JPH0379702B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION This invention relates to products suitable for use in photography, particularly in the formation of photographic diffusion transfer images. More particularly, this invention relates to diffusion transfer photographic film units that include a diffusion control layer containing certain polymers that are hydrolyzable in the presence of alkali. SUMMARY OF THE INVENTION According to the present invention, certain polymers containing repeating units that can undergo hydrolysis in an alkaline environment have been discovered. A layer containing one or more of these polymers undergoes hydrolysis in an alkaline environment and becomes soluble in the alkaline or aqueous alkaline treatment composition, or is insoluble to the substances solubilized by the composition. It is possible to change from a state of permeability to a state of being substantially permeable to these. Layers containing these hydrolyzable polymers can be used as diffusion control interlayers or overcoats of diffusion transfer film units, or as timing layers to control the default diffusion transfer of such film units. According to the present invention, the layer comprises at least one diffusion control layer comprising a hydrolyzable polymer, which layer is soluble in, or is made soluble in, an alkali or aqueous alkaline treatment composition. from a state of impermeability to a state of permeability to them by subjecting the polymer to a predetermined hydrolysis by contact with an alkali, and this hydrolyzable polymer Formula (1) [wherein R is hydrogen, halogen (e.g. chloro) or lower alkyl (e.g. methyl);
and D are hydrogen, alkyl (e.g. methyl, ethyl), alkoxy (e.g. methoxy), aryl (e.g. phenyl), alkaryl (e.g. tolyl), aralkyl (e.g. benzyl); and Z is It then either represents an electron-withdrawing group that activates the hydrolytic decomposition of the polymer with concomitant formation of an acrylate anion, or when the polymer comes into contact with an alkali it degrades itself with concomitant formation of a residual carboxylate anion. represents a hydrolyzable electron-withdrawing group],
A diffusion transfer photographic film unit is provided. The diffusion control layer of the photographic film unit of the present invention is either soluble in an alkaline or aqueous alkaline processing composition, or the material solubilized by the composition is present over a predetermined length during processing of the film unit. time, forming an impermeable "barrier" layer that prevents it from passing or diffusing through this layer,
The polymer then undergoes a defined hydrolysis which serves to render it substantially permeable to these substances in a relatively short period of time. This diffusion control layer therefore allows the substance whose diffusion is to be controlled to be "held" in place for a predetermined period of time and then "released" substantially quantitatively over a relatively short period of time. It is a "retention-release" layer that allows for rapid diffusion through the layer. The present invention will be more easily understood from the following detailed description and in consideration of the accompanying drawings. FIG. 1 is a cross-sectional view of a photographic film unit containing a diffusion control layer of the present invention. FIG. 2 is a cross-sectional view of a receiving element including a diffusion control timing layer of the present invention. FIG. 3 shows an exemplary arrangement for measuring the "retention time" of the interlayer of the present invention. FIG. 4 graphically depicts dye concentration as a function of time in a system containing an interlayer of the present invention. DETAILED DESCRIPTION As noted above, the hydrolyzable polymers of the present invention are soluble to alkali or in an aqueous alkaline processing composition, or impermeable to substances solubilized by this composition. The polymer contains one or more polymers that can be changed from a state to a state substantially permeable to them by undergoing a hydrolysis reaction in an alkaline environment. Therefore, this polymer can be used in various ways as a diffusion control layer in diffusion transfer photographic film units. For example, the diffusion control layer of the present invention can be an overcoat layer or an interlayer of a photosensitive element or negative part of a diffusion transfer film unit;
Alternatively, it can be a timing layer or overcoat layer of a receiver element or positive part of a diffusion transfer film unit. The desired "retention-release" behavior of the diffusion control layer of the present invention is not amenable to the expected changes in permeability, but rather is initially permeable to some degree and free of substances from the beginning of the process. This can be contrasted with the diffusion control features of a diffusion control layer that undergoes significant leakage and becomes progressively more permeable during the processing period. The polymer of the diffusion control layer of the present invention contains basic repeating units capable of undergoing hydrolytic decomposition in the presence of an alkali, and has the formula () [In the formula, R is hydrogen, halogen (e.g. chloro),
or lower alkyl (e.g. methyl);
A and D are hydrogen, alkyl (e.g. methylethyl), alkoxy (e.g. methoxy), aryl (e.g. phenyl), alkaryl (e.g. tolyl), aralkyl (e.g. benzyl); and Z is then either represents an electron-withdrawing group that activates the hydrolytic decomposition of the polymer, with concomitant formation of an acrylate anion, or, when the polymer is contacted with an alkali, with concomitant formation of a residual carboxylate anion. represents an electron-withdrawing group which itself hydrolyzes]. Considering the repeating unit of formula (), it is clear that the polymer of the present invention has an ester side chain.

It can be seen that it is derived from a monomer-based compound containing the radical character [formula] and that this ester contains the substituent Z. For convenience, the repeating unit of formula () will hereinafter be simply referred to as "hydrolyzable unit". The nature of the Z group of the hydrolyzable unit predetermines the desired diffusion control properties for the layer containing this polymer;
It may vary depending on the nature of any comonomer units that may be present in the polymer or other polymeric materials that may be present in the diffusion control layer in admixture with the polymer. Generally, the Z group activates or facilitates the degradation of the polymer by alkaline hydrolysis of the side chain ester groups, or is itself degraded with concomitant formation of residual carboxylate anions, as explained below. It is a group that undergoes hydrolysis. Examples of suitable electron-withdrawing groups Z include the formula

The group [formula] [wherein Y represents -R ² or -OR ² , where R ² is alkyl (e.g. methyl,
ethyl), aryl (e.g. phenyl), alkaryl (e.g. tolyl) or aralkyl (e.g. benzyl);

[Formula], where R ³ and R ⁴ each represent hydrogen, alkyl, aryl, alkaryl or aralkyl, or R ³ or R ⁴ together with the nitrogen atom to which they are attached represent a nitrogen-containing heterocyclic ring. represents the atoms required to complete the process, or Y is a group

represents the formula where R ⁵ , R ⁶ and R ⁷ are each methyl or phenyl, provided that more than one of R ⁵ , R ⁶ and R ⁷ is not methyl or phenyl, and W
represents an electron-withdrawing group (eg, methylsulfonyl) capable of activating β-elimination. Other suitable electron-withdrawing Z groups include cyano, pyridinium and _-SO2 - ^R8 , where ^R8 is alkyl, aryl, alkaryl or aralkyl. Cyano groups are not preferred Z groups due to the possible by-product of hydrogen cyanide. Preferred Z groups in the present invention have the formula

An electron-withdrawing group having the formula: ##STR1## where Y is alkyl (eg, methyl) or alkoxy (eg, methoxy or ethoxy). Accordingly, polymers suitable in the present invention are those containing repeating units of the following formula () or (): or (In each formula R is hydrogen or lower alkyl and R ² is alkyl). A and D are each preferably hydrogen, but in the case of a repeating unit of the type represented by formula (),
Preferably A and D are each methyl. The mechanism of alkali-activated ester hydrolysis, although the manner in which polymers containing repeating units according to formula (), (), or () serve to perform the retention-release function is not completely understood. is considered to be included. Depending on the particular nature of the Z electron-withdrawing group, one or more mechanisms may be involved. In some cases, the Z group activates the hydrolysis of side chain ester groups, as shown by the reaction scheme below which illustrates the alkali-initiated hydrolytic decomposition of a polymer with repeating units from acetonyl acrylate. do: The Z group in the acetonyl acrylate polymer exemplified above (i.e.

