver halide emulsion layer.
The image-receiving element 27 illustrated in Figure 1 comprises in order, an image-receiving layer 21, a spacer or timing layer 22, a neutralizing layer 23 and a support layer 24. During processing the image-receiving layer is situated closest to the photosensitive element.
After the photosensitive element has been exposed, aqueous alkaline processinq composition 20 is introduced between the photosensitive and image-receiving elements and permeates the emulsion layers to initiate development of the latent imaqe carried therein and provide a medium for dye diffusion transfer to the image-receiving element. Dye image-forming materials associated ~ith unexposed portions - 22 ~
~481)09 of the emulsion layers diffuse to the image-receiving element in known manner. As set forth in U. S. Patent No. 3,362,819, situated beneath the image-receiving layer is a neutralizing layer containing a polymeric acid to neutralize alkali in the processing composition after a predetermined period.
The timing or spacing layer, comprised of polymeric material and located between the image-receiving and neutralizing layers is used to control the pH reduction.
Diffusion control layers comprising a ~-elimination polymeric material in accordance with this invention comprise, in one preferred embodiment, interlayers 13 and/or 16. Alternatively, overcoat layer 19 can comprise a diffusion control layer of a ~-eliminating polymeric material. In another preferred embodiment the spacer layer 22 comprises a diffusion control lS layer of the invention.
The image-receiving element 27 illustrated in Figure 2 comprises in order, a support layer 28, a neutralizing layer 29, a spacer or timing layer 30, an image-receiving layer 31 and an overcoat 32. During processing the image-receiving element overcoat is situated closest to the photosensitive element. In one embodiment of this invention, a diffusion control layer comprising a ~-elimination polymeric material in accordance with this invention comprises overcoat layer 32.
A measure of time of pH r~duction can be had from a quantity which can be referred to as a "clearing time"
which can be measured by use of the following system. An image-receiving element comprising in order on a support, a polymeric acid layer, a test timing layer and a mordanting layer, is spread with an alkaline procecsing material of high pH comprising an indicator dye which is highly colored at pH's of about 12 to 14 and colorless below about 10. A
~1~80~)9 transparent cover sheet is superposed the processing material.
The view through the cover sheet toward the image-receiving element is dark until the alkali has penetrated to the polymeric acid layer where the pH is reduced by alkali consumption and the indicator dye becomes colorless, the system has "cleared". A skilled operator can determine when the ~learing begins and when it is complete. A "leaky"
timing layer allows a trickle of alkali through from the moment of first contact and shows no precipitous change in beginning to clear nor in the final clearing. A timing layer comprising the polymers of the instant invention will hold the alkali back for a definite timed period, and then, over a very short time interval, allow sufficient alkali through to drop the pH below the transition range of the indicator dye.
Clearing time can be measured for a structure that comprises an entire image-receiving element or it can be measured for a model simplified structure that includes only the timing layer coated over the polymeric acid layer on the support. The first clearing time is referred to as "clearing through the mordant" while the second model structure clearing is referred to as "clearing through the timing layer".
The diffusion control layer of this invention used as a top coat for an image-receiving element is located on top of the strata that comprise the image-receiving element. Por example, in an image-receiving element comprising in order, a support, a polymeric acid layer, a spacer layer and an alkali permeable and dyeable polymeric layer, the ~iffusion control layer is located next adjacent ` 114~09 the alkali permeable and dyeable polymeric layer, furthest from the support and acts to delay permeation to the image-receiving element of the processing composition and materials solubilized by it.
The capacity of polymeric diffusion control layers of the invention to delay permeation therethrough of image-forming dye until conversion by a 3-elimination reaction to a relatively dye-permeable polymer can be evaluated by resort to utilization of a test structure shown in Fig. 3. In accordance with such structure, dye transfer through the polymeric test material, e.g., an interlayer test material, is monitored in relation to time. The "hold-release" properties of a polymeric test material can be evaluated in simulation of the functioning of a material as, e.g., an interlayer in a photosensitive element.
Such test structure and a suitable method of evaluation are set forth in detail in Examples 1 to 15 hereof.
The following examples are presented for illustrative purposes only and are not intended to be in any way limiting. Measurements were made at ambient room temperature, about 25C, unless otherwise specified.
Examples 1-10 On a transparent support, 33 in Fig. 3, a 2~S.~ ~51~
layer 34 comprising 20 mg/ft~ of a cyan dye developer 8~9 CH
HC - NH - O2S ~
N = C C _N
~ ~ I \N ~ ll fH3 HO ~ ~ S2 - NH IH
N _ CUL_N~
ICH2 N - C ~ - N
HO ~ OH ~ S2 - NH - ?H
~ H
HO ~
40 mg/ft (430.6 mgs/m2) gelatin and 1.5 mg/ft2 (16.1 mgs/m2) of succinaldehyde was coated using a conventional loop coater. Over this layer, a layer 35 containing 200 mg/ft2 (2153 mgs/m2) of the polymeric material being tested was coated.
A transparent element 38 comprising a polyester clear film base was superposed with test elements to form sandwiches and an opaque alkaline processing composition 36 comprising:
Potassium hydroxide (45% aqueous solution) 22.9 g.
Lithium hydroxide 0.55 g.
Benzotriazole 1.53 g.
6-Bromo-5-methyl-4-azabenzimidazole 0.08 g.
6-methyl uracil 0.82 g.
Ethylene diamine tetraacetic acid 2.27 g.
Bis-(2-aminoethyl) sulfide 0.06 g.
Carbowax (mw 6000)* 1.5 g.
Colloidal silica 5.05 g.
6-benzylaminopurine 1.09 g.
Titanium dioxide 115.23 g.
N-phenethyl a-picolinium bromide 3.91 g.
(50% aqueous solution) N-benzyl o~-picolinium bromide 5.09 g.
~50% aqueous solution) Lithium nitrate 0.27 g.
Carboxymethyl hydroxyethyl cellulose 4.82 g.
Water 100 g.
was introduced between the polymeric test material layer and the transparent element 38 at a gap of 0.0028 in, (about 0.07 mm).
The optical reflection density to red light of the processed sample, viewed through support 33 in Figure 3~ as a function of time was continuously read using a MacBeth Quanta-Log* densitometer equipped with a Hewlett-Packard*
17505A strip-chart recorder. This density comprises contributions from the dye image-forming material remaining in the dye layer and dye image-forming material in the polymeric *Trademark - 27 1148~09 test layer. The titanium dioxide in the processing composition masks dye image-forming material in the processing composition layer. A typical curve of density as a function of time is given in Figure 4 wherein tl is the time for dye image-forming material to solubilize, t2 is the total time the dye image-forming material is held back by the polymeric interlayer, Do is the density after the initial dissolution of the dye image-forming material, Df is the density after dye transfer through the interlayer, and the slope of the line segment between A and B is calculated as the rate of change of densit .
Values for tl, t2 and slope are given below for the following hold-release polymer systems of the present invention:
1. 100 parts by weight of 2-cyanoethyl acrylate mixed with 100 parts by weight of a 95.5/4.5 copolymer of diacetone acrylamide and acrylic acid and polymerized.
2. 35 parts by weight of 2-cyanoethyl acrylate mixed with 65 parts by weight of a 95.5/4.5 copolymer of diacetone acrylamide and acrylic acid and polymerized.
3. A 47.5/50/2.5 interpolymer of diacetone acrylamide, 2-cyanoethyl acxylate and acrylic acid.
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.
With multicolor diffusion transfer products such as those described above employing two or more sets of silver halide emulsion layers, each layer having its own dye image-forming material associated therewith, premature migration of the color~providing material during processing can produce undesirable inter-image effects wherein the dye or other color providing material is controlled at least in part by the "wrong" silver halide layer, i.e., a silver halide layer other than the one with which it was initially associated in the film unit.
This problem may be further illustrated by reference to a conventional tripack negative employing dye developers, wherein the negative is comprised of a support carrying a 3~ red-sensitive silver halide layer having a cyan dye developer ~148~:)Q9 associated therewith, a green-sensitive silver halide layer having a magenta dye developer associated therewith and a blue-sensitive silver halide layer having a yellow dye developer associated therewith. Ideally, solubilized dye '; developer should diffuse to its associated silver halide layer, and if not bound in that layer it diffuses further to 'he image receiving element. Diffusion through the silver halide layer is generally controlled by development of the silver halide layer. If the dye developer is permitted to migrate to other silver halide layers before its associated silver halide layer has been developed, the resultant transfer image will have something less than the desired color fidelity due to dye loss and/or transfer of the wrong dye.
