JPS6226457B2 - - Google Patents

Description

[Detailed description of the invention]

Various diffusion transfer systems have been disclosed in the art. Generally speaking, the transferred image exposes a photosensitive element or negative component having at least one photosensitive silver halide layer;
forming a developable image; this image is then developed by application of an aqueous alkaline processing fluid, and as a result of this development function a soluble, diffusible imaging substance (which may be a dye, dye intermediate or soluble silver complex compound) is formed; ) and then transferring at least a portion of this imagewise distribution by diffusion to a laminated image-receiving element or positive member having an image-receiving layer to impart a transferred image thereto. It is obtained by The dye-imaging materials used in such methods are materials that are initially soluble or diffusible in the processing composition and then become selectively non-diffusive in an imagewise pattern as a result of development; It can be generally characterized as a material that is insoluble or non-diffusible in the processing composition and then becomes selectively diffusive in an imagewise pattern as a result of development. Many examples of both types of dye imaging materials are listed in the patent literature. A particularly useful group of such materials are the dye developers (which dyes are also silver halide developers) described in US Pat. No. 2,983,606 and several other patents. In any of these systems, at least 2
having two selectively sensitized silver halide layers;
By using photosensitive elements or negative members each containing dye imaging materials exhibiting the desired spectral absorption characteristics associated therewith,
A multicolor image can be obtained. The most commonly used element of this type is the so-called tripack structure, in which yellow,
Blue-, green- and red-sensitive silver halide layers containing a combination of magenta and cyan dye image-providing materials, respectively, are used. The negative and positive members in such systems can be separate elements that are superimposed during development and then held together or separated to produce the desired transferred image, or These two members may constitute a unitary structure, a so-called integrated negative-positive film unit, in which each member is held together prior to exposure and during subsequent imaging. In the latter system,
A reflective material such as a white pigment, eg titanium dioxide, is provided between the two parts. This may be a pre-formed layer or may be formed during development to provide the desired background that masks the negative member and makes the image formed on the positive member visible as a reflective print. provide. 1 like this
Each member in the embodied film unit can have a single dimensionally stable layer or support, or they can be disposed between integral such supports. Of course, any support combined with the positive member should be transparent so that the transferred image can be viewed. Examples of such integrated negative-positive film units that produce visible color transfer images without separation are those described in the following US patents: No. 3,415,644; No. 3,415,645. issue;
No. 3415646; No. 3473925; No. 3550515;
No. 3573042; No. 3573043; No. 3573044; No.
No. 3576625; No. 3578540; No. 3589904; No.
No. 3594164; No. 3594165; No. 3607285; No.
No. 3615421; No. 3615436; No. 3615539; No.
No. 3615540; No. 3619192; No. 3619193; No.
No. 3621768; No. 3647437; No. 3652281; No.
No. 3652282; No. 3672890; No. 3679409; No.
No. 3689262; No. 3690879; and others. Using multicolor diffusion transfer products such as those described above, which use two or more sets of silver halide emulsion layers, each layer having its own dye imaging material associated therewith, color transfer during processing is possible. Premature transfer of the donor material can result in undesirable interimage effects. In this interimage effect, the dye or other color-providing substance is placed in a ``wrong'' silver halide layer, i.e., in a layer other than the silver halide layer with which the dye or color-providing substance was originally combined in the film unit. Controlled at least in part by the silver layer. The problem is that the negative member has a red-sensitive silver halide layer having a cyan dye developer associated therewith, a green-sensitive silver halide layer having a magenta dye developer associated thereto, and a yellow dye developer associated therewith. Further explanation may be made with reference to a conventional tripack negative using a dye developer, which consists of a support carrying a blue-sensitive silver halide layer. Ideally, the soluble dye developer should diffuse into its associated silver halide layer and, when unconstrained by that layer, further diffuse into the receiving element. Diffusion through the silver halide layer is generally controlled by development of the silver halide layer. If the dye developer is transferable to another silver halide layer before developing its combined silver halide layer, the resulting transferred image may be affected by dye loss and/or incorrect dye transfer. It will have somewhat less color fidelity than is desired. To further illustrate, if the magenta dye developer can diffuse back into the red-sensitive silver halide layer before it is developed with the cyan dye developer, some of the magenta dye developer will The silver halide can be developed in the layer where it becomes bonded or non-diffusible. This development results in a loss of magenta dye in the transferred image, so-called "magenta drop off." Furthermore, development of the red-sensitive silver halide layer with a magenta dye developer causes some of the cyan dye developer to be oxidized when it should be diffused into the image-receiving layer, resulting in undesirable cyan transfer. In order to eliminate or minimize these interimage effects, layers of various materials may be inserted between the emulsions and their separate supplies of dye imaging materials so that the dye imaging materials are combined. This prevents premature diffusion in silver halide emulsions that do not contain silver halide. Such interlayers are permeable to the passage of processing compositions and thus development can occur in the emulsion on either side of the interlayer. This intermediate layer is impermeable for a short period of time to the dye-imaging materials that are dissolved by the processing composition, so that the emulsion is such that the dye materials combined in one emulsion layer pass through the intermediate layer to the dye-imaging materials that are combined in one emulsion layer. It is substantially developed before it can be transferred to the emulsion layer. Diffusion control of color-providing materials by postponing or delaying their ability to diffuse into the image-receiving layer until after the desired development has occurred is disclosed in U.S. Pat.
No. 3,345,163, the controls in that patent include, for example, slowly hydrating the outer emulsion and its associated color-providing materials as a barrier layer separating it from the inner emulsion and its associated color-providing materials. This is done by using decomposable substances. Several other forms of photosensitive element interlayer systems are disclosed in the art. For example, as shown in U.S. Pat. No. 3,615,422, two emulsion layers are made transparent to processing compositions but impermeable to color-providing substances until the polymer is hydrated. separation by an intermediate layer consisting of a metal-free polymeric material. This polymer hydration rate is such that the required hydration occurs subsequent to substantial development of the silver halide emulsion with the lowest development rate and before substantial fogging of the emulsion layer with the most rapid fogging rate. Select as follows. This intermediate layer can then retard the diffusion of color-providing substances or dyes in both the forward and backward directions. This retards the backward diffusion of the dye associated with the next outer silver halide emulsion layer and the forward diffusion of the dye associated with the next inner silver halide emulsion layer. Various polymeric materials found to be particularly useful in systems of this type are described in US Pat. No. 3,421,892, which relates to the use of a polyvinylamide interlayer. These interlayers act like molecular sieves whose spaces enlarge upon hydration of the polymer, allowing dyes or other color-providing substances to pass through. The intermediate layer material disclosed in US Pat. No. 3,384,483 consists of a film-forming, alkali-permeable, alkali-permeable water-soluble polymer with free carboxylic acid groups, and a water-insoluble polyvalent metal salt. This polymeric salt has lower permeability to dye developers in aqueous alkaline solutions than the polymeric carboxylic acid used to make it, and has a crosslinking mechanism (i.e., the polyvalent metal moieties are (by cross-linking with acid moieties to form the necessary alkaline permeable, water-insoluble salts) retards the diffusion of dye developer into emulsion layers with which it is not associated during development. When this salt is hydrated during processing,
The salt swells sufficiently to allow the unoxidized dye developer to diffuse into the receiving element through the small interstices of the salt. In addition to using intermediate layers consisting essentially of only a single phase of substance, intermediate layers consisting of mixtures of substances can also be used. Such a system is covered by U.S. Patent No.
No. 3,625,685, in which the silver halide stack is closely mixed with a latex or continuous phase (consisting of a processing composition permeable material) combined with a dye permeation-inducing component or a discontinuous phase (consisting of a processing composition permeable material). The two phases are separated by an intermediate layer containing two phases (consisting of the combined essence of an aqueous dispersion of a film-forming synthetic polymer). In this system, a dye permeation inducing material which can be permeable or impermeable to the processing composition and which is also impermeable to the dye imaging material forms a combined latex which is permeable to the processing composition. This forms a latitude structure. Upon contact with the treatment composition, the dye permeation inducing material, which is preferably a polymer, becomes permeable to the solubilized dye material;