[Formula] group) is accompanied by decomposition and formation of anionic acrylate,
It is thought that it activates the hydrolysis of the side chain ester group. Hydrolytic degradation occurs after a predetermined "hold" time so that an increase in permeability of the polymer-containing layer is obtained. In some cases, hydrolytic decomposition can also occur with concomitant formation of a carboxylic acid anion group as a result of hydrolysis of the Z group itself. It is understood that this carboxylic acid anion group can activate or facilitate subsequent hydrolysis to form the acrylate anion. This can be shown by the following reaction equation: While there is no desire to associate the explanation of the hydrolytic action of alkali on substituted esters of polymers with any particular theory or mechanism, it is possible that one or both of the aforementioned mechanisms are involved in the decomposition of ester-substituted esters. This can be clearly seen from the following reaction equation: Examples of polymers useful in the present invention include polymers containing hydrolyzable repeat units of the formula:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] The polymers of the present invention may be copolymers containing substituted-ester hydrolyzable units and various comonomer units incorporated therein to impart predetermined properties to the polymer. can. For example, the "retention time," or the period of time during which a diffusion control layer remains impermeable during processing, is the time period during which a specified comonomer or mixture of comonomers is formulated into a hydrolyzable polymer. , can be varied by making the layer relatively hydrophilic. Generally, the more hydrophobic the polymer, the slower the rate of permeation of the alkali into the diffusion control layer to initiate the hydrolysis reaction, ie, the longer the retention time. Adjustment of the hydrophobic/hydrophilic balance of the polymer by including different appropriate comonomer units can be used to selectively apply the diffusion control layer to its assigned role within the film unit. It is also possible to add transparency properties. For example, as explained in more detail below, the diffusion control interlayer within the film unit is initially substantially permeable to alkali, water, and various other components in the processing composition; It is highly desirable that the film unit be substantially impermeable to the image-providing material up to a predetermined point in processing. This selective permeability is
generally by incorporating appropriate comonomer units of relatively hydrophilic nature into the hydrolyzable polymer, or more particularly by balancing hydrophobic and hydrophilic groups to obtain the desired permeability. By this,
This can be achieved according to the present invention. Examples of comonomers suitable for use in the present invention include acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-
Methylacrylamide, methacrylamide, ethyl acrylate, butyl acrylate, methyl methacrylate, N-methylmethacrylamide, N
-ethylacrylamide, N-methylolacrylamide, N,N-dimethylacrylamide,
N,N-dimethylmethacrylamide, N-(n
-propyl)acrylamide, N-isopropylacrylamide, N-(β-hydroxyethyl)
Acrylamide, N-(β-dimethylaminoethyl)acrylamide, N-(t-butyl)acrylamide, N-[β-(dimethylamino)ethyl]
Methacrylamide, 2-[2'-(acrylamido)ethoxy]ethanol, N-(3'-methoxypropyl)acrylamide, 2-acrylamido-3-methylbutyramide, acrylamide acetamide, methacrylamide acetamide, 2
-[2'-methacrylamide-3'-methylbutyramide]acetamide, and diacetone acrylamide. Examples of suitable copolymers useful in this invention as retention/release polymers in photographic products include the following copolymers: 1 diacetone acrylamide/butyl acrylate/acrylic acid/ethyl acrylate/ Carbomethoxymethyl acrylate (18.6/37.5/1.4/
21.0/20.0 parts by weight) copolymer; and 2 diacetone acrylamide/butyl acrylate/acrylic acid/ethyl acrylate/carbomethoxymethyl acrylate (39.25/30.00/
0.25/15.25/15.25 parts by weight) copolymer. The hydrolytic degradation experienced by the hydrolyzable polymer of the diffusion control layer of the present invention is such that the substance whose diffusion is to be controlled is "held" in place by the diffusion control layer for a predetermined period of time, and then for a relatively short period of time. Ensure that it is released in time. A relatively rapid increase in hydrophilicity and water swellability occurs in this polymer layer as a result of the hydrolysis reaction. The predetermined retention time adjusts the molar ratio or proportion of hydrolyzable units in the polymer; the appropriate comonomer units are incorporated into the polymer to give it the desired hydrophobic/hydrophilic balance or degree of aggregation. do;
Use of different electron-withdrawing groups Z to influence the rate of hydrolysis; or use of other materials in the diffusion control layer, especially polymeric materials, to influence the permeability of the alkaline or aqueous-alkaline treatment composition therethrough. can be adjusted to suit a given photographic method by such means as by varying the time required for substantial hydrolysis to occur. An example of means for adjusting the retention time of this last-mentioned layer is a matrix weight having a predetermined permeability to the alkali or aqueous alkaline treatment composition, for example as measured by its hydrophobic/hydrophilic balance or degree of aggregation. This may include the use of coalescent materials. Generally, increased permeability to alkaline or aqueous alkaline treatment compositions, ie, shorter retention times, can be obtained by increasing the hydrophilicity or decreasing the degree of aggregation of the matrix polymer. In addition to influencing the retention time of the diffusion control layer of the present invention, the matrix polymer may also affect the retention time of the layer for substances that are soluble in or are solubilized by alkaline or aqueous alkaline processing compositions. It can also be used to adjust the permeability and influence the functionality of the layers within the film unit. For example, a matrix polymer having a relatively high degree of cohesion or a relatively hydrophobic matrix polymer may render this diffusion control layer substantially impermeable until hydrolysis occurs, and such a layer may be coated with a diffusion transfer film. It can help serve as an alkali-neutralizing timing layer or overcoat layer in the receiver element or other element of the unit. Alternatively, a relatively hydrophilic matrix polymer or a matrix polymer having a relatively low degree of aggregation may make the diffusion control layer soluble in the aqueous alkaline treatment composition or the composition. initially permeable to alkalis, while remaining impermeable to substances that are solubilized by the dye, such as image dye-providing substances, thus imparting to such a layer the light-sensitivity of the diffusion transfer film unit. It can also help serve as an intermediate layer or overcoat layer in elements, negative parts, or other elements. Therefore, the use of matrix polymers is an alternative to the use of suitable comonomers in the hydrolyzable copolymers described above as a way to adjust the retention time or function of the diffusion control layer of the present invention. Or you can provide assistance. However, it should be understood that hydrolysis of the hydrolyzable units is essential to achieving a relatively rapid change in layer permeability. Matrix/hydrolyzable unit polymer systems suitable for use in diffusion control layers can be prepared by physically mixing the individual polymers and by preparing the matrix polymer in the presence of a hydrolyzable polymer. . For example, a polymer containing hydrolyzable units can be produced in the presence of a preformed matrix polymer. Polymers that can be used as matrix polymers generally include acrylic acid, methacrylic acid, methyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, acrylamide, methacrylamide, N,N-dimethylacrylamide, ethyl acrylate, It is a copolymer containing comonomer units such as butyl acrylate, diacetone acrylamide, acrylamide acetamide, and methacrylamide acetamide. The comonomer units and their proportions should be selected based on the physical properties desired for the matrix polymer and the diffusion control layer in which it is intended to be used.
