JPS5930260B2 - photo elements - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic element having a temporary barrier layer that retards contact between reactants, and more particularly, when an aqueous alkaline solution penetrates the layer,
The present invention relates to photographic elements for use in color diffusion transfer processes in which portions of the element are temporarily isolated from other portions by a timing layer comprised of a polymeric latex having an activation energy greater than or equal to Kcal/mole.

``Photography, its materials and processes'' by Neblett
(Photography, ltsMaterials
andProcess) (published in 1962), promotes differential processing of various silver halide emulsions after exposure, and when two layers are simultaneously subjected to similar processing, one layer Interlayers have traditionally been used in multicolor photographic elements to minimize effects on other layers.

The use of improved interlayers in multicolor image transfer film units is well known and is reported, for example, in Becker (1) US Pat. Nos. 3,411,904 and 3,418,117. The intermediate layer in many known film units acts as a temporary barrier, thereby isolating the reactants of the surrounded layer for a predetermined period of time. Image transfer methods are known in the art in which a single processing liquid is used to develop an exposed image record to produce a visible image record. These image transfer methods often do not use post-processing such as washing or fixing baths. This is because a completely built-in film unit is one of its elements. Various timing, spacer or barrier layers have been used in certain cases to retard the interaction between the components of each layer of the image transfer film unit.

A spacer layer is used between the polymeric acid layer and the silver halide emulsion layer of the image transfer film unit. Processing at a high pH value is continued for a predetermined period of time before the silica layer becomes effective in neutralizing the processing composition. Make it possible. This point is disclosed in US Pat. No. 2,584,030 (issued January 29, 1952). Frie (by Han, 6 History of Color Photography
(1968) pages 538-543, describes the use of spacers or barriers in conjunction with neutralizing layers in image transfer products.

In this type of product, an alkaline composition penetrates the timing layer and the alkali is depleted into its structure by the acid of the neutralization layer. In certain cases, the breakdown of the timing layer releases a substance that acts as a blocking mechanism and sets the amount of silver halide development and the amount of dye formation according to the respective exposure value. U.S. Patent No. 25431
No. 81, No. 2983606, No. 3362819, No. 3362821, No. 3415645, No. 34156
No. 46, No. 3647437, No. 3635707 and No. 3756815, and Canadian Patent No. 9285
No. 59 and No. 674,082, etc., report various systems of color diffusion transfer mechanisms.

In these systems, the image-receiving layer containing the photographic image for viewing can be separated from the photographic layer after processing, or in certain embodiments, a transparent support is used on the viewing side of the mechanism. When used, the imaging layer and ancillary layers present in the structure can be permanently attached and made integral therewith. Color-forming substances emitted by the image-generating units diffuse through the layers in the structure and reach the dyed image-receiving layer to form an image. After exposure, the alkaline processing composition permeates each layer, and development of the exposed photosensitive silver halide emulsion layer begins. Each emulsion layer is developed in proportion to its respective degree of exposure and the image dye formed or released in the respective image generating layer begins to diffuse into the structure. At least a portion of the imagewise distributed or released color-forming substance migrates to the dye image-receiving layer to form an image of the original object. The timing layer for these purposes was published in Research Discl. July 1954.
Osurel 233l, Volume 123 ``Neutralizing Materials in Photographic Elements'' (Neut-Ralizing Materia
lsinPhOtOgraphicElements)
and U.S. Pat. No. 2,584,030;
No. 3421893, No. 3419389, No. 3433
No. 633, No. 3856522, No. 3362819,
No. 3455686, No. 3415644, No. 3414
No. 4111, No. 3785815, and No. 35757
No. 01, Canadian Patent No. 928,559 and British Patent No. 134,034. However, in the use of timing layers in known techniques, development is carried out over a wide temperature range. At temperatures well below room temperature encountered in cold environments, temperature-dependent development methods are slow, and the timing layer, which is penetrated or destroyed by the less temperature-dependent alkali, cannot produce clear images with sufficient development. inhibits the formation of On the other hand, at temperatures considerably above room temperature,
These known timing layers delay the decrease in pH value and result in overdevelopment of the emulsion layer. In image transfer processes where the diffusible dye is released imagewise from an immobile or non-diffusible dye-releasing compound in the area where the silver development takes place, underdevelopment is caused by a low density wash-out of the dye in the image-receiving layer. dye is applied and over-development results in too dark images with high dye density.