This allows the dye to pass through the intermediate layer. In a preferred embodiment of the above system, the intermediate layer is made permeable by hydration of the discontinuous phase. This phase swells when hydrated, creating spaces in the latitude structure of the interlayer large enough for the solubilized dye to pass through. The rates of hydration and swelling are usually selected to prevent migration of the dye-image-forming material until development of all emulsion layers in the light-sensitive element is substantially complete, but layered development of emulsions and dye-image formation It can also be chosen such that diffusion of the substance is achieved. In the latter type of system, an intermediate layer between the two emulsion layers preferably inhibits dye diffusion until the outer (closer to the receiver element) emulsion layer is substantially developed. As can be seen from the foregoing description, polymers which enable the passage of solubilized dye-imaging substances by hydration can be used alone or in mixtures with other substances and can be used between two emulsions. to form a barrier intermediate layer. Such interlayer systems can act as selective barriers due to the large size of the dye (or dye precursor) molecules. Whereas many of the molecules of the processing composition, e.g., water, alkalis, etc., are small enough to escape through the spaces of this interlayer latitude, the molecules of the solubilized dye-imaging material are small enough to escape through these spaces. , is too large to pass through it for the short time intended for the treatment composition until the barrier polymer swells upon hydration. Although such polymers have proven useful in retarding the diffusion of dye imaging materials, it has been found that they sometimes allow premature diffusion. This is because hydration of the polymer and swelling of the resulting intermediate layer begins as soon as the polymer comes into contact with the treatment composition. That is, some dye diffusion may occur before substantial development of the silver halide emulsion is prevented by the interlayer.
Furthermore, these polymers tend to produce rather slow interlayer expansion. Although it is often desirable to switch quickly from a very non-permeable state to a very permeable state, permeability of the interlayer usually occurs more slowly, sometimes starting too quickly, and sometimes It's taking too long. U.S. Pat. No. 3,362,819 describes an image receiving element, particularly suitable for use in the aforementioned diffusion transfer process, which in turn comprises on one surface a polymeric acid layer, preferably an inert timing or It comprises a support layer having a spacer layer and an image-receiving layer suitable for providing a visible image by transfer of a diffusible dye imaging material to the image-receiving layer. This acid polymer layer is removed after a predetermined period of time.
Reduce the PH of the image receiving layer from about 12 to 14 PH to at least 11
is disclosed to have at least sufficient acid groups to reduce the PH to a PH of about 5 to 8, preferably about 5 to 8. Of course, the effect of this polymeric acid must be controlled so that it is not impaired by either negative development or dye image forming agent transfer. For this reason, until a positive dye image is formed,
The PH of this image layer is maintained at around PH 12 to 14 and then the PH is reduced very quickly to the desired final PH. The inert spacer layer of the patent, for example made of polyvinyl alcohol or gelatin, functions to "temporally" control the PH reduction caused by the polymeric acid layer. This timing adjustment is stated to be a function of the rate at which the alkali diffuses through the inert spacer layer. The use of diffusion control layers, such as timing layers to control the neutralization layer, in silver diffusion processes is known in the art, eg, Edwin H., November 23, 1973. U.S. Patent No. issued to Edwin H. Land
No. 3772025, which is incorporated herein by reference. It is a principal object of the present invention to provide a novel diffusion control layer for use in diffusion transfer photographic products and methods, which diffusion control layer can be added to or attached to a layer of a photosensitive element or positive member of a diffusion transfer film unit. Controls the diffusion transfer of components passing through. Another object of the present invention is to provide a photosensitive element for use in diffusion transfer color photography comprising an interlayer that substantially prevents diffusion of solubilized dye imaging material through the interlayer until after a predetermined period of time. Our goal is to provide products. Yet another object of the present invention is to provide an intermediate layer that rapidly switches from a state of being substantially impermeable to solubilized dye imaging material to a state of being substantially permeable to this material. It's about doing. Yet another object of the present invention is to provide a polymeric interlayer that is initially impermeable to solubilized dye-imaging materials, the intermediate layer being impermeable to dye-imaging materials passing through the layer. Following a predetermined short period of time after the alkaline processing composition that solubilizes and transports the material contacts this interlayer, it becomes permeable to the dye-imaging material so solubilized. It is a further object of the present invention to provide an article for use in diffusion transfer photography that includes a neutralizing system for lowering the pH of an aqueous alkaline processing fluid, the neutralizing system comprising a neutralizing layer and a neutralizing system for use in diffusion transfer photography. a timing layer, the timing layer being substantially impermeable to alkali, in which the treatment composition is first diffused through the timing layer and then deposited in contacting relationship with the neutralization layer; can quickly switch from a state of sexual activity to a state of substantially permeability thereto. Yet another object of the present invention is to provide a polymeric overcoat layer for an image receiving element that rapidly switches from being substantially impermeable to processing fluids to being substantially permeable to such materials. Our goal is to provide the following. Other objects of the invention will be apparent in part, and in part will become apparent from the description that follows. β-elimination (β-