For example, by increasing the relative proportion of hydrophilic comonomers such as acrylic acid or methacrylic acid within the matrix polymer, more hydrophilic
Thus, generally more permeable matrix materials can be produced. A particularly preferred matrix/hydrolyzable unit polymer system is a 50.5/44/5/0.5 parts by weight matrix copolymer of diacetone acrylate/butyl acrylate/acrylic acid/2-acrylamido-2-methylpropanesulfonic acid, from about 80 to 50 parts by weight. 90 parts by weight and the remaining amount up to 100 parts of 75/25 parts by weight of carbomethoxymethyl acrylate/diacetone acrylamide,
That is, it is a matrix system containing 10 to 20 parts. The hydrolyzable polymers of this invention can be used in many diffusion transfer products and processes based on the imagewise transfer of diffusible image-providing materials, such as diffusible dyes, dye intermediates, or soluble silver complexes. Diffusion transfer film units of the present invention have as basic layers a support layer; at least one light-sensitive silver halide emulsion layer having in combination therein a diffusion transfer image-providing material; an alkaline processing composition permeable image-receiving layer; and Includes at least one diffusion control layer comprising a hydrolyzable polymer. After exposure, the silver halide emulsion is developed with an aqueous alkaline processing composition, resulting in the formation of an imagewise distribution of diffusive image-providing material, which is applied at least partially to the stacked image-receiving layer. Transcribe. Such film-based diffusion control layers can be used as described herein to control the diffusion of alkali or image-providing materials. Film units within the scope of this invention also include those in which the silver halide emulsion layer and the image-receiving layer are initially contained in separate elements. Such films include (a) a light-sensitive element comprising a negative part comprising a support layer, which is preferably opaque, and at least one light-sensitive silver halide emulsion layer having in combination therein a diffusion transfer image-providing material; (b) an image receiving element comprising a positive part comprising a support layer and an image receiving layer which may be opaque or transparent as appropriate for a given method; and (c) present in at least one of said photosensitive element or image receiving element. A diffusion control layer containing the polymer of the present invention may be included. Each element can be stacked after or before exposure. After exposure, an aqueous alkaline processing composition is distributed between the stacked elements to initiate development. If the receiving element provides an opaque reflective background, the image produced can be viewed as a reflective print due to separation of the elements. By using transparent receiver elements, the resulting image can be viewed as a transparency due to the separation of the elements. Alternatively, if the photosensitive element and/or processing composition contains a light-reflecting layer, e.g. a white pigment such as titanium dioxide, the image is imparted by the light-reflecting layer without separating the elements. It can be seen as a reflective print against the background. The photosensitive element can also have a neutralizing layer, such as an acid polymer layer and a timing layer, disposed between the support layer and the negative part, with the neutralizing layer adjacent the support. By causing a neutralization reaction between the acid-reactive sites of the neutralization layer and the alkali provided by the processing composition, the environmental PH of the film unit can be lowered. The timing layer is caused by premature pH due to slow diffusion of alkali toward the neutralization layer.
Works to prevent decline. Diffusion control layers of the present invention also include diffusion transfer film units in which the photosensitive layer and the image-receiving layer are in a single element, i.e., a negative part and a positive part are included within the photosensitive laminate, at least before exposure; Alternatively, it may be used in integrated negative-positive film units held together in stacked relationship. For example, the diffusion control layer of the present invention can be used in an integrated film unit of the type described in US Pat. No. 3,415,644, which film unit is particularly suited for forming color images. A film unit of this type comprises, for example, at least one light-sensitive silver halide emulsion layer having in combination (a) an opaque support layer, preferably an actinic radiation-opaque flexible sheet material; an image dye-providing substance; a negative part comprising; a positive part comprising an image-receiving layer dyeable with an image dye-providing substance; and a photosensitive laminate comprising a composite structure comprising a transparent support layer, preferably a flexible sheet material transparent to actinic radiation ( The photosensitive laminate also includes a diffusion control layer containing the polymer of the invention); (b) integrated with the film unit so that the processing composition is distributed between the negative and positive parts; a film unit containing an aqueous alkaline processing composition containing means; In this type of film unit, a light-reflecting pigment is applied by a processing composition, and when the processing composition is distributed between a negative part and a positive part, a light-reflecting layer is formed, and the dye formed in the image-receiving layer is Preferably, the image is visible against this background without separating the two parts. The diffusion control layer of the present invention can also be used in integrated negative-positive film units of the type described in U.S. Pat. No. 3,594,165. A film unit of this type comprises, for example, (a) a transparent support layer, preferably a flexible sheet material transparent to actinic radiation; a positive part comprising an image-receiving layer; (b) a photosensitive laminate comprising a negative part comprising a light-reflecting layer transparent to a processing composition through which an image can be viewed; and at least one photosensitive silver halide emulsion layer having in combination an image dye-providing substance; (c) transparent sheets stacked in substantially the same area on opposite sides of the transparent support of the photosensitive laminate; (c) a film such that the processing composition is distributed between the photosensitive laminate and the transparent sheet; means for having an aqueous alkaline processing composition containing an opacifier integrated with the unit; and (d) a component of the photosensitive laminate or one side of the transparent support adjacent to the photosensitive laminate. a diffusion control layer comprising a polymer of the present invention, which can be a coating on the film. The color image formed in the image-receiving layer can be viewed against the background of the light-reflecting layer without separating the transparent sheet from the photosensitive laminate. If desired, the basic light-sensitive layer and the image-receiving layer as well as the diffusion control layer of the present invention can be provided on one support layer, as exemplified in the film unit of Example 7. Such film units can be developed, for example, by imbibing a photographic processing composition onto the exposed film unit. The multicolor image comprises at least two selectively sensitized halogens each having in combination an image dye-providing material that provides an image dye with spectral absorption characteristics that are substantially complementary to the primary sensitivity range of the combined emulsion. A film unit of the present invention can be produced including a silveride emulsion layer. The most commonly used negative parts for forming polychromatic images are of tripak construction, each containing blue, green and red light sensitive halogens having a combination of yellow, magenta and cyan image dye-providing materials in the same or adjacent layers. Contains a silver oxide layer. Each silver halide emulsion layer and its combined image dye-providing material is separated from the remaining emulsion layers and their combined image dye-providing material by a separate alkaline solution permeable interlayer such as that provided by the present invention. It is preferable if As described in U.S. Pat. No. 2,983,606 and many other patents, an image dye-providing material that is particularly useful in the formation of color images by diffusion transfer is a dye developer, i.e., in the same molecule, the color developing agent of the dye. It is a compound containing both group-based and also silver halide developable functional groups. In a typical diffusion transfer system, each dye developer is associated with a separate silver halide emulsion layer, most preferably substantially only in reduced form at the initial PH provided by the processing composition. soluble and have a spectral absorption range that is substantially complementary to the primary sensitivity range of the emulsion with which it is associated. After exposure, a processing composition is applied and penetrates the emulsion layer to initiate development of the latent image contained therein. The dye developer is fixed or precipitated in the exposed areas as the latent image is developed. In the unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffusive, thus dissolving in the liquid processing composition depending on the degree of point-to-point exposure of the silver halide emulsion. An imagewise distribution of unoxidized dye developer is provided. At least a portion of this imagewise distribution of unoxidized dye developer is transferred by imbivision to the stacked image-receiving layer. This transfer substantially eliminates oxidized dye developer. The image-receiving layer accepts diffusion with a depth of unoxidized dye developer from the developed emulsion without appreciable loss of its imagewise distribution, providing a reversal of the developed image or a positive color image. The image-receiving layer may contain suitable auxiliaries to mordant or otherwise fix the diffused unoxidized dye developer.