To illustrate further, if it is possible for the magenta dye developer to back-diffuse to the red sensitive silver halide layer before development of this layer by the cyan dye developer, some of the magenta dye developer may develop silver halide in this "wrong" layer and be tied up or rendered nondiffusible. This will produce a loss of magenta dye, or so called "magenta drop off", in the transfer image. Moreover, development of the red-sensitive silver halide layer by magenta dye developer permits some of the cyan dye developer which should have instead been o~idized to diffuse to the image-receiving element, thereby resulting in unwanted cyan transfer.
To obviate or minimize these inter-image effects, layers comprised of various materials have been inserted between the emulsions and their individual supplies of dye image-forming material to prevent premature diffusion of the 3~ latter to an unassociated silver halide emulsion. Such an 1148~5)9 interlayer is permeable to the passage of processing composition so that development can take place in the emulsions on either side of the interlayer. The interlayer is impermeable for a short time to the dye image-forming material solubilized by the processing composition so that the emulsions will be substantially developed before the dye material associated with one emulsion layer can travel through the interlayer to another emulsion layer.
Control of the diffusion of color-providing substances by deferring or retarding their ability to diffuse to the image-receiving layer until after desired development has occurred is disclosed in U. S. Patent No. 3,345,163 wherein said control is effected, e.g., by the use of a slowly hydrolyzable material as a barrier layer separating an outer emulsion and its associated color-providing substance from an inner emulsion and its associated color-providing substance.
Several other types of photosensitive element interlayer systems have been disclosed in the art. For example, as seen in U. S. Patent No. 3,615,422 two emulsion layers may be separated by an interlayer comprised of metal-free polymeric material permeable to processing composition but impermeable to color providing substances until the polymer has become hydrated. The polymer's hydration rate is chosen so that the requisite hydration will occur subsequent to substantial development of the silver halide emulsion having the slowest development rate and prior to substantial fogging of the emulsion layer with the most rapid fogging rate. The interlayer can then retard both forward and rearward diffusion of color-~481~09 providing substances or dy~s. It retards rearward diffusion of dye associated with the next outer silver halide emulsion layer and forward diffusion of dye associated with the next inner silver halide emulsion layer. A variety of polymeric material found especially useful in this type of system is disclosed in U. S. Patent No. 3,421,892 which relates to the use of polyvinyl amide interlayers. These interlayers function like molecular sieves whose interstices become so enlarged by hydration of the polymer that a molecule of dye or other color-providing substance can pass through.
The interlayer material disclosed in U. S. Patent No. 3,384,483 is comprised of an alkali permeable, water insoluble polyvalent metal salt of a film forming, alkali permeable and water soluble polymer with free carboxyllc acid groups. It appears that this polymeric salt, which is less permeable to dye developer in aqueous alkaline solution than the polymeric carboxylic acid used to prepare it, retards diffusion of dye developer to an unassociated emulsion layer during development via a cross-link mechanism, i.e., polyvalent metal moieties form the requisite alkali permeable, water insoluble salts by cross-linking with carboxylic acid moieties of the polymeric carboxylic acid. When this salt becomes hydrated during processing, it swells enough to permit diffusion of unoxidized dye developer through its interstices to the image receiving element.
Rather than employing an interlayer consisting essentially of only a single phase of material, an interlayer comprised of an admixture of materials may be utilized.
Such a system is disclosed in U. S. Patent No. 3,625,685, where silver halide strata are separated by interlayers ~L~4~9 containing two phases which are intimately admixed, the dye permeation-inducing component or discontinuous phase (comprised of processing composition permeable material) and a coalesced latex or continuous phase (comprised of the ~j coalesced essence of an aqueous film-forming synthetic polymeric dispersion). In this system tne dye permeation-inducing material, which may be permeable or impermeable to the processing composition and is impermeable to dye image forming material, forms a lattice structure with the coalesced latex which is permeable to processing composition. Upon contact with processing composition, the dye permeation-inducing material, which is preferably a polymer, becomes permeable to solubilized dye material, thereby making it possible for dye to pass through the lS interlayer.
In a preferred embodiment of the above described system, the interlayer is rendered permeable by hydration of the discontinuous phase. This phase expands when hydrated to create interstices in the interlayer's lattice structure of sufficient size to permit the passage of solubilized dye therethrough. The rate of hydration and swelling is usually chosen so as to block migration of the dye image forming material until development of all emulsion layers in the photosensitive element is substantially completed, although it can also be chosen so as to achieve layerwise development of the emulsions and diffusion of the dye image forming material. In the latter type of system, an interlayer between two emulsion layers would preferably prevent such dye diffusion until there had been substantial development of the outer (closer to the image-receiving ~148009 element) emulsion layer.
As can be seen from the discussion above, polymers rendered permeable to the passage of solubilized dye image forming material by hydration may be used alone or in a mixture with other materials to form a barrier interlayer between two emulsions. It is believed that such an interlayer system can act as a selective barrier because of the large size of the dye (or dye precursor) molecules. While many of the molecules of processing composition e.g., water, alkali, etc., are small enough to slip through interstices in the interlayer lattice, those of the solubilized dye image forming material are too large to do so in the time span contemplated for photographic processing unless these interstices are expanded by hydration of the barrier polymer.
Although such polymers have proven to be useful in delaying the diffusion of dye image-forming material, it has been found that they sometimes permit premature diffusion. This is because polymer hydration and the resultant interlayer expansion generally begin as soon as the polymer is contacted with processing composition. Thus, some dye diffusion could occur before substantial development of the silver halide emulsion protected by the interlayer. Further-more, these polymers tend to produce rather slow interlayer expansion. Instead of switching quickly from a very impermeable condition to a highly permeable one as would often be desired, interlayer permeability usually occurs more gradually, sometimes beginning too soon and taking too long.
U. S. Patent No. 3,362,819 discloses image-receiving elements, particularly adapted for employment in the preceding diffusion transfer processes, which comprise a 8~09 support layer possessing on one surface thereof, in sequence, a polymeric acid layer, preferably an inert timing or spacer layer, and an image-receiving layer adapted to provide a visible image upon transfer to said layer of diffusible dye image-forming substance.
~8~g The acid polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 12 to 14 to a pH
of at least 11, and preferably to a pH of about 5 to 8 after a predetermined period.
It is, of course, necessary that the action of the polymeric acid be so controlled as not to interfere with either development of the negative or transfer of image dye formers. For this reason, the pH of the image layer is kept at a level of pH 12 to 14 until the positive dye image has been formed, after which the pH is reduced very rapidly to the desired final pH.
1~48C~9 The inert spacer layer of the aforementioned patent, for example, an inert spacer layer comprising polyvinyl alcohol or gelatin, acts to "time" control the pH reduction by the polymeric acid layer. This timing is disclosed to be a ~unction of the rate at which the alkali diffuses through the inert spacer layer.
1148~09 The use of diffusion control layers in silver trans-fer processes, such as timing layers to control a neutralizing layer, is known in the art; see, for example, United States Patent 3,772,025, issued November 23, 1973 to Edwin H. Land.
The present invention seeks to provide novel diffusion control layers for use in photographic diffusion transfer prod-ucts and processes, said diffusion control layers controlling the diffusion transfer of a reagent to or through a layer of a photosensitive component or a positive component of a diffusion transfer film unit.
Thus additionally the present invention seeks to provide products for use in photographic diffusion transfer color processes which include a photosensitive element interlayer which substantially prevents diffusion of solubilized dye-form-ing material through said interlayer until after a predetermined period.
Alternatively this invention seeks to provide such an interlayer which rapidly switches from a condition of substan-tial impermeability to solubilized dye image-forming material to one of substantial permeability to such material.
In another aspect this invention seeks to provide such an interlayer of a polymer which is initially impermeable to solubilized dye image-forming material, which interlayer becomes permeable to such solubilized dye image-forming material following a predetermined, short time period after said inter-layer has been contacted with an alkaline processing composition, which composition solubilizes and transports said dye image-forming material through the interlayer.
A still further alternative aspect of the present invention is to seek to provide products for use in photo-graphic diffusion transfer processes which include a neutraliz-ing system for lowering the pH of an aqueous alkaline process-, - 12 -~"
114~ 9 ing fluid, said neutralizing system including a neutralizing layer and a timing layer so disposed with respect to the neutral-izing layer that said processing fluid must first diffuse through the timing layer before contacting said neutralizing layer, said timing layer being capable of rapidly switching from a condition of substantial impermeability to alkali to a condi-tion of substantial permeability thereto.