Therefore, there is a need for a timing layer or barrier layer that is more responsive to temperature changes than timing layers according to known techniques.

By using a polymer latex having an activation energy for permeation by an aqueous alkaline solution of 18 Kca1 or more per mole, the present inventor has developed a timing layer that increases alkali permeability at high temperatures and decreases this at low temperatures. It has been found that temporary barrier walls can be created. The timing layer comprised of the electrolyte latex retards the neutralization of the alkaline processing composition by the acid layer and increases the reproducibility of producing good quality dye images over a wide temperature range. The activation energy of a polymer latex for penetration by an aqueous alkaline solution can be determined by the simple test described below. Add thymolphthalein dye or cresol red indicator dye to 6.6 gm/l of gelatin for thymol phthalein dye and 2.6 gm/l for cresol red.
It is coated on a film support of polyethylene terephthalate at a rate of 210 mg/l with 2 gm/wl.

A processing composition consisting of a pot (POd) containing an aqueous solution of about 0.8N potassium hydroxide and about 5% carboxymethyl cellulose, along with other conventional developer components, is added to the element containing the indicator dye and the cover sheet sample. Spread between. This operation is carried out by passing the 6-sandwich structure between a pair of juxtaposed pressure rollers, resulting in a developer layer thickness of 0.1 mTfL. The above cover sheet has a poly(butyl acrylate-CO-acrylic acid) copolymer of 30:70 (by weight) as the first layer and a poly(styrene-CO-anhydride) copolymer of 50:50 (mole ratio) as the second layer. It consists of a support of polyethylene terephthalate containing maleic acid (maleic acid) polymer (2.29/m), the outer layer being the polymer that determines the portrait energy.

PHlO as measured by the color change of the thymolphthalein dye from blue to colorless under various temperatures within the temperature range of 13-45°C.
Up to PH8 due to changes in cresol/retsuB abrasion charges.
The time required to lower the pH to 1 was measured.

Time in seconds was plotted on a logarithmic scale as the reciprocal of temperature expressed in 0K. Activation energy is Kcal
//MOle was determined from the slope of the straight line portion of the curve according to the formula below. Here, T2 is high temperature, T, is low temperature,
Y2 is the time at T2, and Y1 is the time at T1. The thickness of the acid layer and the polymer layer are not critical to determining the activation energy. For information on this calculation method, please refer to “Kinetics and Mechanism”.
Mechanism) (New York JOhnWllll)
Published by eyandSOns, 1961 2nd edition) 22-2
It is described on page 5.

Latex polymers having an activation energy of 18 Kca1/RnOle or more include poly(methyl acrylate-CO-itaconate-CO monosalt hibinylidene) and the like.

Preferred latexes include a terpolymer of about 5 to about 35 weight percent polymerized ethylenically unsaturated monomer, about 2 to about 10 weight percent polymerized ethylenically unsaturated carboxylic acid, and about 55 to about 85 weight percent polymerized vinylidene chloride. (Three-component co-bundle coalescence)
can be given.

Any ethylenically unsaturated monomer that is different from the other monomers in the polymer latex can be used to prepare the terpolymer. Alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, etc.: vinyl esters, amides, nitriles,
Ketones, halides, ethers, olefins, diolefins, etc., such as acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, acrylamide,
methacrylamide, vinyl chloride, methyl vinyl ketone,
Fumarate, maleate and itaconate, 2-chloroethyl vinyl ester, dimethylaminoethyl methacrylate, dihydroxyethyl methacrylate, vinyl succinimide, N-vinylphthalimide, N-vinylpyrrolidone, butadiene, This includes ethylene. Examples of preferred monomers include methyl acrylate and acrylonitrile. Ethylenically unsaturated carboxylic acids that can be included in the polymer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, anhydrides thereof, and the like.