It has been found that polymerization products of monomers that undergo elimination are useful in providing temporal diffusion control to diffusion transfer photographic film units. Diffusion control layers of these polymerization products can be adapted for use as diffusion control interlayers or overcoats of photosensitive elements and as diffusion control layers, such as timing layers, or overcoats of image-receiving elements. These polymeric materials must undergo β-elimination before substantial swelling can occur, and the β-elimination and swelling must be soluble in or solubilized by the aqueous alkaline processing composition. A prerequisite for penetration by the selected substance. The β-elimination reaction that the polymeric material of the diffusion control layer of the present invention undergoes ensures a retardation of permeability after the diffusion control layer comes into contact with the treatment composition, allowing the diffusion of alkaline or soluble or solubilized materials to ``hold'' and then ``release'' allowing this soluble or solubilized substance to pass through.
(release) or bring about an opening. The polymeric material is soluble in the alkali or treatment composition or allows diffusion of the material solubilized by the composition therethrough for a predetermined period of time, e.g.
It can be thought of as a "retention-release" polymer with a time delay of less than a second to several hundred seconds. The diffusion control layer of the present invention is sensitized to different regions of the spectrum and can be used as an interlayer between silver halide emulsion layers, each emulsion layer containing dye imaging material associated therewith. . These include, for example, the aforementioned U.S. Pat. No. 3,615,422;
and No. 3,421,892, using the retention-release polymers of the present invention in place of the interlayer polymer compositions described herein. The time required for β-elimination and subsequent hydration to occur following contact with the processing composition is such that at least substantial development of the emulsion between the interlayer and image-receiving layer occurs, and most Substantial fogging of the emulsion layer due to rapid fogging rate (before fogging occurs) for a period of time sufficient to maintain the interlayer substantially impermeable to the solubilized dye imaging material. The diffusion control layer of the present invention can be used as a timing or spacer layer between an alkaline processing composition introduced into the film unit and a neutralizing layer, such as a polymeric acid layer, to ensure that β-elimination occurs. PH by acting as a virtually impermeable barrier to alkaline processing compositions until
The onset of decline can be controlled. The diffusion control layer of the present invention can also be used as a topcoat layer, such as topcoat layer 19, as shown in FIG. The use of such an overcoat layer can be utilized to control the desired dye transfer, for example by converting a substantially dye-impermeable layer into a substantially dye-permeable layer. The introduction of a double bond into a molecule having a single bond involves the removal of a group from an atom or an adjacent atom. When the elimination reactions involve β-substituted esters, acids, ketones, aldehydes, and nitro compounds, these reactions are referred to as β-eliminations. Organic Chemistry by Hendrickson, Cram and Hammond (3rd edition, Matsuku Glow)
McGraw-Hill Book
Company), 1970], the electron-withdrawing group has a strong acid-strengthening effect on the α-protons that are removed by the base during the reaction. This 1,2-elimination under basic conditions is very common as illustrated by Figure 14-3 from Hendricks, Crum and Hammond as follows. (where L is a leaving group, B is a base,
and _-NO2 is a typical active group). Generally speaking, this can also be written as: (where Y is an active group). Substituents that activate β-elimination under basic conditions are known. The nature of this β-withdrawal activation is as follows. J. Crosby and C. J.A. M. By CJMStirling. Chemi. Soci (J.Chem.Soc.) (B)1970,
It is studied in 670 pages. This article concludes that resonance stabilization of carboanionic species is the key factor for activation. Incorporating such a β-elimination compound into a polymer,
After β-elimination breaks the bonds, it liberates the water-absorbing groups, swells, and renders the polymer soluble in or solubilized by an alkali or alkaline processing composition. a polymer that is substantially impermeable to these soluble or solubilized substances, and that such a polymer can be used as a diffusion control layer; It has been discovered that the resulting predetermined time delay can prevent premature diffusion of alkali or soluble or solubilized substances. By adjusting the molar ratio or proportion of β-elimination moieties in the polymer, as well as the thickness of the polymer layer, one can provide the predetermined permeability time desired for a particular diffusion transfer system. Referring to the general formula for β-elimination above, the leaving group L is a polymeric structure from which the β-substituted substance is removed, or alternatively such a polymer is described by Bedell, Sullivan. ) and JP 55-41490 co-filed in the name of Taylor and further contain grafted moieties as claimed. That is, β-departure can be written as either of the following equations: (In the formula, L is