In a still further alternative aspect this invention seeks to provide a polymeric overcoat for an image-receiving element which rapidly switches from a condition of substantial impermeability to processing fluid to one of substantial permea-bility to such material.
Thus in a first embodiment the invention provides a photographic diffusion transfer film unit comprising:
a. a photosensitive element comprising at least one photosensitive silver halide emulsion layer having associated therewith a processing composition soluble and diffusible image-forming materials;
b. an image-receiving element;
c. means for discharging an alkaline processing composition within said film unit; and d. a diffusion control layer in at least one of said photosensitive element or said image-receiving element;
said diffusion control layer including a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula f~
~8~g -- R~-C=O
A - C - E
D - l - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E, or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a second embodiment the invention provides a photo-sensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment;
said polymerization product comprising recurring units of the formula ~ 8~1g)9 ---R" -C = O
o A - C - E
D - C - H
y wherein R" ~s the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a third embodiment the invention provides a photo-sensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least one photosensitive silver halide emulsion layer coated upon said support, said emulsion layer having associated therewith a processing composition soluble and diffusible dye image~-forming material; and a diffusion control layer positioned as an overcoat including a polymerization product of a monomer capable of under-going ~-elimination in an alkaline environment; said polymeriza-tion product comprising recurring units of the formula R~ -C = O
f A - C - E
D - f H
y - 14a -~8~09 wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a fourth embodiment the invention provides a photo-sensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer comprises a mixture of polymers, at least one of which polymers includes a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula R"
C=o o A - C - E
D - C - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of r~
- 14b -~8~ 9 hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In a fifth embodiment the invention provides a photo-graphic film unit comprising in combination a photosensitive element and a diffusion transfer image-receiving element, said combination comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula - R~
C = O
o A - C - E
D - C - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
~ - 14c -11~8~;)9 In a sixth embodiment the invention provides a photo-graphic film unit comprising in combination a photosensitive element and a difEusion transfer image-receiving element, said combination comprising:
a support layer;
at least two selectively sensitiziod silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which polymers comprises a polymerization product of a monomer capable of undergoing ~-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula R~ -l = O
A - f E
D - f H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D
may be methyl or phenyl, and Y is an activating group for said ~-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
In a seventh embodiment the invention provides an ele-ment for use in diffusion transfer photographic processes com-prising:
` ` - 14d -1~8~)9 a support layer, a polymeric acid layer, and a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going ~-elimination in an alkaline environment, said polymerizat-ion product including recurring units of the formula R"
C = O
D - C - H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E and D
may be methyl or phenyl; and Y is an activating group for said ~-elimination.
In an eighth embodiment the invention provides an image-receiving element for use in diffusion transfer photograph-ic processing comprising:
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a mixture of polymers, at least one of which polymers comprises a polymerization product of a monomer capable of under-going 3-elimination in an alkaline environment, said polymerizat-ion product comprising recurring units of the formula ~ - 14e -1~8~9 - R~ -C = O
o A - C - E
D - f H
y wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, meth-yl, and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said ~-elimination; and an alkali permeable and dyeable image-receiving layer.
In a ninth embodiment the invention provides a photo-graphic film unit comprising in combination a silver halide photosensitive element and a diffusion transfer image-receiving element, said image-receiving element comprising:
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going ~-elimination in an alkaline environment, said polymeriza-tion product comprising recurring units of the formula R"
C = O
A - C - E
E - C - H
y wherein - - 14f -1~48009 R" is the addition polymerization product of an ethylenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl, provided that no more than one of A, E or D
may be methyl or phenyl; and Y is an activating group for said ~-elimination; and an alkali permeable and dyeable image-receiving layer.
FIGURE 1 is a cross-sectional view of a photographic film unit including diffusion control layers of this invention;
FIGURE 2 is a cross-sectional view of an image-receiv-ing element including a diffusion control timing layer of this invention;
FIGURE 3 illustrates a model arrangement for measuring the "hold-time" of the interlayers of this invention; and FIGURE 4 is a graphical depiction of dye density as a function of time in a system including an interlayer of the present invention.
- 14g --8~3~)9 It has been found that polymerization products of monomers capable of undergoing ~-elimination in an alkaline environment are useful for providing timed diffusion control in diffusion trans~fer photographic film units. Diffusion 5 control layers of these polymerization products may be formulated for use as diffusion control interlayers or overcoats in photosensitive elements, and as diffusion control, e.g., timing layers or overcoats in image-receiving elements. These polymeric materials must undergo 3-elimination before substantial swelling occurs, ~-elimination and swelling being a prerequisite to permeation by selected materials soluble in or solubilized by an aqueous alkaline processing fluid.
The ~-elimination step which the polymeric materials of the diffusion control~layers of this invention undergo ensures that there is a delay in permeability after contact of the diffusion control layer with the processing composition, and provides a "hold" of the alkali or soluble or solubilized material followed by a rapid "release" or opening to permit the soluble or solubilized material to pass. The polymeric materials may be thought of as "hold-release"
polymers which delay diffusion therethrough of alkali or material soluble in or solubilized by processing fluid by a predetermined time, e.g., from less than five seconds to more several hundred seconds.
- The diffusion control layers of this invention may be used as interlayers between silver halide emulsion layers sensitized to different regions of the spectrum, each emulsion having an associated dye image-forming material.
They may be utilized, e.g., in the manner described in aforementioned ~. S. Patent Nos. 3,615,422 and 3,421,892, substituting the hold-release polymers of this invention for the interlayer polymer compositions disclosed therein.
1~8~09 The time for ~-elimination to occur subseguent to contact with processing compositioncnd for subsequent hydration should be sufficient to maintain the interlayer substantially impermeable to solubilized dye image-forming material until there has been at least substantial development of the emulsions bètween the interlayer and the image-receiving layer but before there has been substantial fogging of the emulsion layer with the most rapid fogging rate.
The diffusion control layers of this invention may be used as timing or spacer layers empIoyed between the alkaline processing composition introduced into the film unit and a neutralizing layer, e.g., a polymeric acid layer, to control the initiation of pH reduction by acting as a substantially impermeable barrier to the alkaline processing composition until ~-elimination occurs.
The diffusion control layers of the invention can also be utilized as an overcoat layer, such as overcoat layer 19 shown in Fig. 1. The employment of such an overcoat layer can be utilized to control, for example, desired dye transfer by conversion of a substantially dye-impermeable layer to a substantially dye-permeable layer.
The introduction of double bonds into a molecule containing single bonds involves the elimination of atoms or groups from adjacent atoms. When elimination reactions involve ~-substituted esters, acids, ketones, aldehydes and nitro compounds,they are called ~-eliminations. According to Hendrickson, Cram and Hamrnond, Organic Chemistry (3rd Edition, McGraw-Hill Book Company, 1970), the electron-withdrawin~ qroups have stronq acid-strenqthening effects on the ~ roton which is removod by base during th~ reaction.
This 1,2-elimination under ~asic conditions i9 very familiar as shown by Fiqure 14-3 from Hendrickson, Cram and Hammond which follow~.
` :1148C~09 I I :B
-------C------C N02 ~ I 1 2 \ NO
> \ ,, 2 where L is a leaving group, B is a base and -N02 a typical activating group. In general terms this might be written:
H
l -BH
> ~ = C\ +L (~
where Y is an activating group.
Substituents which activate ~-elimination under basic conditions are known. The nature of the activation in ~-eliminations was studied by J. Crosby and C.J.M.
Stirling in J. Chem. Soc. (B) 1970 page 671. It was concluded that resonance stabilization of a carbanionic species was an important component of activation.
It has been discovered that such a ~-substituted compound may be incorporated into a polymer to provide a polymer which is substantially impermeable to alkali or certain materials which are soluble in or solubilized by alkaline processing fluid until after ~-elimination breaks bonds liberating groups capable of absorbing water, swel-ling and causing the polymer to become permeable to these soluble or solubilized materials and that such polymer may be used as a diffusion control layer, the resulting pre-determined time delay preventing premature diffusion of the alkali or soluble or solubilized materials. By controlling the mole proportion or ratio of such ~-elimination moieties in the polymer, as well as the thickness of the polymeric layer, one may provide a predetermined permeability time desired for the particular diffusion transfer system.
With reference to the above general formulation for ~-elimination, the leaving group, L, is the polymeric structure from which a ~-substituted material is eliminated or such a polymer additionally containing grafted moieties as disclosed and claimed in Canadian application Serial No. 322,011*, in the names of Bedell, Sullivan and Taylor and filed concurrently herewith.
The ~-elimination reaction can then be written either *See also United States Patent 4,297,431.