Preferred carboxylic acids are acrylic acid and itaconic acid. For example, acrylonitrile 17.4% by weight, vinylidene chloride 75.3% by weight, acrylic acid 7.3% by weight.
A terpolymer consisting of the following can be prepared as follows.

2.25 potassium metabisulfite in distilled water of 42009
A solution of 9 was placed in a reactor, stirred, and cooled to 20°C.

Purge with nitrite and acrylonitrile 333.7
g, vinylidene chloride 14539, acrylic acid 1419 and Triton J Mo V0 (surfactant) 1419 were added,
To this was added 4.59 g of potassium persulfate, and the reaction was continued by stirring at a temperature of 30 DEG C. and a rotation speed of 150 r-p-MD. Another preferred terpolymer consisting of 15% by weight ethyl acrylate, 83% by weight vinylidene chloride, and 2% by weight itaconic acid is prepared in a manner generally similar to that described above.

In another embodiment of the invention, the photographic products described herein employ temporary barriers.

The barrier consists of two adjacent timing layers, one of which is comprised of a polymeric latex having an activation energy of aqueous alkali penetration of approximately 18 kca1/MOle or less, as described above, and the other of which has an activation energy of aqueous alkali penetration of less than or equal to 18 kca1/MOle. It consists of a polymer layer that has activation energy. An example of a polymer having an activation energy for permeation of an aqueous alkaline solution of 18 kca1/RnOle or less is a mixture of acetylcellulose and maleic anhydride copolymer.

The mixing ratio of the above-mentioned symphonic combination is French patent No. 229069.
5 to 50% by weight as described in No. 8. The maleic anhydride co-polymer in this timing layer is about 20 to about 20, taking into account any other copolymers
It should be used in a concentration of % by weight.

Particularly good results are obtained using concentrations between 5 and 20%.

The thickness of the timing layer is such as to provide a coverage of about 1 to about 59/I. The acetylcellulose used here typically has an acetyl content of about 37-40% by weight, with 37% acetyl being substantially more permeable than 400t). Mixed esters such as cellulose acetate propinate and cellulose acetate butyrate can also be used. The maleic anhydride co-assembly can be selected from a wide variety of materials as long as they are compatible with the acetylcellulose used and provide a transparent film.

Particularly good results are obtained with poly(styrene-CO-maleic anhydride), poly(ethylene-CO-maleic anhydride) and poly(methynovinyl ether-CO-maleic anhydride). The anhydride portion of the maleic anhydride copolymer used can be hydrolyzed to the corresponding acid prior to use.

For example, analysis of poly(styrene-CO-maleic anhydride) revealed that it contained 8 mol% of maleic anhydride and monomethyl maleate.

The mole percent of free maleic acid in the copolymer can therefore vary over a wide range and is generally about 3
0% to about 50% gives good results. 1
Examples of other layers containing polymers with activation energy below 8 kcal/MOle include polyvinyl acetate, cellulose acetate phthalate, the acetal moiety of polyvinyl alcohol, U.S. Patent No. 378,581.
Polymer latex of butyl acrylate-diacetone acrylamide styrene-methacrylic acid (60/30/4/6) described in No. 5, a mixture of polyvinyl acetate and polyvinyl alcohol, for example French Patent No. 2290698
A mixture of polyvinyl acetate latex and polyvinyl alcohol in a ratio of 78/22, acetyl cellulose (40% acetate) and poly(styrene-CO-maleic anhydride) in a ratio of 95/5, as described in No. (molar ratio 50/50).

In this two-layer embodiment of the invention, 18 kcal/M
A layer having an activation energy of aqueous alkaline solution penetration of Ole or less is first applied on the neutralized acid layer,
It is most desirable to configure the timing layer(s) such that a layer having an activation energy for aqueous alkaline solution penetration greater than or equal to MOle is applied directly onto the first timing layer.