[Formula], R' is hydrogen or methyl, and Y is -SO ₂ W,

【formula】

[Formula] and −CN, W is −C ₆ H ₅ CH ₃ , −
_CH3 , _-OC2H5 , _{-C6H5 , -NR2} or _-N
( _{CH2C6H5 ) 2} ; T is _{-OC2H5 , -CH3 ,} -
H, _-NH2 or _-NR2 ; G is phenyl,
methyl or ethyl and R is alkyl, such as methyl or ethyl); or (In the formula, L is

[Formula] and R' and Y are as defined above.) More generally, this reaction is (wherein R'' is an addition polymerized unit of ethylenically unsaturated alkyl groups having 2 or 3 carbon atoms, including grafts such as ethylenically unsaturated alkyl groups on the organic backbone of the polymeric system; A, E and D are selected from the group consisting of hydrogen, methyl and phenyl, with the proviso that not more than one of A, E or D can be methyl or phenyl, and Y is an active group as defined above. Typical monomers that impart β-leaving activating groups to the polymerization product include 2-cyanoethyl acrylate, 2
-cyanoethyl methacrylate and 2-carboethoxyethyl methacrylate.
Other monomers that should impart the same functionality to the polymerization product include, for example, 2-p-toluenesulfonylethyl acrylate and 2-methanesulfonylethyl acrylate. The reaction using the polymerization product of ethyl 2-cyano-acrylate can therefore be expressed as: The diffusion control layer of the present invention may be comprised of a homopolymer or copolymer including the graft copolymer described above. Mixtures of polymers can also be used. Copolymers suitable for use as diffusion control layers contain, in addition to the beta-leaving component, units from comonomeric materials that impart the polymer with certain desirable properties. Such substances can, for example, modulate cohesion or viscosity;
Film integrity and costability can be improved, or even greater fluid permeability and ion permeability can be imparted. For example, butyl acrylate is useful in providing hydrophobic balance and dye permeation rate control. non-hydrolyzable,
Alternatively, cross-linking comonomers can also be used. Acrylic acid, methacrylic acid, 2-sulfoethyl methacrylate, and 2-acrylamido-2-methylpropane sulfonic acid all allow the diffusion control layer to pass through the treatment composition at substantially the same time and rate, thereby increasing the permeability. It has been found to be a useful comonomer because of its claim to promote uniform β-elimination and hydration of the inducing component. Cross-linking materials, such as ethylene glycol dimethacrylate, are useful in diffusion control layers used as interlayers because they moderate the rate of dye transfer after initial retention. As shown in FIG. 1, the diffusion control layer of the present invention comprises a photosensitive element 26 and an image receiving element 2.
7 can be used for photographic film units. Intermediate layers 13 and 16 are the red and green layers of this photosensitive element.
and between the blue- and green-sensitized silver halide emulsions, respectively. These interlayers and the associated dye image-forming material, e.g. an emulsion with a dye developer, are preferably arranged on a support 10 from this support in the following order: cyan dye developer layer 11 , a red-sensitive silver halide emulsion layer 12, an intermediate layer 13, a magenta dye developer layer 14, a green-sensitive silver halide emulsion layer 15, an intermediate layer 16, a yellow dye developer layer 17, and a blue-sensitive silver halide emulsion layer 18. An overcoat layer 19 may be coated on top of this blue-sensitive silver halide emulsion layer. The image receiving element 27 illustrated in FIG. 1 includes, in order, an image receiving layer 21, a spacer or timing layer 22,
It consists of a neutralizing layer 23 and a support layer 24. The image-receiving layer is placed adjacent to the photosensitive element during processing. After exposing the photosensitive element, an aqueous alkaline processing composition 20 is introduced between the photosensitive element and the image receiving element. The processing composition passes through the emulsion layer to initiate development of the latent image carried in the emulsion layer and provides a medium for dye diffusion transfer to the image receiving element. The dye-imaging material associated with the unexposed areas of the emulsion layer diffuses into the image-receiving element in a known manner. US Patent No.
As described in US Pat. No. 3,362,819, a polymeric acid-containing neutralizing layer located below the image-receiving layer neutralizes the alkali of the processing composition after a predetermined period of time. A timing or spacer layer comprised of a polymeric material and located between the image receiving layer and the neutralizing layer is used to control PH reduction. Diffusion control layers of β-leaving polymeric materials according to the invention constitute intermediate layers 13 and/or 16 in one preferred embodiment. Alternatively, the overcoat layer can also constitute a diffusion control layer of the beta-leaving polymeric material. In another preferred embodiment, spacer layer 22 constitutes the diffusion control layer of the present invention. The image receiving element 27 illustrated in FIG.
Support layer 28, neutralization layer 29, spacer or timing layer 30, image receiving layer 31 and topcoat layer 32
It becomes more. During processing, an image receiving element overcoat layer is placed adjacent the photosensitive element. In one embodiment of the invention, a diffusion control layer comprising a β-leaving polymeric material according to the invention constitutes overcoat layer 32. Measuring the PH reduction time is the "clearing time".