After substantial transfer image formation, the film-based environment
Preferably, the PH is adjusted toward a second PH that causes residual dye developers remaining within the negative structure to precipitate or otherwise become non-diffusible in either their reduced or oxidized state. This PH adjustment is generally accomplished using an acid neutralizing layer, preferably a polymeric acid layer, as described below. For illustrative purposes, the invention is described below using a dye developer having the functions described above, but the invention is not limited to this exemplary image dye-providing material. Referring to the accompanying drawings, FIG.
A perspective view of an integral film unit of the type described in No. 3,415,644 is shown showing the processing composition 26 distributed between the negative and positive parts. The film unit 10 includes, in order, an opaque branch layer 12; a cyan dye developer layer 13; a red light-sensitive silver halide emulsion layer 14; an intermediate layer 15; a magenta dye developer layer 16; a green light sensitive silver halide emulsion layer 17; Intermediate layer 18; yellow dye developer layer 19; blue-sensitive silver halide emulsion layer 20; overcoat layer 21;
The photosensitive laminate 11 includes an image receiving layer 22; a spacer layer 23; a neutralizing layer 24; and a transparent support layer 25. After exposure through the transparent support layer 25, a processing composition 26, initially held in a rupturable container (not shown), is distributed between the overcoat layer 21 and the image-receiving layer 22, and the silver halide Begin development of the emulsion layer. The treatment composition may contain an opacifying agent of the type described in, for example, U.S. Pat. No. 3,647,437, and the treatment composition may include
However, it is preferred to prevent further exposure of the photosensitive layer of the film unit during processing of the film unit outside the camera. As a result of development, an imagewise distribution of diffusible dye developer is produced, which is at least partially transferred to image-receiving layer 22. layer 26 provided by the treatment composition contains a light-reflecting pigment such as titanium dioxide;
It is preferable that the color image formed on the image-receiving layer 22 can be viewed against the background. After substantial transfer imaging, a sufficient portion of the alkali provided by processing composition 26 is transferred to image-receiving layer 22.
and penetrates the spacer layer and across the neutralization layer where alkali neutralization lowers the pH of the system to a pH at which the dye developer is insoluble and non-diffusible, thus providing a stable color transfer image. . The spacer layer 23 and the neutralization layer 24 are the image receiving layer 2
2 and support layer 25, intermediate between support layer 12 and cyan dye developer layer 13,
It is also possible to arrange the neutralization layer adjacent to the support layer 12. In this embodiment, the alkali provided by the treatment composition permeates layer 13 through layer 21 and spacer layer 23 and neutralizes layer 24.
, where alkali neutralization takes place as described above. In the case of multicolor diffusion transfer products such as those described above, a given dye developer or other image dye-providing material may be associated with an emulsion layer other than the silver halide emulsion layer with which it is initially associated within the film unit. This may result in undesirable interimage effects. This unintended association generally results from the transfer of the image dye-providing material to a silver halide layer other than the one with which it was initially associated, after which this "wrong" emulsion layer is developed. As a result of this premature migration, the image dye-providing material may acquire diffusion properties opposite to those it would normally have if it remained associated with its intentionally controlled silver halide layer. For example, if dye development is prematurely transferred to a silver halide layer other than the one with which it was originally associated, the result of development of this "wrong" layer is that it becomes oxidized and becomes non-diffusive. , which prevents the image from being transferred to the image-receiving layer as intended. As a result, color reproduction and color saturation within the transferred image are adversely affected. Furthermore, as a result of the development of this "wrong" layer, a portion of the second dye developer to undergo oxidation remains in a reduced, diffusive state;
They may also be transferred and contaminate the resulting color transfer image. These internal image effects can be explained in more detail with reference to FIG. That is, layer 16
of magenta dye developer can diffuse back into red-sensitive silver halide emulsion layer 14 before this layer is substantially developed and substantial formation of an imagewise distribution of cyan dye developer in layer 13 occurs. If possible,
A portion of the magenta dye developer is oxidized as a result of red exposure and development of the red-sensitive emulsion layer;
May be non-diffuse. Therefore, there is a loss of magenta dye density in the transferred image. Furthermore, this portion of the cyan dye developer, which should be oxidized before the magenta dye developer, remains in the reduced form and diffuses into the image receiving layer 22, resulting in cyan dye contamination of the transferred image. Thus, accurate color reproduction of the subject is prevented by such interimage effects. To eliminate or minimize interimage effects, a diffusion control layer of the present invention is located between each silver halide layer and its combined dye developer, such as layers 15 and 18 in FIG. Can be used as an intermediate layer. The hydrolysis process that the hydrolyzable polymer(s) in these layers undergo retards the alkaline permeability of these layers during initial processing of the film unit, thus allowing the dye developer to '' and diffusion into the uncombined silver halide layers is prevented at least until substantial development of these layers and the intended imagewise distribution of the dye developer have been completed. "Release" of the diffusible dye developer should occur before substantial fogging of the emulsion layer, which has the fastest fogging rate, occurs. The "retention-release" behavior of the interlayer of the present invention has an advantage over interlayers that allow slow leakage of dye developer at the beginning of the processing period, i.e. during the critical initial development period. , which have the advantage of being well confined to their combined emulsion layer and then being released rapidly and in substantial amounts to enable rapid and substantially simultaneous transfer of color imaging materials. It's obvious. In addition to minimizing the aforementioned interimage effects, interlayers comprising the polymers of the present invention can also be used to increase the ability to reproduce accurate color over a range of temperatures. Generally, the lower the temperature at which processing occurs, the slower both the development rate and dye diffusion rate. If each of these rates is unduly slowed, i.e., the decrease in development rate is proportionally greater than the decrease in diffusion rate, color reproduction will be affected by dye removal from that combined emulsion layer prior to substantial development of this layer. Diffusion over a distance may cause harmful effects. This type of premature migration can be minimized by the use of an interlayer comprising a polymer of the invention, and the "retention" observed at even higher temperatures, e.g. ” even lower temperature for time,
For example, it has been found that longer "holding" times are obtained at 70°C. This interlayer can therefore be used to hold the dye developer in combination with the silver halide emulsion for longer periods of time at lower temperatures to adapt the system to slower development rates at lower temperatures, while the other The temperature and development speed can be increased to allow the dye developer to be "released" reasonably quickly. The polymers of the present invention useful as interlayer materials as described above can also be used in overcoat layers of photosensitive elements or negative parts, such as overcoat layer 21 in FIG.