,: ' ' ' .009 H-h~H
i H-C-H + CH2=cH-Y
where L is ~H l ' 1 L H ~ ~ and R' is hydrogen or methyl and Y is selected from the group O O
consisting of _SO2WJ -C-T, -S-GJ and -CN where W is 6 5 3J CH3J OC2HsJ -C6H5J -NR2 -n(CH2C6H5)2; T
is -OC2H5J -CH3J -HJ -NH2J -NR2; G is phenylJ methyl or ethyl and R is alkyl J e.g. J methyl or ethyl; or CH2 IC ~ 2 Cl ~:H2 1~ ECH2 H~ H
H--Cl--H
B + CH2=cH-Y
~8~0g where L is t CH2 ~ R' CH--f ~
C=O
1~
and R'and Y are as defined above.
More generally, the reaction is:
~R"~ n C=O C=O +n A-C=c-y O ~ O ~ E D
A ~ C - E
D - C H
y wherein R" is the addition polymerizatiorl unit of an ethylenically unsaturated alkyl group of from two to five carbon atoms, including a graft of such an ethylenically unsaturated alkyl group onto a polymeric organic backbone, A, E and D are selected from the group consisting of hydrogen, methyl and phenyl provlded that no more than one of A, E or D may be methyl or phenyl, Y is an activating group as defined above. Typical monomers which have demonstrated that they provide to their polymerization product a ~-elimination activating group include 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, and 2-carbethoxy-ethyl methacrylate.
Other monomers which should provide the same functionality to their polymerization products include, for example, 2-p-toluenesulfonyl-ethyl acrylate and 2-methane sulfonyl-ethyl acrylate.
The reaction usin~ the polymerization product of 2-cyanoethyl acrylate can be visualized thusly;
~1~8~109 ll l l l H H
----C--C -- ----C--C----El C--O > I H C=O
H- C-H + CH2=CHC.--N
C -N
The diffusion control layers of the invention can comprise homopolymers or copolymers, including graft copolymers as mentioned hereinbefore. Mixtures of polymers can also be employed. Suitable copolymers for use as diffusion control layers will include, in addition to the ~-eliminating component, units from comonomeric materials which provide the polymers with certain desired properties. Such materials may, for example, modulate coalescence or viscosity, improve film integrity and coatability, or provide for more even fluid permeation and ion penetration~ For exampIe, butyl acrylate is useful in providing hydrophobic balance and control to the dye permeation rate.
Comonomers which are non-hydrolyzable or cross-linking may be used. Acrylic acid, methacrylic acid, 2-sulfoethyl methacrylate and 2-acrylamido-2-methylpropane sulfonic acid have been found useful comonomers in assuring that all parts of the diffusion control layer allow processing composition to pass through at essentially the same time and rate so as to promote uniform ~-elimination and hydration of the permeation-inducing component. Ethylene glycol dimethacrylate, a cross-linking monomer, for example, is useful in the diffusion control layer 1~48~0g used as an interlayer to modulate dye transfer rate after the initial hold.
As shown in Figure 1, the diffusion control layers of this invention may be employed in a photographic film unit having a photosensitlve element 26 and an image-receiving element 27. Interlayers 13 and 16 are positioned between red- and green-, and blue- and green- sensitive silver halide emulsions, respectively, in the photosensitive element. These interlayers and the emulsions with their associated dye image-forming material, e.g., dye developer, are preferably arranged on a support 10 in the following order from that support: cyan dye developer layer 11, red-sensitive silver halide emulsion layer 12, interlayer 13, magenta dye developer layer 14, green-sensitive silver halide emulsion 15, lS interlayer 16, yellow dye developer layer 17 and blue-sensitive silver halide emulsion layer 18. An overcoat layer 19 may be coated on top of the blue-sensitive silver halide emulsion layer.
The image-receiving element 27 illustrated in Figure 1 comprises in order, an image-receiving layer 21, a spacer or timing layer 22, a neutralizing layer 23 and a support layer 24. During processing the image-receiving layer is situated closest to the photosensitive element.
After the photosensitive element has been exposed, aqueous alkaline processinq composition 20 is introduced between the photosensitive and image-receiving elements and permeates the emulsion layers to initiate development of the latent imaqe carried therein and provide a medium for dye diffusion transfer to the image-receiving element. Dye image-forming materials associated ~ith unexposed portions - 22 ~
~481)09 of the emulsion layers diffuse to the image-receiving element in known manner. As set forth in U. S. Patent No. 3,362,819, situated beneath the image-receiving layer is a neutralizing layer containing a polymeric acid to neutralize alkali in the processing composition after a predetermined period.
The timing or spacing layer, comprised of polymeric material and located between the image-receiving and neutralizing layers is used to control the pH reduction.
Diffusion control layers comprising a ~-elimination polymeric material in accordance with this invention comprise, in one preferred embodiment, interlayers 13 and/or 16. Alternatively, overcoat layer 19 can comprise a diffusion control layer of a ~-eliminating polymeric material. In another preferred embodiment the spacer layer 22 comprises a diffusion control lS layer of the invention.
The image-receiving element 27 illustrated in Figure 2 comprises in order, a support layer 28, a neutralizing layer 29, a spacer or timing layer 30, an image-receiving layer 31 and an overcoat 32. During processing the image-receiving element overcoat is situated closest to the photosensitive element. In one embodiment of this invention, a diffusion control layer comprising a ~-elimination polymeric material in accordance with this invention comprises overcoat layer 32.
A measure of time of pH r~duction can be had from a quantity which can be referred to as a "clearing time"
which can be measured by use of the following system. An image-receiving element comprising in order on a support, a polymeric acid layer, a test timing layer and a mordanting layer, is spread with an alkaline procecsing material of high pH comprising an indicator dye which is highly colored at pH's of about 12 to 14 and colorless below about 10. A
~1~80~)9 transparent cover sheet is superposed the processing material.
The view through the cover sheet toward the image-receiving element is dark until the alkali has penetrated to the polymeric acid layer where the pH is reduced by alkali consumption and the indicator dye becomes colorless, the system has "cleared". A skilled operator can determine when the ~learing begins and when it is complete. A "leaky"
timing layer allows a trickle of alkali through from the moment of first contact and shows no precipitous change in beginning to clear nor in the final clearing. A timing layer comprising the polymers of the instant invention will hold the alkali back for a definite timed period, and then, over a very short time interval, allow sufficient alkali through to drop the pH below the transition range of the indicator dye.
Clearing time can be measured for a structure that comprises an entire image-receiving element or it can be measured for a model simplified structure that includes only the timing layer coated over the polymeric acid layer on the support. The first clearing time is referred to as "clearing through the mordant" while the second model structure clearing is referred to as "clearing through the timing layer".
The diffusion control layer of this invention used as a top coat for an image-receiving element is located on top of the strata that comprise the image-receiving element. Por example, in an image-receiving element comprising in order, a support, a polymeric acid layer, a spacer layer and an alkali permeable and dyeable polymeric layer, the ~iffusion control layer is located next adjacent ` 114~09 the alkali permeable and dyeable polymeric layer, furthest from the support and acts to delay permeation to the image-receiving element of the processing composition and materials solubilized by it.
The capacity of polymeric diffusion control layers of the invention to delay permeation therethrough of image-forming dye until conversion by a 3-elimination reaction to a relatively dye-permeable polymer can be evaluated by resort to utilization of a test structure shown in Fig. 3. In accordance with such structure, dye transfer through the polymeric test material, e.g., an interlayer test material, is monitored in relation to time. The "hold-release" properties of a polymeric test material can be evaluated in simulation of the functioning of a material as, e.g., an interlayer in a photosensitive element.
Such test structure and a suitable method of evaluation are set forth in detail in Examples 1 to 15 hereof.
The following examples are presented for illustrative purposes only and are not intended to be in any way limiting. Measurements were made at ambient room temperature, about 25C, unless otherwise specified.
Examples 1-10 On a transparent support, 33 in Fig. 3, a 2~S.~ ~51~
layer 34 comprising 20 mg/ft~ of a cyan dye developer 8~9 CH
HC - NH - O2S ~
N = C C _N
~ ~ I \N ~ ll fH3 HO ~ ~ S2 - NH IH
N _ CUL_N~
ICH2 N - C ~ - N
HO ~ OH ~ S2 - NH - ?H
~ H
HO ~
40 mg/ft (430.6 mgs/m2) gelatin and 1.5 mg/ft2 (16.1 mgs/m2) of succinaldehyde was coated using a conventional loop coater. Over this layer, a layer 35 containing 200 mg/ft2 (2153 mgs/m2) of the polymeric material being tested was coated.