It can be measured using the following system. A receiving element having, in order, a polymeric acid layer, a test timing layer, and a mordant layer on a support is coated with a highly pigmented image receiving element containing an indicator dye that is highly colored at a pH of about 12 to 14 and colorless at a pH of about 10 or less. Spread the PH alkaline treatment composition. A transparent cover sheet is overlaid on top of this treated material. Looking through this cover sheet towards the receiver element, it is dark colored until the alkali penetrates the polymeric acid layer and its PH decreases due to alkali consumption and the indicator dye becomes colorless; become a state. Those skilled in the art will be able to determine when this nip-off begins and when the nip-off completes. The "leaky" timing layer allows the alkali to drip through from the moment of initial contact and exhibits no undesirable changes at the beginning or end of the shedding. The timing layer of the polymer of the present invention inhibits the alkali for a limited period of time and then allows the alkali to pass through for a very short period of time until the PH is below the range of change of the indicator dye. descend. Blank time can be measured on a structure consisting of a complete receiver element, or on a simplified model structure that includes only a timing layer coated entirely over a polymeric acid layer on a support layer. The removal time of the first structure is "removal through mordant"
(clearing through the mordant), while the omission of the second model structure is called "clearing through the timing layer" (clearing through the timing layer).
layer). The diffusion control layer of the present invention, used as a top coating for the receiver element, is located on top of the stack of layers that make up the receiver element. For example, in order the support,
In an image-receiving element comprising a polymeric acid layer, a spacer layer and an alkali-permeable dyeable polymer layer,
A diffusion control layer is located furthest from the support and immediately adjacent to the alkali-permeable dyeable polymer layer and serves to retard the transmission of the processing composition and thereby solubilized materials to the image receiving element. The ability of the polymeric diffusion control layer of the present invention to retard the passage of imaging dyes therethrough until it is converted into a relatively dye-permeable polymer by a β-elimination reaction is demonstrated in the tests shown in FIG. It can be evaluated by using a structure for According to such a structure, dye transfer through a polymeric test material, such as an interlayer test material, is tracked over time. The "retention-release" properties of a polymeric test material can be evaluated, for example, by mimicking the behavior of the material as an interlayer in a photosensitive element. Such test structures and suitable evaluation methods are described in detail in Examples 1 to 15 below. The following examples are presented for the purpose of illustrating the invention only and are not intended to limit it in any way. Measurements were performed at ambient room temperature, approximately 25°C, unless otherwise noted. Examples 1-10 Transparent support, 33 in Figure 3, cyan dye developer on top: 20mg/ft ² (215.3mg/m ² ), gelatin 40mg/ft ²
(430.6 mg/m ² ) and succinic aldehyde 1.5
A layer 34 of 16.1 mg/ft ² (16.1 mg/m ² ) is coated using a conventional loop coater. 200mg/ft ² of polymeric material to be tested on top of this layer
(2153 mg/m ² ) is applied. A transparent element 38 consisting of a polyester clear film base is overlaid with the test element to form a sandwich, with a gap of 0.0028 inches between the polymeric test material layer and the transparent element 38 consisting of the following components: Introduce the opaque alkaline treatment composition: 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 Ethylenediaminetetraacetic acid 2.27g Bis-(2-aminoethyl)sulfide 0.06g Carbowax (molecular weight 6000)
1.5g Colloidal silica 5.05g 6-benzylaminopurine 1.09g Titanium dioxide 115.23g N-phenethyl-α-picolinium bromide (50
% aqueous solution) 3.91g N-benzyl-α-picolinium bromide (50%
Aqueous solution) 5.09g Linatium nitrate 0.27g Carboxymethylhydroxyethyl cellulose
4.82 g water 100 g The optical reflectance density of the treated sample for red light as viewed through support 33 in FIG.
Packard) 17505A Strip-Chart
Macbeth Quanta-Log densitometer (Macbeth Quanta-Log)
densititometer).
This concentration is made up of the remaining dye imaging material in the dye layer and that provided by the dye imaging material in the polymeric test layer. The titanium dioxide in the processing composition masks the dye imaging material in the processing composition.
A typical graph of concentration as a function of time is shown in Figure 4; in this figure t ₁ is the time required for the dye imaging material to solubilize and t ₂ is the time required for the dye imaging material to be absorbed by the polymeric intermediate layer. is the total time inhibited, and D
_p is the concentration of the dye imaging substance after initial dissolution;
D _f is the density after the dye has been transferred through the interlayer, and the line segment between A and B is
The slope of segment) is calculated as the speed of concentration change. The values for t ₁ , t ₂ and slope are given below for the following retention-release polymer systems according to the invention: 1 100 parts by weight of 2-cyanoethyl acrylate are mixed with diacetone acrylamide and acrylic acid.
Mix with 100 parts by weight of 95.5/4.5 copolymer and polymerize. 2 35 parts by weight of 2-cyanoethyl acrylate was mixed with diacetone acrylamide and acrylic acid.
Mix with 65 parts by weight of 95.5/4.5 copolymer and polymerize. 3 Diacetone acrylamide, 2-cyanoethyl acrylate and acrylic acid 47.5/50/
2.5 copolymer. 4 63/35/2 of diacetone acrylamide, 2-cyanoethyl acrylate and acrylic acid
Copolymer. 5 Butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid 85/
10/2/3 copolymer. 6 85/10/2/3 copolymer of butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-sulfoethyl methacrylate. 7 2-35 parts by weight of 2-cyanoethyl acrylate
- Mix with 100 parts by weight of a 99.25/0.75 copolymer of cyanoethyl acrylamide and acrylic acid and polymerize. 8 63/35/2 copolymer of diacetone acrylamide, 2-carboethoxyethyl methacrylate and acrylic acid. 9 Diacetone acrylamide, 2-cyanoethyl methacrylate and acrylic acid 63/
35/2 copolymer. 10 Diacetone acrylamide and acrylic acid
100 parts by weight of the 94/6 copolymer are mixed with 100 parts by weight of the 63/35/2 copolymer of diacetone acrylamide, 2-cyanoethyl methacrylate and acrylic acid. All copolymer proportions are based on weight.