Such an overcoat layer may be used, for example, to prevent premature migration of the dye developer closest to the distributed processing composition, or to provide substantially simultaneous transfer of the various color imaging materials at fixed sites within the image-receiving layer. It can be used to provide a means of making the information available to the public. Processing compositions used in diffusion transfer methods of the type contemplated by the present invention are typically highly alkaline and 12
have a greater PH, often 14 or more. Generally, a highly alkaline environment facilitates the performance of dye diffusion and provides satisfactory diffusion rates and image dye concentrations. As described in U.S. Pat. No. 3,362,819, reducing the film unit environmental PH to at least 11 or less after substantial transfer image formation to impart improved stability to the dye image. is highly desirable. US Patent No.
No. 3415644 discloses that in an integrated film unit in which a negative part and a positive part are stacked in a continuous relationship even after substantial transfer image formation, the environmental PH of the film unit can be changed from a PH that can be manipulated by the transfer process to a PH that cannot be manipulated by dye transfer. After substantial transfer image formation, in-process adjustments to the PH may be made in terms of the chemical and photostability of the image dye molecules and the post-process transfer of residual image dye-providing material within the negative structure to the image-receiving layer. From the viewpoint of prevention, it is disclosed that it is extremely desirable to obtain a more stable dye transfer image. As described in the above-cited U.S. Pat. No. 3,362,819, the reduction in film unit environmental PH is achieved by combining the alkali provided by the processing composition with a layer containing immobilized acid-reactive sites, i.e., a neutralization layer. This is preferably achieved by carrying out a neutralization reaction between the two. Suitable neutralizing layers are layers containing polymeric acids such as cellulose acetate hydrogen phthalate; polyvinyl hydrogen phthalate; polyacrylic acid; polystyrene sulfonic acid; and partial esters of polyethylene/maleic anhydride copolymers. Premature PH reduction, as evidenced by a decrease in image dye concentration, for example, can be caused by interposing a spacer or timing layer between the neutralizing layer and the processing composition layer that slowly diffuses the alkali toward the neutralizing layer. This can be prevented by As noted above, the diffusion control layer of the present invention forms an alkali-impermeable barrier for a predetermined period of time and then, as hydrolysis occurs, converts to a relatively alkali-permeable state where alkali is rapidly and substantially quantified. It can be used as a timing layer to allow crossing the neutralization layer in a targeted manner. A timing layer comprising a hydrolyzable polymer of the present invention may be applied to a receiving element of the type described in U.S. Pat. No. 3,362,819, or of the type described in U.S. Pat. It can be used as a constituent layer of the positive portion of an integrated negative-positive film unit. Alternatively, the timing layer and neutralization layer may be used, for example in U.S. Pat.
It can also be used in combination with negative parts, as described in 3362821 and 3573043. In the film units of the present invention of the type described in the above-cited US Pat. No. 3,594,165, these layers can also be supported by transparent sheets used to facilitate application of the processing composition. FIG. 2 illustrates an image receiving element of the present invention. Image receiving element 27 includes, in order, a support layer 28; a neutralizing layer 29; a spacer or timing layer comprising a hydrolyzable polymer of the invention; and an image receiving layer 31. During processing, the image-receiving layer is placed adjacent to the layer of processing composition. The processing composition penetrates into the image-receiving layer 31, imparts thereto a pH sufficient for imaging, and then penetrates through the timing layer 30 by hydrolysis of the diffusion control polymer contained therein. crosses the Japanese layer and is neutralized. As mentioned above, the permeability of the diffusion control layer of the present invention to alkali can be achieved by using comonomer units that impart an appropriate hydrophilic/hydrophobic balance and/or an appropriate degree of aggregation to the polymer. Alternatively, it can be controlled in a predetermined manner by using a matrix material that imparts the necessary hydrophilicity or cohesiveness. Generally, increased hydrophilicity or cohesiveness makes the permeability of the diffusion control layer relatively low to alkalis and to treatment compositions prior to its hydrolysis reaction. In another embodiment of the invention, an overcoat layer containing the polymer of the invention may be applied to the image receiving element or to the positive part of the film unit adjacent to the image receiving element and opposite the neutralizing layer. can. This type of overcoat at this location within the film unit can serve to control the diffusion of substances that are soluble in, or are solubilized by, alkaline or aqueous alkaline processing compositions. The transmission properties of the polymers of the present invention used in the timing layer are preferably such that the indicator dye initially included in the processing composition changes from a colored form at an initial high processing composition PH to a colorless form at a predetermined lower PH level. As evidenced by changing the color to
It can be evaluated by measuring the time required to adjust the environmental PH to a predetermined lower level. This type of evaluation can be performed using a test structure that includes, in order, a support, a polymeric acid layer, a test timing layer, and an image receiving layer. A transparent cover sheet is stacked on the test structure adjacent to the image-receiving layer with the same area and an indicator dye that is highly colored at a PH of 12 or above and colorless below a predetermined lower PH of about 9 or 10. An alkaline processing composition containing an alkaline processing composition is spread between the cover sheet and the image-receiving layer. The indicator dye has a pH level such that the alkali permeates through the test timing layer and crosses the polymeric acid to a level where neutralization of a substantial portion of the alkali present occurs and the indicator dye is colorless.
It remains colored and visible through the transparent cover sheet until it is lowered. This measurement of the time required for substantial "bleaching" of the indicator is commonly referred to as the "bleach time." Whereas the test structures containing a timing layer that allowed for a slow initial leakage of alkali and became progressively more permeable did not show an abrupt change in color, but were rather gradually bleached, Structures containing the described timing layer exhibit a rapid change in color after an initial delay, demonstrating the rapid change in alkali permeability caused by the timing layer upon hydrolysis. The ability of a diffusion control layer containing a polymer of the present invention to retard the passage of dye image-providing materials therethrough until hydrolyzed to a relatively dye-permeable state is illustrated in FIG. It can be evaluated by using a test structure. With such a structure, the transfer of the image dye-providing material through the test diffusion control layer is tracked over time. The "retention-release" properties of a hydrolysable polymeric test material can be evaluated by simulating the function of this material, for example, as an interlayer in a photosensitive element.