A transparent element 38 comprising a polyester clear film base was superposed with test elements to form sandwiches and an opaque alkaline processing composition 36 comprising:
Potassium hydroxide (45% aqueous solution) 22.9 g.
Lithium hydroxide 0.55 g.
Benzotriazole 1.53 g.
6-Bromo-5-methyl-4-azabenzimidazole 0.08 g.
6-methyl uracil 0.82 g.
Ethylene diamine tetraacetic acid 2.27 g.
Bis-(2-aminoethyl) sulfide 0.06 g.
Carbowax (mw 6000)* 1.5 g.
Colloidal silica 5.05 g.
6-benzylaminopurine 1.09 g.
Titanium dioxide 115.23 g.
N-phenethyl a-picolinium bromide 3.91 g.
(50% aqueous solution) N-benzyl o~-picolinium bromide 5.09 g.
~50% aqueous solution) Lithium nitrate 0.27 g.
Carboxymethyl hydroxyethyl cellulose 4.82 g.
Water 100 g.
was introduced between the polymeric test material layer and the transparent element 38 at a gap of 0.0028 in, (about 0.07 mm).
The optical reflection density to red light of the processed sample, viewed through support 33 in Figure 3~ as a function of time was continuously read using a MacBeth Quanta-Log* densitometer equipped with a Hewlett-Packard*
17505A strip-chart recorder. This density comprises contributions from the dye image-forming material remaining in the dye layer and dye image-forming material in the polymeric *Trademark - 27 1148~09 test layer. The titanium dioxide in the processing composition masks dye image-forming material in the processing composition layer. A typical curve of density as a function of time is given in Figure 4 wherein tl is the time for dye image-forming material to solubilize, t2 is the total time the dye image-forming material is held back by the polymeric interlayer, Do is the density after the initial dissolution of the dye image-forming material, Df is the density after dye transfer through the interlayer, and the slope of the line segment between A and B is calculated as the rate of change of densit .
Values for tl, t2 and slope are given below for the following hold-release polymer systems of the present invention:
1. 100 parts by weight of 2-cyanoethyl acrylate mixed with 100 parts by weight of a 95.5/4.5 copolymer of diacetone acrylamide and acrylic acid and polymerized.
2. 35 parts by weight of 2-cyanoethyl acrylate mixed with 65 parts by weight of a 95.5/4.5 copolymer of diacetone acrylamide and acrylic acid and polymerized.
3. A 47.5/50/2.5 interpolymer of diacetone acrylamide, 2-cyanoethyl acxylate and acrylic acid.
4. A 63/35/2 interpolymer of diacetone acrylamide, 2-cyanoethyl acrylate and acrylic acid
5. An 85/10/2/3 interpolymer of butylacrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-acrylamido-2-methyl propane sulfonic acid.
6. An 85/10/2/3 interpolymer of butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-sulfoethylmethacrylate.
7. 35 parts by weight of 2-cyanoethylacrylate mixed with 100 parts by weight of a 99.25/0.75 copolymer of 2-cyanoethylacrylamide and acrylic acid and polymerized.
:L~48~ )9
:L~48~ )9
8. A 63/35/2 interpolymer of diacetone-acrylamide, 2-carbethoxyethyl methacrylate and acrylic acid.
9. A 63/35/2 interpolymer of diacetone acrylamide, 2-cyanoe~hyl methacrylate and acrylic acid.
10. 100 parts by weight of 94/6 copolymer of diacetone acrylamide and acrylic acid mixed with 100 parts by weight of a 63/35/2 interpolymer of diacetone acrylamide, 2-cyanoethyl methacrylate and acrylic acid.
All interpolymer constituent proportions are on a weight basis Sample tl t2 slope . _ .
6 10 16.5 737 It is apparent from the foregoing table that the present invention provides a significant hold time before solubilized dye image forming material is released, and accomplishes the dye release in a relatively short time span.
Hold time is longer at 45F ~about 7 C) and shorter at 95 F (about 35 C), paralleling development time. For ex-ample, sample 2 above has a t2 of 215 sec. at 45F and a slope of 87, and has a t2 of 11 sec. at 95F and a slope of 654.
1148~09 Examples 11-15 Test elements were prepared as in Example 1:10. A second transpar-ent element comprising a polyester clear film base was superposed to the test elements to form sandwiches and an opaque alkaline processing composition comprising:
Potassium hydroxide (45% aqueous solution) 13.63 g.
Cesium hydroxide ~50% aqueous solution) 10.65 g.
Benzotriazole 1.18 g.
5-hydroxyazabenzimidazole 0.118 g.
10 6-bromo-5-methyl-4-azabenzimidazole 0.059 g.
2-methylimidazole 0.42 g.
Sodium carboxymethyl cellulose 0.43 g.
Titanium dioxide 59.27 g.
N-phenethyl-~-picolinium bromide 4.2 g.
(50% aqueous solution) Water 100 g.
was introduced between the polymeric material and the uppermost transparent element at a gap of 0.0028 in ~about 0.07 mm).
Theitime, T, needed for the dye material to permeate the polymeric material was determined by monitoring optical density of the dye through the uppermost transparent element using the densitometer designated in Examples 1-10 .
Values for T in seconds are given below for the following hold-re-lease polymer systems of the present invention:
All interpolymer constituent proportions are on a weight basis Sample tl t2 slope . _ .
6 10 16.5 737 It is apparent from the foregoing table that the present invention provides a significant hold time before solubilized dye image forming material is released, and accomplishes the dye release in a relatively short time span.
Hold time is longer at 45F ~about 7 C) and shorter at 95 F (about 35 C), paralleling development time. For ex-ample, sample 2 above has a t2 of 215 sec. at 45F and a slope of 87, and has a t2 of 11 sec. at 95F and a slope of 654.
1148~09 Examples 11-15 Test elements were prepared as in Example 1:10. A second transpar-ent element comprising a polyester clear film base was superposed to the test elements to form sandwiches and an opaque alkaline processing composition comprising:
Potassium hydroxide (45% aqueous solution) 13.63 g.
Cesium hydroxide ~50% aqueous solution) 10.65 g.
Benzotriazole 1.18 g.
5-hydroxyazabenzimidazole 0.118 g.
10 6-bromo-5-methyl-4-azabenzimidazole 0.059 g.
2-methylimidazole 0.42 g.
Sodium carboxymethyl cellulose 0.43 g.
Titanium dioxide 59.27 g.
N-phenethyl-~-picolinium bromide 4.2 g.
(50% aqueous solution) Water 100 g.
was introduced between the polymeric material and the uppermost transparent element at a gap of 0.0028 in ~about 0.07 mm).
Theitime, T, needed for the dye material to permeate the polymeric material was determined by monitoring optical density of the dye through the uppermost transparent element using the densitometer designated in Examples 1-10 .
Values for T in seconds are given below for the following hold-re-lease polymer systems of the present invention:
11. 2 parts by weight of an 85/10/3/2 interpolymer of butyl acrylate, 2-cyanoethyl acrylate, 2-sulfo-ethyl methacrylate with 1 part by-weight of a 94/6 copolymer of butyl acrylate.
12. An 85/10/2/3 interpolymer of butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-acrylamido-2-methylpropane sulfonic acid.
1:148009
1:148009
13. An 89/6/2/3 interpolymer of butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-sulfoethyl-methacrylate.
14. 85 parts of an 68/10/2/5 interpolymer of butyl acrylate, 2-cyanoethyl methacrylate, 2-sulfoethylmethacrylate and ethyleneglycol dimethacrylate polymerized around a seed of
15 parts by weight of butyl acrylate.
15. An 85/10/2/3 interpolymer of butyl acrylate, 2-cyanoethylacrylate, methacrylic acid and 2-sulfoethyl methacrylate.
Sample T
-T, while measuring the time before solubilized dye image forming material becomes available to an image receiving layer, includes the time necessary for this solubilized dye image forming material to diffuse through the alkaline processing composition and has a component related to the thickness of that alkaline processing composition layer.
The relative proportions of ingredients in the processing composition may naturally be altered where desired. For example, substitution of various preservatives, alkalies, silver halide solvents, etc. is contemplated, as well as inclusion of such components as restrainers and accelerators. The concentration of various components may also be varied over a wide range.