【table】

TABLE It is clear from the above table that the present invention provides significant retention time before the solubilized dye imaging material is released and achieves dye release in a relatively short length of time. be. Holding time is 45〓 (approximately 7℃) parallel to development time.
longer at 95〓 (approximately 35°C) and shorter at 95〓 (approx. 35°C). For example, sample 2 above has t ₂ of 215 seconds at 45〓 and 87
and has a slope of 11 seconds at 95〓 t ₂ and
It has 654 slopes. Example 11-15 Create test elements in the same way as Examples 1-10. The second layer is made of polyester Seimei film base.
of the transparent element is superimposed on the test element to form a sanderch and the gap between the polymeric material and the top transparent element is
Introduce an opaque alkaline treatment composition into the 0.0028 inch gap consisting of the following ingredients: Potassium hydroxide (45% aqueous solution) 13.63 g Cesium hydroxide (50% aqueous solution) 10.65 g Benzotriazole 1.18 g 5 -Hydroxyazabenzimidazole 0.118g 6-Bromo-5-methyl-4-azabenzimidazole 0.059g 2-methylimidazole 0.42g Sodium carboxymethylcellulose 4.43g Titanium dioxide 59.27g N-phenethyl-α-picolinium bromide (50
% aqueous solution) 4.2 g water 100 g The time T required for the dye material to pass through the polymeric material was determined by tracing the optical density of the dye through the top transparent element using the densitometer specified in Examples 1-10. T values in seconds are shown below for the following retention-release polymer systems of the invention: 11 Butyl acrylate, 2-cyanoethyl acrylate, 2-sulfoethyl methacrylate.
2 parts by weight of 85/10/3/2 copolymer and 1 part by weight of 94/6 copolymer of acrylic acid. 12 Butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid 85/
10/2/3 copolymer. 13 89/6/2/3 copolymer of butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-sulfoethyl methacrylate. 14 Butyl acrylate, 2-cyanoethyl acrylate, 2-sulfoethyl methacrylate and ethylene glycol dimethacrylate
85 parts of 68/10/2/5 copolymer are polymerized around a core of 15 parts by weight of butyl acrylate. 15 85/10/2/3 copolymer of butyl acrylate, 2-cyanoethyl acrylate, methacrylic acid and 2-sulfoethyl methacrylate. Sample T 11 70 12 30 13 12 14 10 15 120 Measures the time before the solubilized dye-imaging material becomes available to the image-receiving layer; It includes the time required for the treatment composition to diffuse through and includes factors related to the thickness of this alkaline treatment composition layer. The relative proportions of the components in the treatment composition can be varied reasonably if desired. For example, it is contemplated to include various preservatives, alkalis, silver halide solvents, and other conversion and inhibitors and accelerators. The concentrations of the various components can also be varied over a wide range. Example 16-19 A transparent 4 mil (0.1 mm) thick polyethylene terephthalate film base is coated with the following layers:
The image-receiving element of the present invention was made by forming the image-receiving element: 1. As the polymeric acid layer, polyvinyl butyral
Polyethylene partial butyl ester/maleic anhydride copolymer mixed with 10% by weight:
coated at a coverage of 2500 mg/ft ² (26910 mg/m ² ); 2 a timing layer containing a polymeric material as detailed in the example below; and 3 a polymeric receiving layer containing 6 parts by weight of polyvinyl alcohol, -3 parts by weight of 4-vinylpyridine and 4 on hydroxy-ethylcellulose
-Vinylpyridine-vinylbenzyltri-methylammonium chloride graft polymer 1
Parts by weight of mixture; 300 mg/ft ² (3229 mg/m ² ) coverage. Label the above elements with (a). For comparison, test elements were made without a polymeric receiver layer on top of the timing layer. Label these elements with (b).