Such test structures and suitable evaluation methods are described in detail in Example 6. The polymer of the present invention has the formula () (In the formula, R, A, D and Z have the above meanings)
It can be produced by polymerizing a polymerizable monomeric ester by a known method. A monomeric ester of the formula () is, for example, a monomeric ester of the formula () Acrylic acid halide (chloride) of (wherein R has the above meaning and Hal represents halide)
and expression () (In the formula, A, D and Z each have the above-mentioned meanings.) Alternatively, monomeric esters can be prepared by the reaction of acrylic acid with a halogen-substituted ester according to the following representative reaction scheme illustrating the preparation of carbomethoxymethyl acrylate: A suitable method for producing the polymerizable monomeric compounds used for producing the hydrolyzable polymers of the present invention is
Bull Chem.Soc. Japan, 45 , 3604 (1972);
Macromol.Chem., 181 , 2495 (1980); and U.S. Patent No. 2376033 (to AMC Clifford)
(published May 15, 1945). Monomers produced by any of the above methods can be polymerized according to different polymerization techniques such as bulk, solution, suspension or emulsion polymerization. moreover,
The polymerization can also be carried out in the presence of other suitable polymers, ie polymeric matrix materials, to produce matrix systems that can be used as diffusion control layers. Polymerization can be initiated chemically, for example by suitable free radical or redox initiators, or by other means such as heat or incident radiation. Examples of chemical initiators include azobisisobutyronitrile, potassium persulfate, sodium bisulfite, benzoyl peroxide, diacetyl peroxide, hydrogen peroxide and diazoaminobenzene. It is clear that the initiation means chosen should be substantially incapable of causing decomposition or other deleterious reactions with either the reactants or the reaction products. The amount of catalyst used and reaction temperature can vary depending on specific needs. Generally, the polymerization is carried out at a temperature between 25°C and 100°C using an amount of initiator of less than 5% by weight based on the starting weight of the polymerizable monomer(s). This should allow for sufficient progress. The invention will be further illustrated by the following examples. These examples are illustrative and are not intended to be limiting. Unless otherwise specified, all parts or percentages are by weight. Example 1 Production of hydroxyacetone acrylate: 5. Three-necked round-bottomed flask (Claisen head with power stirrer, 1 addition funnel with stopper, thermometer and condenser with drying tube)
head) and cooling bath], acrylic acid (275 ml; 4 mol), methylene chloride (1.6), t
- Add butylpyrocatechol (0.40 g) and chloroacetone (320 ml; 3.6 mol). Charge the addition funnel with triethylamine (558 ml; 4 moles). The flask is placed in an ice bath and the solution is stirred at 10°C.
Cool until . Triethylamine is added over 20 minutes while maintaining the temperature at 18-20°C. Replace the ice bath with a water bath to achieve a mildly exothermic reaction 22-27
Control at ℃ for 28 hours. The mixture is filtered under vacuum and the filter cake is washed with methylene chloride (2 x 100 ml) and then compressed to dryness on a rubber drum. The filtrate was washed with cold saturated NaCl (2 x 2), dried (Na ₂ SO ₄ ), filtered and further added t-butylpyrocatechol (1.5) before vacuum (35°C).
Evaporate with The crude dark amber oil (524-532 g) is distilled under reduced pressure through a standard Claisen head to give, after an initial pre-distillate (30-35 g), hydroxyacetone acrylate as a colorless liquid (307- 320
g; Yield: 60-64%; Boiling point: 52-55°C/1.5-0.9
mm). Example 2 Preparation of 40/58/2 (parts by weight) copolymer of hydroxyacetone acrylate/methyl methacrylate/methacrylic acid; 128 g deionized water and emulsifier [American
A mixture of 0.20 g of dioctyl sodium sulfosuccinate available as Aerosol OT-75 from Cyanamid Company was heated at 80°C under nitrogen atmosphere.
Heat to. To this mixture 25 g of hydroxyacetone acrylate prepared as described in Example 1;
Methyl methacrylate 36.2g, methacrylic acid
A first portion (5 parts by weight of the total) of the monomer mixture consisting of 1.25 g and 0.12 g of Aerosol OT-100 emulsifier is added. After 5 minutes, 0.25 g of ammonium peroxydisulfate is introduced into the resulting mixture. Then, one minute later, slowly add the remaining portion of the mixture (remaining 95 parts). This remaining portion addition is completed in 3 hours, after which the reaction contents are held at 80°C for 1 hour. A latex with a solids content of 30% by weight is obtained (yield: 180
g). Example 3 The hydrolysable polymer prepared by the method described in Example 2 is evaluated using a test structure, shown at 32 in FIG. 3, having the following configuration: transparent support 33; cyan dye developer approx. 215 mg/m ² , gelatin approx. 430
and layer 34 containing about 2150 mg/m ² of ^polymeric material ^. Layers 34 and 35 are applied sequentially onto support 33 using a conventional loop coater. A transparent sheet 37 containing a polyester film base is stacked with the test structure and an opaque alkaline treatment composition 36 containing the following ingredients is introduced between the polymeric test material layer 35 and the transparent sheet 37 with a gap of 0.071 mm: : Potassium hydroxide (45% aqueous solution) 23.93g Benzotriazole 1.33g 6-Methyluracil 0.72g Bis-(β-aminoethyl)-sulfide 0.05g Colloidal silica, aqueous suspension (30% SiO ₂ )
4.48g Titanium dioxide 92.1g N-phenethyl α-picolinium bromide (50
% aqueous solution) 6.18g N-2-hydroxyethyl-N,N',N'-triscarboxymethylethylenediamine 1.81g 4-aminopyrazolo[3,4d]pyrimidine
0.60g carboxymethylhydroxyethyl cellulose
4.84 g water 100 g Immediately after introducing the treatment composition, the optical reflection density for red light of the sample was measured as a function of time through a transparent support 33 using a Mac Beth Quanta-Log densitometer equipped with a tape recorder. Monitor using. The concentrations measured as a function of time are the concentrations of the cyan dye developer in the initial dye-containing layer 34 and the cyan dye developer in the polymeric test layer 35. The dye developer that diffuses into the processing composition through test layer 35 is masked by the titanium dioxide contained therein and therefore does not contribute to red absorption. In this way the dye developer can be observed diffusing through the test layer and into the processing composition. FIG. 4 graphically depicts red absorption concentration as a function of time. In this graph, t ₁ is the time for the cyan dye developer to become wet due to processing; t ₂ is the total time that the cyan dye developer is retained by the polymeric interlayer, and D _p is the absorbed concentration of dye developer after dissolution; and D _f is the final absorbed concentration of residual dye developer remaining in layers 34 and 35 after completion of dye diffusion. Calculate the slope of the line between A and B. This indicates how quickly the test layer undergoes changes in dye transparency. a polymeric material prepared as described in Example 2 above is blended with a matrix polymer and applied as a diffusion control test layer 35 of the test structure;
evaluate. Measure the numbers (in seconds) and slope of t ₁ and t ₂ . In Table 1, the polymeric material of Example 2 is designated as component X. The formulation consists of 30 parts of component X and component Y (diacetone acrylamide/butyl acrylate/acrylic acid/2-acrylamide-
2-methylpropanesulfonic acid: 50.5/44/5/
0.5 parts by weight of each copolymer) 70 parts. The results are shown in Table 1 below.