~1~8~g Examples 16-19 Image-receiving elements of the invention were prepared by coating a transparent 4 mil (0.1 mm) polyethylene terephthalate film base with the following layers to form an image-receiving component:
1. as a polymeric acld layer, the partial butyl ester of poly-ethylene/maleic anhydride copolymer mixed with about 10% by weight of poly-vinyl butyral and coated at a coverage of about 2500 mg/ft2 (26910 mgs/m2);
2. a timing layer containing polymeric materials described in de-tail in the examples that follow; and 3. as a polymeric image-receiving layer a mixture of 6 parts by weight of polyvinyl alcohol, 3 parts by weight of poly-4-vinylpyridine and 1 part by weight of a graft polymer of 4-vinyl pyridine-vinylbenzyltri-methyl ammonium chloride on hydroxy-ethylcellulose at a coverage of 300 mg/ft (322~ mgs/m ~ The elements are labeled (a).
For comparison, test elements were prepared which did not have the polymeric image-receiving layer on top of the timing layers. These elements are labeled (b).
. ~
Timing Layer Permeation Time (sec) _ . . , _ .__ _ ExampleMaterial Coverage StartFinish Control (a) I 500 (5370) 180 210 (b) I 500 (5370) 60 87
15. An 85/10/2/3 interpolymer of butyl acrylate, 2-cyanoethylacrylate, methacrylic acid and 2-sulfoethyl methacrylate.
Sample T
-T, while measuring the time before solubilized dye image forming material becomes available to an image receiving layer, includes the time necessary for this solubilized dye image forming material to diffuse through the alkaline processing composition and has a component related to the thickness of that alkaline processing composition layer.
The relative proportions of ingredients in the processing composition may naturally be altered where desired. For example, substitution of various preservatives, alkalies, silver halide solvents, etc. is contemplated, as well as inclusion of such components as restrainers and accelerators. The concentration of various components may also be varied over a wide range.
~1~8~g Examples 16-19 Image-receiving elements of the invention were prepared by coating a transparent 4 mil (0.1 mm) polyethylene terephthalate film base with the following layers to form an image-receiving component:
1. as a polymeric acld layer, the partial butyl ester of poly-ethylene/maleic anhydride copolymer mixed with about 10% by weight of poly-vinyl butyral and coated at a coverage of about 2500 mg/ft2 (26910 mgs/m2);
2. a timing layer containing polymeric materials described in de-tail in the examples that follow; and 3. as a polymeric image-receiving layer a mixture of 6 parts by weight of polyvinyl alcohol, 3 parts by weight of poly-4-vinylpyridine and 1 part by weight of a graft polymer of 4-vinyl pyridine-vinylbenzyltri-methyl ammonium chloride on hydroxy-ethylcellulose at a coverage of 300 mg/ft (322~ mgs/m ~ The elements are labeled (a).
For comparison, test elements were prepared which did not have the polymeric image-receiving layer on top of the timing layers. These elements are labeled (b).
. ~
Timing Layer Permeation Time (sec) _ . . , _ .__ _ ExampleMaterial Coverage StartFinish Control (a) I 500 (5370) 180 210 (b) I 500 (5370) 60 87
16(a) II 250 (2690) 215 245 16(b) II 250 (2690) 60 68
17(a) II 500 (5370) 280 325 17(b) II S00 (5370) 92 105
18(a) III 500 (5370) 33 40 18(b) III 500 (5370) 25 29 l9(a) III 250 (2690) 25 32 (b) III 250 (2690) _ 20 ~48C~09 where I is a 60/30/4/6 interpolymer of butyl acrylate, diace-tone acrylamide, styrene and methacrylic acid blended with 9% by weight of polyvinylalcohol; II is a seed of 100 parts of a 87.5/2/0.5 interpolymer of diacetone acrylamide, acrylic acid and 2-acrylamido-2-methyl propane sulfonic acid, sodium salt around which is polymerized 49 parts of 2-cyanoethyl acrylate; and III is a 63/35/2 interpolymer of diacetone acrylamide, 2-cyanoethyl acrylate and acrylic acid.
100 g water 4.02 g hydroxyethyl carboxymethyl cellulose 4.15 g 50% potassium hydroxide solution 1.12 g benzotriazole 0.50 g thymolphthalein was introduced between the polymeric test material layer and the transparent element at a gap of 0.0028 in.(about 0.07 mm). The time denoted as permeation time and measured in sec-onds, for the sandwich to change color from blue to colorless is a measure of the time necessary for the processing composi-tion to permeate the timing layer and react with the polymeric acid layer lowering the pH. Times are recorded as "start", when the sandwich first starts to clear and "finish" when the sandwich has substantially completed clearing.
Examples 20-27 On a transparent 4 mil (0.1 mm) polyethylene tere-phthalate film base was coated the partial butyl ester of poly-ethylene/maleic anhydride copolymer mixed with about 10% by weight of polyvinyl butyral at a coverage of about 2500 mg/ft (26910 mgs/m23. On this layer was coated the following timing layers and image receiving layers at the coverages indicated.
Permeation time was measured as detailed above.
11~8~9 __ _ _ Image Receiving Permeation Timlng Layer Layer Time (sec) Example Material Cover2age Material cove2rage 5tart Finish mg / f t ( /m2) mg / f t ( /m2 A 200 (2153) 31 21 A 200 (2153) D 500 (5380) 54 58 _ 22 B 200 (2153) 31 23 B 200 (2153) D 500 (5380) 62 _ 24 C 600 (6459) 41 48 C 100~ 41 45 26 C 600 (6459) D 500 (5380) 80 92 _ 27 C 1000 (10765) D 500 ~5380) 80 110 where A is a seed of an 56.7/25/5/1/2 interpolymer of butyl-acrylate, 2-cyanoethylacrylate, ethylene glycol dimethyacrylate, acrylic acid and styrene around which is polymerized a 10~3 mix-ture of diacetone acrylamide and acrylic acid. The pH of A is 2.6; B comprises the material of A with sufficient potassium hydroxide added to bring the pH to 8.0; C is a 59/40/1 interpoly-mer of diacetone acrylamide, 2-cyanoethylacrylate and acrylic acid; and D is a graft copolymer of 4-vinyl pyridine, vinly ben-zyl trimethyl ammonium chloride on polyvinyl alcohol.
Cyano-substituted acrylates have been disclosed in United States Patent 4,120,727 as silver halide grain-growing protective colloids; there is no disclosure or suggestion of a diffusion control effect
100 g water 4.02 g hydroxyethyl carboxymethyl cellulose 4.15 g 50% potassium hydroxide solution 1.12 g benzotriazole 0.50 g thymolphthalein was introduced between the polymeric test material layer and the transparent element at a gap of 0.0028 in.(about 0.07 mm). The time denoted as permeation time and measured in sec-onds, for the sandwich to change color from blue to colorless is a measure of the time necessary for the processing composi-tion to permeate the timing layer and react with the polymeric acid layer lowering the pH. Times are recorded as "start", when the sandwich first starts to clear and "finish" when the sandwich has substantially completed clearing.
Examples 20-27 On a transparent 4 mil (0.1 mm) polyethylene tere-phthalate film base was coated the partial butyl ester of poly-ethylene/maleic anhydride copolymer mixed with about 10% by weight of polyvinyl butyral at a coverage of about 2500 mg/ft (26910 mgs/m23. On this layer was coated the following timing layers and image receiving layers at the coverages indicated.
Permeation time was measured as detailed above.
11~8~9 __ _ _ Image Receiving Permeation Timlng Layer Layer Time (sec) Example Material Cover2age Material cove2rage 5tart Finish mg / f t ( /m2) mg / f t ( /m2 A 200 (2153) 31 21 A 200 (2153) D 500 (5380) 54 58 _ 22 B 200 (2153) 31 23 B 200 (2153) D 500 (5380) 62 _ 24 C 600 (6459) 41 48 C 100~ 41 45 26 C 600 (6459) D 500 (5380) 80 92 _ 27 C 1000 (10765) D 500 ~5380) 80 110 where A is a seed of an 56.7/25/5/1/2 interpolymer of butyl-acrylate, 2-cyanoethylacrylate, ethylene glycol dimethyacrylate, acrylic acid and styrene around which is polymerized a 10~3 mix-ture of diacetone acrylamide and acrylic acid. The pH of A is 2.6; B comprises the material of A with sufficient potassium hydroxide added to bring the pH to 8.0; C is a 59/40/1 interpoly-mer of diacetone acrylamide, 2-cyanoethylacrylate and acrylic acid; and D is a graft copolymer of 4-vinyl pyridine, vinly ben-zyl trimethyl ammonium chloride on polyvinyl alcohol.