In certain cases, excellent interlayer adhesion is obtained when the layers are applied in this order. This is especially the case when the acid is applied with an organic solvent. Preferably, the particle size of the polymer latex is about 25 to 160 nm. Although the temporary barrier can consist of two layers separated by an intermediate layer, in a preferred embodiment of the invention the two layers are continuous with each other.

In certain cases, substances such as development inhibitors,
It can be used in the timing layer (if either material is used) or in one or both layers (if both materials are used) to achieve the desired results. Timing layers of polymers such as cellulose esters, polyvinyl esters and acetals can be applied by conventional techniques from solutions in organic solvents such as acetone and methylene chloride. A timing layer consisting of a mixture of acetylcellulose and poly(styrene-CO monomaleic anhydride) is generally used in a ratio of 2 to 89/Trl, preferably 2.5 to 4.59/Trl. Latex timing layers are generally more widely available.

The preferred coating weight for each layer is from about 1.09/I to 6.09/I, with particularly good results obtained when distributed at a ratio of about 1 to 39/I. A wide variety of interfacial agents can be applied to latex layers useful in this invention.

For example, adding up to 4% by weight of a surfactant such as Triton The uniformity of the coating is improved. Other examples of latex polymers that can be used herein include U.S. Pat. No. 3,271.
No. 345, No. 2627088, No. 2491023,
No. 2779684, No. 3437484, No. 2943
No. 937, and No. 3,143,421.

According to the invention, a temporary barrier separating one part of a photographic product from another can be used for a desired period of time as long as it is between the substance to be isolated and the remaining parts of the layers of the photographic product. The latex timing layer can be applied by any conventional water-based coating method.

Critical to proper timing characteristics are the drying time and temperature of the latex layer. An important factor in the fusion of Cartesian latex is AnderhOff.
and “Mechanism of Film Formation of Latex” by Bradf Ord.
tiOnOfLatices) TAPPI, 46, 2l
5-221 (1963). Latex coatings can be dried over a wide temperature range;
Particularly good results are obtained when drying at 55-95°C.

The drying time can be from 30 seconds to 5 minutes, preferably from 30 seconds to 2 minutes. Generally, the shorter the drying time, the more suitable it is for high temperatures, and the longer the drying time, the more suitable it is for lower temperatures. In order to achieve a certain level of permeability in fused or partially fused natexes, higher drying temperatures are generally required for latexes with higher acid content in the copolymer. The photographic film unit according to the present invention is composed of the following:

(a) a support carrying at least one light-sensitive silver halide emulsion layer, preferably in combination with a dye-imaging material;
(b) an image-receiving layer; (c) means for releasing an alkaline processing composition within the assembly; (d) a neutralizing layer for neutralizing said alkaline processing composition; and (e) a neutralizing layer and said photosensitive layer. A temporary barrier placed between the silver halide emulsion layer and the dye imaging material.

The film unit of the present invention includes a silver halide developer, the temporary barrier comprising a polymer latex layer having a talkative energy of aqueous alkaline solution penetration of 18 kcal/MOle or more, and optionally a polymer latex layer having a talkative energy of aqueous alkaline solution penetration of 18 kcal/MOle or more.
A second layer of polymer latex having an activation energy of aqueous alkaline solution penetration of less than 1/MOle is provided.

A dye imaging material is generally disposed between the image-receiving layer and the timing layer. In one embodiment of the invention, the film unit is a laminated integral negative receiver color diffusion transfer film unit and the temporary barrier of the invention is used on the cover sheet as disclosed in Canadian Patent No. 928,559. can do.