[Table] Example 4 Production of carbomethoxymethyl acrylate: A 5.5 three neck round bottom flask (equipped with a magnetic stirrer, thermometer and one addition funnel topped with a drying tube) is charged with 527.9 ml of acrylic acid, 662.7 ml of methyl bromoacetate and 1750 ml of ethyl acetate. The resulting solution is cooled to about 15° C. and then 1073.2 ml of triethylamine are added over about 1 hour. An exotherm is observed and the reaction temperature is maintained between 15° and 25°C with an ice/salt cooling bath. Upon completion of the triethylamine addition, the cooling bath is removed and the reaction mixture is stirred at room temperature (25-30°C) overnight. Pour the resulting sticky slurry into 1750 ml of distilled water.
Separate the organic layer. The aqueous layer was purified with ethyl acetate (twice,
500ml each time), and the collected organic liquid was extracted with 0.5N hydrochloric acid.
500 ml of saturated aqueous sodium bicarbonate solution and then 500 ml of saturated aqueous sodium chloride solution.
The organic solution (approx. 3.5-3.75) was then dried (magnesium sulfate) and vacuumed (water aspirator).
Evaporate at 30 °C to obtain a very pale yellow product. The product is purified by adding 1 g of 2,6-di-tert-butyl-p-cresol as a free radical initiator and then passing it through a distillation column and distilling it under reduced pressure. The purified product is heated between 50℃ (1.2mm) and 56℃ (1.9mm).
mm) indicates the boiling point. Example 5 80 parts of a 50.5/44/4/0.5 copolymer of diacetone acrylamide/butyl acrylate/acrylic acid/2-acrylamido-2-methylpropanesulfonic acid and a 75/25 copolymer of carbomethoxymethyl acrylate/diacetone acrylamide. polymer
Production of a matrix/hydrolysable unit polymer system containing 20 parts. In 12 flasks [equipped with a mechanical stirrer, nitrogen inlet tube, thermometer, condenser and monomer inlet], diacetone acrylamide/butyl acrylate/acrylic acid/2-acrylamide-2-
Methylpropanesulfonic acid (50.5/44/5/0.5
10 kg of copolymer-based latex (solids content of this latex is 29.5% by weight) of 29.5% by weight) are charged. The latex is stirred and the pH is adjusted to 3 by adding 478 g of 1% by weight sodium hydroxide solution over a period of 30 minutes. The nitrogen inlet tube is placed below the surface of the liquid contents of the flask and the nitrogen flow is
Introduce at cc/min. The latex is slowly heated to 80°C for 2 hours under continuous stirring and nitrogen flow. A solution of polymerization initiator (prepared by dissolving 2.66 g of ammonium persulfate in 167 ml of deionized water purged with nitrogen for at least 2 minutes) is charged to the dropping funnel and added to the reaction flask at maximum rate. After 1 minute, the subsurface nitrogen flow is changed to a blanket and the flow rate is increased to 5 c.c./min. 1.5 minutes after adding the initiator solution, add the monomer solution.
Start with a feed rate of 8.15cc/min. This addition is 1.5
Do this evenly over time. Monomer feed solution [prepared by stirring together 183.3 g diacetone acrylamide, 550 g carbomethoxymethyl acrylate prepared as described in Example 4, and 0.62 g Aerosol OT-100 and filtering the mixture] is each polymerizable monomer 25/75 (weight)
Contained in a ratio of Once the monomer feed charge is complete, the reactor contents are heated to a temperature of 80° C. for 90 minutes. The polymerization product is cooled to room temperature and filtered through cheesecloth. The solids content of the polymer product is approximately 31.3% by weight. Example 6 Diacetone acrylamide/butyl acrylate/acrylic acid/ethyl acrylate/carbomethoxymethyl acrylate 39.25/30.00/
Production of 0.25/15.25/15.25 copolymer: 1721.6 g of water was charged into a 5 three-necked round-bottomed flask [equipped with a mechanical stirrer, a nitrogen inlet tube, a thermometer, a condenser, and a monomer inlet tube]. . Stir the water and heat it to 80℃ while nitrogen flow (1200c.c./
infuse for at least 45 minutes. Charge emulsifier (Aerosol OT-75 4.8 g) to the container. The monomer feed solution was in a beaker containing 509.4 g of diacetone acrylamide, 389.4 g of butyl acrylate, 3.0 g of acrylic acid, 198 g of ethyl acrylate, 198 g of carbomethoxymethyl acrylate, and
Mix 3.2g of Aerosol OT−75 and store the mixture at 35℃.
It is prepared by placing in a water bath, stirring the contents while maintaining the temperature below 25°C to promote dissolution, and then filtering the resulting solution. An initiator solution is prepared by mixing 40 ml of water and 7.3 g of ammonium persulfate, and this initiator solution is set aside. The first portion of the monomer feed solution (65 g;
%) into the reaction vessel without opening the vessel to the atmosphere. After charging this one part,
After 1 minute, place the nitrogen inlet tube above the liquid surface.
Apply a nitrogen atmosphere and then reduce the flow rate to 80 c.c./min. The initiator solution is then charged to the reaction vessel without opening the vessel to the atmosphere. After 2 minutes, the remaining portion (95%) of the monomer feed solution is introduced evenly over a period of 4 hours. Upon completion of this addition, the reaction batch was heated to 80° C. for 1 hour, cooled to room temperature, and then filtered through cheesecloth.
A polymeric latex is obtained. Example 7 A diffusion transfer photographic film unit is manufactured as follows. A 7 mil (0.18 mm) primed polyethylene terephthalate transparent sheet (containing a small amount of carbon black to protect against light leakage and halation effects) is coated with each of the following layers in sequence: 1 approximately 10000 mg/m a polymeric acid layer comprising about 9 parts of a half-butyl ester of a polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral applied at a coverage of ² ; 2 as a timing layer at a coverage of about 6000 mg/ ^m2 ; A layer of a polymer prepared by the method described in Example 6, coated; 3. A blue-sensitive silver iodobromide emulsion layer coated at a coverage of about 1300 mg/m ² of silver (1.11 microns) and about 650 mg/m ² of gelatin. ; Quaternary yellow dye developer Approximately 1150mg/m ² , gelatin approximately 566g/m ² , 4-
(1-phenyl-1,2,3,4-tetrazolyl-5-thiomethyl)-imidazole approximately 45 mg/
m ² , and a yellow dye developer layer made from about 115 mg/m ² of 4'-methyl-phenyl-hydroquinone; 5 as an interlayer diacetone acrylamide/
Butyl acrylate/acrylic acid/2-acrylamido-2-methylpropanesulfonic acid
85 parts of 50.5/44/4/0.5 copolymer and 15 parts of carbomethoxymethyl acrylate/diacetone acrylamide 75/25 copolymer, approximately 3000 mg/m ² of this polymer mixture, approximately 143 mg/m ² of triethanolamine. and succindialdehyde approx.