[Table] Here, 60% of butyl acrylate, diacetone acrylamide, styrene and methacrylic acid blended with 9% by weight of polyvinyl alcohol.
is a 30/4/6 copolymer; is a 2-
It is obtained by polymerizing 49 parts of cyanoethyl acrylate; and diacetone acrylamide,
It is a 63/35/2 copolymer of 2-cyanoethyl acrylate and acrylic acid. A treatment composition consisting of the following ingredients is applied between the polymeric test material layer and the transparent element:
mm) was introduced into the gap. 100 g Water 4.02 g Hydroxyethylcarboxymethyl cellulose 4.15 g 50% potassium hydroxide solution 1.12 g Benzotriazole 0.50 g Thymolphthalein The color change from blue to colorless for this sandwich structure was expressed in transmission time and was measured in seconds. Time is a measure of the time required for the treatment composition to penetrate the timing layer and react with the polymeric acid layer to lower its PH. The time is recorded as the start time when the Sandermanch structure first begins to vacate, and as the end time when the Sandermanchi structure substantially completes vacating. Example 20-27 Approximately 2500 mg
It was coated with a partial butyl ester of polyethylene/maleic anhydride copolymer mixed with about 10% by weight polyvinyl butyral at a coverage of ft ² (26910 mg/m ² ). The timing layer and image receiving layer described below were coated over this layer at the indicated coverages. Permeation times were measured as detailed above.

[Table] Here, A is 56.7% of butyl acrylate, 2-cyanoethyl acrylate, ethylene glycol dimethacrylate, acrylic acid and styrene.
A 10/3 mixture of diacetone acrylamide and acrylic acid is polymerized around the core of a 25/5/1/2 copolymer. The pH of A is 2.6. B
consists of material A plus enough potassium hydroxide to bring its pH to 8.0. C is a 59/40/1 copolymer of diacetone acrylamide, 2-cyanoethyl acrylate and acrylic acid;
D is a copolymer in which 4-vinylpyridine and vinylbenzyltrimethylammonium chloride are grafted onto polyvinyl alcohol. Cyano-substituted acrylates are described in US Patent Application No. 806,150 as silver halide grain-growth inhibiting colloids, but this patent application does not disclose or suggest anything about diffusion control effects.

[Brief explanation of the drawing]

FIG. 1 shows a cross-section of a photographic film unit including a diffusion control layer of the invention; FIG. 2 shows a cross-section of a receiver element including a diffusion control timing layer of the invention; FIG. 4 shows a model arrangement for measuring the "retention-time" of a layer; and FIG. 4 graphs dye concentration as a function of time in a system containing an interlayer of the present invention.

Claims (1)

Claims: 1. (a) at least one light-sensitive silver halide emulsion layer having in combination an imaging substance that is soluble and diffusible in a processing composition; (b) an image-receiving layer permeable to an alkaline processing composition. (c) a means for delivering an alkaline processing composition into the film unit; (d) at least one diffusion control layer for providing temporal diffusion control within the diffusion transfer photographic film unit; The diffusion control layer of the lever is comprised of a polymerization product of a monomer capable of undergoing β-elimination in an alkaline environment, and this polymerization product has the formula (wherein R″ is an addition polymerization product of an ethylenically unsaturated alkyl group having 2 or 3 carbon atoms;
A, D and E are selected from the group consisting of hydrogen, methyl and phenyl, with the proviso that not more than one of A, E or D may be methyl or phenyl; and Y is an active group). A diffusion transfer photographic film unit having the following properties. 2 an intermediate layer having at least two silver halide emulsion layers, each having in combination an imaging substance that is soluble and diffusible in the processing composition, and a diffusion control layer located between these silver halide emulsion layers; A diffusion transfer photographic film unit according to claim 1, which constitutes a layer. 3. The diffusion transfer photographic film unit of claim 1, wherein the diffusion control layer constitutes a negative element overcoat layer. 4. The diffusion transfer photographic film unit of claim 1, wherein the diffusion control layer is an alkali neutralization timing layer. 5. The diffusion transfer photographic film unit of claim 1, wherein the diffusion control layer constitutes a positive element overcoat layer. 6. The film unit of claim 1, wherein the imaging substance is a dye developer. 7 The active group is -SO ₂ W, [Formula] [Formula] -CN and -NO ₂ (where W is -C ₆ H ₅ CH ₃ , -
_CH3 , _-OC2H5 , _{-C6H5 , -NR2} or _-N
( _{CH2C6H5 ) 2} ; T is _-OC2H5 , _{-CH3 , -}
H, _-NH2 or _-NR2 ; G is phenyl,
methyl or ethyl, and R is methyl or ethyl. 8. The film unit according to claim 1, wherein the polymerization product is poly(2-cyanoethyl acrylate). 9. The film unit according to claim 1, wherein the polymerization product is poly(2-cyanoethyl methacrylate). 10. The film unit according to claim 1, wherein the polymerization product is poly(2-carboethoxyethyl methacrylate). 11. The film unit of claim 1, wherein the polymerization product further contains a non-hydrolyzable comonomer. 12. The film unit of claim 1, wherein the polymerization product further contains a unit of a cross-linking comonomer.