In this embodiment, the photosensitive element support is transparent and coated with a photosensitive layer that combines an image-receiving layer, an opaque white reflective layer, a black opaque layer, and a dye imaging material. A rupturable container containing an alkaline treatment composition and an opacifier such as carbon black is placed adjacent to the top layer and transparent cover sheet. The cover sheet consists of a transparent support coated with a neutralizing layer and a temporary barrier of the invention. The film unit is placed in the camera, exposed through the transparent cover sheet, and then passed through a pair of push members in the camera when removed from the camera. The pusher ruptures the container and spreads the processing composition and opacifying agent over the imaging portion of the film unit. The silver halide layer is developed, a dye image is formed as a result of the development, and the dye diffuses into the image-receiving layer to provide the image. The image is viewed through a transparent support with a background of an opaque reflective layer. The temporary barrier disintegrates after a period of time and the agent that neutralizes the alkaline processing composition acts to stop further development of the silver halide. Details regarding this type of laminated monolithic film unit are described in Canadian Patent No. 928,559. I will only cite the literature here. Another embodiment of a laminated monolithic color diffusion transfer film unit in which the temporary barrier of the present invention may be used in a dye image-receiving element is disclosed in U.S. Pat. No. 3,415.
It is described in No. 644.

In this embodiment, the photosensitive compound comprises an opaque support coated with a photosensitive layer in combination with a layer of dye imaging material. A rupturable container containing an alkaline processing composition TiO2 and an indicator dye (US Pat. No. 3,647,437) is placed adjacent to the top layer and transparent receiver. The image receptor is coated with a neutralizing layer, a temporary barrier and an image receiving layer. The film unit is placed in the camera and exposed through the transparent image receptor, and then passes through a pair of pushers as it is removed from the camera. The pusher ruptures the container and spreads the processing composition TjO and indicator dye over the imaging portion of the film unit, preventing its exposure. The processing composition develops each silver halide layer, leaving an imagewise distribution of diffusible dye in the undeveloped areas, which dye diffuses into the image-receiving layer and is viewed through the transparent support with a white background. be able to. The indicator dye shifts to a colorless state as the alkali is consumed by the neutralization layer. As before, the neutralizing layer then neutralizes the alkaline composition after the temporary barrier collapse of the present invention. This particular film unit format is described in the above-mentioned US Pat. No. 3,415,644, and the reference will only be cited here and its details will be omitted. Another embodiment of a color diffusion transfer system in which temporary barriers according to the present invention can be used in dye image-receiving elements is described in US Pat. No. 3,362,819. The image-receiving element comprises a support (which can be opaque) carrying a neutralizing layer, a temporary barrier of the invention and a dye image-receiving layer.
It becomes more. The use of such elements in color transfer film units is described in U.S. Pat.
It is detailed in No. 9, and I will only cite the literature here. Useful laminate formats in which the present invention can be used include:
In addition, US Patent Nos. 3415645 and 34156
No. 46, No. 3647437, No. 3635707 and No. 3594165, and British Patent No. 13305
There is one described in No. 24.

The photosensitive elements useful in this invention can be treated with an alkaline processing composition to initiate development by any method.

A preferred method of applying the treatment composition is to use a rupturable container or pot (POd) containing the composition. Generally, the processing composition used in the present invention contains a developer for development, but if a developer is incorporated into the photosensitive element, the composition may include an alkaline solution. . In this case, the alkaline solution serves to activate the incorporated developer. Dye imaging materials that can be used in this invention include those that (1) are initially soluble or diffusible in the processing composition, but become selectively imagewise non-diffusible as a result of development, such as those described in U.S. Pat. 2
No. 647079, No. 2661293, No. 269824
No. 4, No. 2698798, No. 2802735.