Cyano-substituted acrylates have been disclosed in United States Patent 4,120,727 as silver halide grain-growing protective colloids; there is no disclosure or suggestion of a diffusion control effect
Claims (78)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A photographic diffusion transfer film unit comprising:
a. a photosensitive element comprising at least one photosensitive silver halide emulsion layer having associated therewith a processing composition soluble and diffusible image-forming materials;
b. an image-receiving element;
c. means for discharging an alkaline processing composition within said film unit; and d. a diffusion control layer in at least one of said photosensitive element or said image-receiving element;
said diffusion controllayer including a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E, or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
a. a photosensitive element comprising at least one photosensitive silver halide emulsion layer having associated therewith a processing composition soluble and diffusible image-forming materials;
b. an image-receiving element;
c. means for discharging an alkaline processing composition within said film unit; and d. a diffusion control layer in at least one of said photosensitive element or said image-receiving element;
said diffusion controllayer including a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E, or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
2. The photographic diffusion transfer film unit of Claim 1 wherein said photosensitive element comprises at least two silver halide emulsion layers having associated therewith a processing composition soluble and diffusible image-forming material and said diffusion control layer comprises an interlayer positioned between said silver halide emulsion layers.
3. The photographic diffusion transfer film unit of Claim 1 wherein said diffusion control layer comprises an overcoat in said photosensitive element.
4. The photographic diffusion transfer film unit of Claim 1 wherein said diffusion control layer is present in said image-receiving element.
5. The photographic diffusion transfer film unit of Claim 4 wherein said diffusion control layer comprises a timing layer of said image-receiving element.
6. The photographic diffusion transfer film unit of Claim 4 wherein said diffusion control layer comprises an overcoat in said image-receiving element.
7. The film unit of Claim 1 wherein said image-forming material is a dye developer.
8. The film unit of Claim 1 wherein said activating group is selected from the group consisting of:
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -C6H5, NR2, -N2(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2;
G is phenyl, methyl or ethyl; and R is methyl or ethyl.
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -C6H5, NR2, -N2(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2;
G is phenyl, methyl or ethyl; and R is methyl or ethyl.
9. The film unit of Claim 1 wherein said polymerization product comprises poly (2-cyano-ethyl acrylate).
10. The film unit of Claim 1 wherein said polymerization product comprises poly (2-cyano-ethyl methacrylate).
11. The film unit of Claim 1 wherein said polymerization product comprises poly (2-carbethoxy-ethyl methacrylate).
12. The film unit of Claim 1 wherein said polymerization product further comprises a nonhydrolyzable comonomer.
13. The film unit of Claim 1 wherein said polymerization product further comprises units of a cross-linking comonomer.
14. A photosensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment;
said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment;
said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
15. The photosensitive element of Claim 14 which comprises, in sequence, a red-sensitive silver halide layer having associat-ed therewith a cyan dye image-forming material, a green-sensitive silver halide layer having associated therewith a magenta dye image-forming material, and a blue-sensitive silver halide layer having associated therewith a yellow dye image-forming material.
16. The photosensitive element of Claim 14 wherein said activating group is selected from the group consisting of:
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -C6H5, NR2, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2, G is phenyl, methyl or ethyl; and R is methyl or ethyl.
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -C6H5, NR2, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2, G is phenyl, methyl or ethyl; and R is methyl or ethyl.
17. The photosensitive element of Claim 14 wherein said polymerization product comprises poly (2-cyano-ethyl acrylate).
18. The photosensitive element of Claim 14 wherein said polymerization product comprises poly (2-cyano-ethyl methacrylate).
19. The photosensitive element of Claim 14 wherein said polymerization product comprises poly (2-carbethoxyethyl methacrylate).
20. The photosensitive element of Claim 14 wherein said polymerization product further comprises units of a nonhydrolyz-able comonomer.
21. The photosensitive element of Claim 14 wherein said polymerization product further comprises units of a cross-link-ing comonomer.
22. A photosensitive element for use in diffusion transfer photographic processes comprising:
a support layer;
at least one photosensitive silver halide emulsion layer coated upon said support, said emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an overcoat including a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment; said polymeriza-tion product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
a support layer;
at least one photosensitive silver halide emulsion layer coated upon said support, said emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an overcoat including a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment; said polymeriza-tion product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
23. The photosensitive element of Claim 22 wherein there is coated upon said support at least two selectively sensitized silver halide emulsion layers.
24. The photosensitive element of Claim 23 wherein said selectively sensitized silver halide emulsion layers comprise, in sequence, a red-sensitive silver halide layer having assoc-iated therewith a cyan dye image-forming material, a green-sensitive silver halide layer having associated therewith a magen-ta dye image-forming material, and a blue-sensitive silver halide layer having associated therewith a yellow dye image-forming material.
25. The photosensitive element of Claim 22 wherein said activating group is selected from the group consisting of:
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, OC2H5, -C6H5, NR2, -N(CH2C6H5)2;
T is -OC2H5, -CH3, H, NH2, -NR2, G is phenyl, methyl or ethyl; and R is methyl or ethyl.
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, OC2H5, -C6H5, NR2, -N(CH2C6H5)2;
T is -OC2H5, -CH3, H, NH2, -NR2, G is phenyl, methyl or ethyl; and R is methyl or ethyl.
26. The photosensitive element of Claim 22 wherein said polymerization product comprises poly (2-cyano-ethyl acrylate).
27. The photosensitive element of Claim 22 wherein said polymerization product comprises poly (2-cyano-ethyl methacrylate).
28. The photosensitive element of Claim 22 wherein said polymerization product comprises poly (2-carbethoxyethyl meth-acrylate).
29. The photosensitive element of Claim 22 wherein said polymerization product further comprises units of a nonhydrolyz-able comonomer.
30. The photosensitive element of Claim 22 wherein said polymerization product further comprises units of a cross-link-ing comonomer.
31. A photosensitive element for use in diffusion transfer photographic processes comprising:
a support layer at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer comprises a mixture of polymers, at least one of which polymers includes a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethylenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
a support layer at least two selectively sensitized silver halide emulsion layers coated upon said support, each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer comprises a mixture of polymers, at least one of which polymers includes a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethylenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
32. A photographic film unit comprising in combination a photosensitive element and a diffusion transfer image-receiving element, said combination comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer includes a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
33. The film unit of Claim 32 wherein said diffusion trans-fer image-receiving element comprises a support layer having coated thereon said alkaline processing composition permeable and dye image-forming material dyeable image-receiving layer, said image receiving element being affixed to at least one edge of said photosensitive element and adapted to be superposed there-with so that the support layer of each element comprises the extremities of the superposed structure.
34. The film unit of Claim 33 wherein said photosensitive element comprises, in sequence, a support layer; a red-sensitive silver halide layer having associated therewith a cyan dye image-forming material; an interlayer comprising a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment;
a green-sensitive silver halide layer having associat-ed therewith a magenta dye image-forming material; a second interlayer comprising a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization products comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D
may be methyl or phenyl, and Y is an activating group for said .beta.-elimination; and a blue-sensitive silver halide layer having associated therewith a yellow image-forming material.
a green-sensitive silver halide layer having associat-ed therewith a magenta dye image-forming material; a second interlayer comprising a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization products comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D
may be methyl or phenyl, and Y is an activating group for said .beta.-elimination; and a blue-sensitive silver halide layer having associated therewith a yellow image-forming material.
35. The film unit of Claim 32 wherein said activating group is selected from the group consisting of:
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2;
G is phenyl, methyl or ethyl; and R is methyl or ethyl.
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2;
G is phenyl, methyl or ethyl; and R is methyl or ethyl.
36. The film unit of Claim 32 wherein the said polymerizat-ion product comprises poly (2-cyano-ethyl acrylate).
37. The film unit of Claim 32 wherein said polymerization product comprises poly (2-cyano-ethyl methacrylate).
38. The film unit of Claim 32 wherein said polymerization product comprises poly (2-carbethoxy-ethyl methacrylate).
39. The film unit of Claim 32 wherein said polymerization product further comprises units of nonhydrolyzable comonomer.
40. The film unit of Claim 32 wherein said polymerization product further comprises units of cross-linking comonomer.
41. A photographic film unit comprising in combination a photosensitive element and a diffusion transfer image-receiving element, said combination comprising:
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer comprises a mixture of polymers at least one of which polymers comprises a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D
may be methyl or phenyl, and Y is an activating group for said .beta.-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
a support layer;
at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer positioned as an interlayer between at least two of said silver halide emulsion layers, which interlayer comprises a mixture of polymers at least one of which polymers comprises a polymerization product of a monomer capable of undergoing .beta.-elimination in an alkaline environment, said polymerization product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E or D
may be methyl or phenyl, and Y is an activating group for said .beta.-elimination; and an alkaline processing composition permeable and dyeable image-receiving layer.