6. A layer coated with a coverage of 24 mg/m ² ; 6. A green-sensitive silver iodobromide emulsion layer coated with a coverage of approximately 896 mg/m ² of silver (1.11 microns) and approximately 394 mg/m ² of gelatin; 7. magenta dye developer Approximately 500mg/m ² , gelatin approximately 321mg/m ² , 4-
(1-phenyl-1,2,3,4-tetrazolyl-5-thiomethyl)-imidazole approx. 30.5
a magenta dye developer layer made of about 115 mg/m ² and 4′-methyl-phenyl-hydroquinone; 8 as an interlayer about 2500 mg/m ² of the 85/15 polymer mixture described in layer 5 above ^; , triethanolamine approximately 119 mg/m ² and succindialdehyde approximately 20
9 a red-sensitive silver iodobromide emulsion layer coated with a coverage of about 866 mg/ ^{m 2 of} silver (1.11 microns) and about 520 mg/m ² of gelatin; cyan dye developer Approx. 425mg/m ² , Gelatin approx. 323mg/m ² , 4-
(1-phenyl-1,2,3,4-tetrazolyl-5-thiomethyl)-imidazole approx. 37.0
121 mg/m ² of 4'-methyl-phenyl-hydroquinone; 11 as an interlayer about 2500 mg/m of the 85/15 polymer mixture described in layer 5 above ^{. 2} and triethanolamine at a coverage of 119 mg/ ^m2 ; 12 carbon black approx. 1500 mg/ ^m2 , polyethylene oxide approx. 309 mg/ ^m2 , Teflon (du Pont
Teflon30) approx. 94mg/ ^m2 and Rhoplex
Opacifying layer made of HA-12 polyacrylamide latex (Rohm & Haas) approx. 750 mg/m ² ; 13 Titanium dioxide approx. 11000 mg/m ² , polyethylene oxide approx. 1467 mg/m ² , Rhoplex HA-12 polyacrylamide Latex (Rohm &
Haas) approx. 917mg/ ^m2 and Teflon (du
Reflective layer made from approximately 1467 mg/ ^m2 of Teflon30 from Pont; 14 on hydroxyethyl cellulose (HEC)
an image-receiving layer coated with 4-vinylpyridine (4VP) and vinylbenzyltrimethylammonium chloride (TMQ) grafted in the ratio HEC/4VP/TMQ2.2/2.2/1 at a coverage of approximately 2000 mg/ ^m2 ; and 15 Topcoat layer made from about 2000 mg/m ² of sodium cellulose sulfate and about 29 mg/m ² of polyacrylamide. This photographic film unit is exposed to the test subject or step wedge from the transparent support side (4 m -
Kindle-Sec). The exposed film unit is then introduced into a light-tight container containing a photographic processing composition having the following composition (room temperature, 22
°C) in a bath of an alkaline photographic processing composition in the dark: Ingredients Parts by weight Potassium hydroxide 5 Aene acetate dihydrate 0.74 Tetramethylreductinic acid 0.20 N-(n-pentyl)-α-picoli nium bromide 2.2 Water Amount to bring the total volume to 100 After a 2.5 minute imbibition time, the film unit is removed from the bath through a pair of rollers (to remove excess liquid) and the film unit is placed in the dark for an additional 1.5 minutes. keep it in the dark. The film unit is then removed into room light. The photographic image is seen as a reflected image against the background of the light-reflecting layer. Red, green and blue D _nax and D _nio values were measured and are shown in Table 4 below.

【table】 [Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a photographic film unit including a diffusion control layer of the present invention; FIG. 2 is a cross-sectional view of an image receiving element including a diffusion control timing layer of the present invention; FIG. and FIG. 4 graphically depicts dye concentration as a function of time in a photographic system containing an interlayer of the present invention.

Claims (1)

Claims: 1. a support layer; a light-sensitive silver halide emulsion layer having in combination a diffusion transfer image-providing material; an image-receiving layer-permeable alkaline processing composition; and at least one layer containing a hydrolyzable polymer.
a diffusion control layer; wherein the diffusion control layer is impermeable to the alkali or the substance soluble in the alkaline treatment composition or is solubilized by the alkaline treatment composition; The layer is suitable for conversion by predetermined hydrolysis of the polymer under the alkaline conditions of an alkaline photographic processing composition into a transparent state, and the hydrolyzable polymer is of the formula [In the formula, R is hydrogen, halogen or lower alkyl; A and D each independently represent hydrogen, alkyl,
alkoxy, aryl, alkaryl or aralkyl, and Z represents an electron-withdrawing group which activates the hydrolytic decomposition of the polymer with concomitant formation of an acrylate anion when the polymer comes into contact with an alkali, or Diffusion transfer photographic film units. 2. Diffusion transfer photographic film units. 2. A patent in which the electron-withdrawing group Z is a group that activates the hydrolytic decomposition of side chain ester groups of the polymer with concomitant formation of carboxylic acid anion groups when the polymer comes into contact with an alkaline treatment composition. A diffusion transfer film unit according to claim 1. 3 The group Z has the formula [Formula] (wherein Y is -R ² or -OR ² and R ² is
3. The diffusion transfer film unit of claim 2, wherein the diffusion transfer film unit is an alkaryl or aralkyl group. 4. The diffusion transfer film unit of claim 3, wherein the Z group is of the formula: where R ² is alkyl. 5. The diffusion transfer film unit of claim 3, wherein the Z group is of the formula: where R ² is alkyl. 6. The diffusion transfer film unit of claim 5, wherein A and D are each hydrogen. 7. A diffusion control layer comprising a hydrolyzable polymer is permeable to alkali but substantially impermeable to processing composition soluble, diffusible dye imaging substances until hydrolysis of the hydrolyzable polymer. 2. The diffusion transfer film unit of claim 1, wherein the layer is a polyurethane. 8. Diffusion transfer according to claim 1, wherein the diffusion control layer comprising a hydrolyzable polymer is a layer that is substantially impermeable to the treatment composition until hydrolysis of the hydrolyzable polymer. Film unit. 9. The diffusion transfer film unit of claim 1, wherein the diffusion control layer contains a matrix polymer in which a hydrolyzable polymer is polymerized. 10 The matrix polymer is acrylic acid; methacrylic acid; methyl methacrylate; 2-acrylamido-2-methylpropanesulfonic acid; acrylamide; methacrylamide; N,N-dimethylacrylamide; ethyl acrylate; butyl acrylate; diacetone 10. The diffusion transfer film unit of claim 9 which is a copolymer comprising repeating comonomer units selected from the group consisting of acrylamide; acrylamide acetamide; and methacrylamide acetamide. 11. The diffusion transfer film unit of claim 1, wherein the image-providing material is a dye developer. 12 At least two selectively sensitized silver halide emulsions having in combination image dye-providing materials that provide an image dye with spectral absorption characteristics that are substantially complementary to the primary sensitivity range of the combined emulsion. 2. A diffusion transfer film unit according to claim 1, wherein the diffusion control layer is an interlayer located between the silver halide emulsion layers and the combined image dye-providing material. 13. The diffusion transfer film unit of claim 12, wherein the diffusion control layer is permeable to alkali but impermeable to image dye-providing materials until hydrolysis of the hydrolyzable polymer.