42. An element for use in diffusion transfer photographic processes comprising:
a support layer, a polymeric acid layer, and a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment, said polymerizat-ion product including recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E and D
may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
a support layer, a polymeric acid layer, and a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment, said polymerizat-ion product including recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl provided that no more than one of A, E and D
may be methyl or phenyl; and Y is an activating group for said .beta.-elimination.
43. An element as defined in Claim 42 including an alkali permeable and dyeable image-receiving layer.
44. The element of Claim 43 wherein said activating group is selected from the group consisting of -SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, NR2, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, NH2, -NR2, G is phenyl, methyl or ethyl, and R is methyl or ethyl.
T is -OC2H5, -CH3, -H, NH2, -NR2, G is phenyl, methyl or ethyl, and R is methyl or ethyl.
45. The element of Claim 43 wherein said polymerization product comprises poly (2-cyano-ethyl acrylate).
46. The element of Claim 43 wherein said polymerization product comprises poly (2-cyano-ethyl methacrylate).
47. The element of Claim 43 wherein said polymerization product comprises poly (2-carbethoxyethyl methacrylate).
48. The element of Claim 43 wherein said polymerization product further comprises units of a nonhydrolyzable comonomer.
49. The element of Claim 43 wherein said polymeric layer comprises a timing layer positioned between said polymeric acid layer and said image-receiving layer.
50. The image-receiving element of Claim 43 wherein said polymeric layer comprises an overcoat layer positioned over said image-receiving layer.
51. An image-receiving element for use in diffusion trans-fer photographic processing comprising:
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a mixture of polymers, at least one of which polymers comprises a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment, said polymerizat-ion product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, meth-yl, and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination, and an alakli permeable and dyeable image-receiving layer.
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a mixture of polymers, at least one of which polymers comprises a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment, said polymerizat-ion product comprising recurring units of the formula wherein R" is the addition polymerization product of an ethy-lenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, meth-yl, and phenyl provided that no more than one of A, E or D may be methyl or phenyl; and Y is an activating group for said .beta.-elimination, and an alakli permeable and dyeable image-receiving layer.
52. The receiving element of Claim 51 wherein said activat-ing group is selected from the group consisting of:
-SO2W, , , -CN, and -NO2 where W is -C6H5CH , -CH3, -OC2H5, NR2, -N(CH@C^H%)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2;
G is phenyl, methyl or ethyl, and R is methyl or ethyl.
-SO2W, , , -CN, and -NO2 where W is -C6H5CH , -CH3, -OC2H5, NR2, -N(CH@C^H%)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2;
G is phenyl, methyl or ethyl, and R is methyl or ethyl.
53. The receiving element of Claim 51 wherein said poly-merization product comprises poly (2-cyano-ethyl acrylate).
54. The receiving element of Claim 51 wherein said poly-merization product comprises poly (2-cyano-ethyl methacrylate).
55. The receiving element of Claim 51 wherein said poly-merization product comprises poly (2-carbethoxy-ethyl meth-acrylate).
56. The receiving element of Claim 51 wherein said poly-merization product further comprises units of a nonhdrolyzable comonomer.
57. The receiving element of Claim 51 wherein said poly-merization product further comprises units of a cross-linking comonomer.
58. The image-receiving element of Claim 51 wherein said polymeric layer comprising said mixture of polymers comprises a timing layer positioned between said polymeric acid layer and said image-receiving layer.
59. The image-receiving element of Claim 51 wherein said polymeric layer comprising said mixture of polymers comprises an overcoat positioned over said image-receiving layer.
60. A photographic film unit comprising in combination a silver halide photosensitive element and a diffusion transfer image-receiving element, said image-receiving element comprising:
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment, said polymeriza-tion product comprising recurring units of the formula herein R" is the addition polymerization product of an ethylenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl, provided that no more than one of A, E or D
may be methyl or phenyl; and Y is an activating group for said .beta.-elimination; and an alkali permeable and dyeable image-receiving layer.
a support layer;
a polymeric acid layer, a diffusion control layer comprising a polymeric layer including a polymerization product of a monomer capable of under-going .beta.-elimination in an alkaline environment, said polymeriza-tion product comprising recurring units of the formula herein R" is the addition polymerization product of an ethylenically unsaturated alkyl group of two to five carbon atoms, A, D and E are selected from the group consisting of hydrogen, methyl and phenyl, provided that no more than one of A, E or D
may be methyl or phenyl; and Y is an activating group for said .beta.-elimination; and an alkali permeable and dyeable image-receiving layer.
61. The photographic film unit of Claim 60 wherein said activating group is selected from the group consisting of:
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2, G is phenyl, methyl or ethyl, and R is methyl or ethyl.
-SO2W, , , -CN, and -NO2 where W is -C6H5CH3, -CH3, -OC2H5, -N(CH2C6H5)2;
T is -OC2H5, -CH3, -H, -NH2, -NR2, G is phenyl, methyl or ethyl, and R is methyl or ethyl.
62. The film unit of Claim 60 wherein said polymerization product comprises poly (2-cyano-ethyl acrylate).
63, The film unit of Claim 60 wherein said polymerization product comprises poly (2-cyano-ethyl methacrylate).
64. The film unit of Claim 60 wherein said polymerization product comprises poly (2-carbethoxy-ethyl methacrylate).
65. The film unit of Claim 60 wherein said polymerization product further comprises units of a nonhydrolyzable comonomer.
66. The film unit of Claim 60 wherein said polymerization product further comprises units of a cross-linking comonomer.
67. The photographic film unit of Claim 60 wherein said polymeric layer of said image-receiving element comprises a timing layer positioned between said polymeric acid layer and said image-receiving layer.
68. The photographic film unit of Claim 60 wherein said polymeric layer of said image-receiving element comprises an overcoat positioned over said image-receiving layer.
69. A photographic film unit comprising in combination a photosensitive element and a diffusion transfer image-receiving element, said photosensitive element comprising:
a photosensitive element support layer, at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer comprising a polymerization product comprising 2-cyano-ethyl acrylate positioned as an interlayer between the silver halide emulsion layers;
and said image-receiving element comprising:
an image-receiving element support;
a polymeric acid layer;
a diffusion control layer comprising poly (2-cyano-ethyl acrylate); and an alkali permeable and dyeable image-receiving layer.
a photosensitive element support layer, at least two selectively sensitized silver halide emulsion layers coated upon said support each emulsion layer having associated therewith a processing composition soluble and diffusible dye image-forming material; and a diffusion control layer comprising a polymerization product comprising 2-cyano-ethyl acrylate positioned as an interlayer between the silver halide emulsion layers;
and said image-receiving element comprising:
an image-receiving element support;
a polymeric acid layer;
a diffusion control layer comprising poly (2-cyano-ethyl acrylate); and an alkali permeable and dyeable image-receiving layer.
70. The photographic diffusion transfer film unit of claim 1 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 1 and R1 repre-sents hydrogen or methyl.
71. The photosensitive element of claim 14 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 14 and R1 repre-sents hydrogen or methyl.
72. The photosensitive element of claim 22 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 14 and R1 repre-sents hydrogen or methyl.
73. The photosensitive element of claim 31 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 31 and R1 repre-sents hydrogen or methyl.
74. The photographic film unit of claim 32 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 32 and R1 repre-sents hydrogen or methyl.
75. The photographic film unit of claim 41 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 41 and R1 repre-sents hydrogen or methyl.
76. An element as defined in claim 42 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 42 and R1 repre-sents hydrogen or methyl.
77. The receiving element of claim 51 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 51 and R1 repre-sents hydrogen or methyl.
78. The photographic film unit of claim 60 wherein said recurring units are of the formula wherein A, E, H and Y are as defined in claim 60 and R1 repre-sents hydrogen or methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000322010A CA1148009A (en) | 1979-02-21 | 1979-02-21 | Diffusion control layers in diffusion transfer photographic products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000322010A CA1148009A (en) | 1979-02-21 | 1979-02-21 | Diffusion control layers in diffusion transfer photographic products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148009A true CA1148009A (en) | 1983-06-14 |
Family
ID=4113594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000322010A Expired CA1148009A (en) | 1979-02-21 | 1979-02-21 | Diffusion control layers in diffusion transfer photographic products |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1148009A (en) |
-
1979
- 1979-02-21 CA CA000322010A patent/CA1148009A/en not_active Expired
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