No. 2,774,668 and No. 2,983,606, or (2) initially insoluble or non-diffusible in the processing composition, but which provides a diffusible image dye-forming material as a result of development, e.g., U.S. Pat. 32275
No. 50, No. 3227551, No. 3227552, No. 3227554, No. 3243294 and No. 344
No. 5,228. These materials can contain preformed dyes or dye precursors, such as color couplers, oxychromic compounds, and the like. In a preferred form of the invention, the dye imaging material is a ballasted redox dye.
redOxdyereleaser). Such compounds are generally oxidized in the form of cross-oxidation by the oxidized developer, such as alkaline hydrolysis, yielding species which release diffusible dyes as a result of the oxidation. Such a redox direlysor is Ande
rsOn and Lum U.S. Pat. No. 3,725,062 (
(published on April 3, 1973), GOmpf and Lum No. 3698897 (published on October 17, 1972)
, Ruschel et al. No. 3628952 (1971
Published on December 21, 2013), No. 34439 of BlOOm et al.
No. 39 (May 13, 1969), BlOOm et al. No. 3443940 (published May 13, 1969), and the following Belgium edition: Fleckenste
No. 788268 of LandhOlm et al. No. 796 of LandhOlm et al.
No. 041 and No. 796042, No. 7 of Haase et al.
No. 96040, Hinshaw et al. No. 810195.
I will not go into details here and will only cite the literature. In this application, the term ``non-diffusive'' refers to ``non-diffusive'' within the layer in which the material is disposed within the photographic element.
Alternatively, it means that it is not substantially diffused from the upper layer.

Similarly, "non-spreadable" means that in the presence of an alkaline solution having a high pH value of 11 or higher, the substance is substantially transferred from that layer in the photographic element into the image-receiving layer where it is mordanted. means to move. In one preferred embodiment of the present invention, the Fleckenstein
Pelkey Patent No. 788,268, et al.

Such compounds are non-diffusible sulfonamide compounds that undergo alkaline cleavage upon oxidation to release a diffusible sulfonamide dye. In certain preferred embodiments,
These compounds have the formula below. Here, (1) CO
l is a dye or dye precursor portion (Dyeprec)
ursOrmOiety), and (2) the ballast is an organic ballistic group (preferably having at least 8 carbon atoms) which contains the compound in the photographic element during processing of the photographic element with the alkaline composition. (3) Y is the carbon atom required to complete the benzene or naphthalene nucleus; (4)
G is 0R or NHRl, where R is hydrogen or a hydrolyzable moiety (MOiety) and R1 is hydrogen or a substituted or unsubstituted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl , propyl, butyl, sec-butyl, tertiary-butyl, cyclopropyl, chlorobutyl, cyclobutyl, nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, docosyl, benzyl, phenethyl, etc. (R1 has 6 carbon atoms) (If it is more than one alkyl group, it can act as a moiety or one ballast group).

The details of the above-mentioned sulfonamide compound and its specific examples are described in detail in the above-mentioned Pelkey Patent No. 788,268 of Fleckenstein et al., and the reference will only be cited here.

Sulfonamide compounds that can be used in the present invention include the following.

Compound 1 Compound 4 Compound 5 Another preferred embodiment of the invention uses an initially diffusible dye image-providing material, such as a dye developer.

U.S. Patent Nos. 3,453,107, 3,544,545, 3,551,406, 3,563,739, 35,972
No. 00, and metal complex dye developers such as those described in No. 3,705,184, and in co-inventors Lestina and Bush, U.S. Pat. This includes the described and claimed oxychrome-based developers. We will not discuss the details here;
I will limit myself to citing the literature. When an oxychrome developer is used, an image is formed by the developer diffusing into the image-receiving layer and undergoing chromodynic oxidation to form an image dye. The film unit of the present invention includes:
It can be used to obtain positive images in monochrome or multicolor or black and white.

In the three-color process, each silver halide emulsion layer of the film assembly has a dye imaging material associated therewith, and this material has a predominant spectral absorption in the region of the visible spectrum to which the silver halide emulsion is sensitive. will be presented.

Specifically, the blue-sensitive silver halide emulsion layer has a yellow image dye-forming material associated therewith, the green-sensitive silver halide emulsion layer has a magenta image dye-forming material associated therewith, and The red-sensitive silver halide emulsion layer will have a cyan image dye-forming material associated therewith. The image dye-forming substances associated with each of the silver halide emulsion layers described above may be contained within the silver halide emulsion layer itself, or may be contained in a layer adjacent to the silver halide emulsion layer. can. The concentration of dye imaging materials used in this invention can vary over a wide range depending on the particular compound used and the desired outcome.

For example, a dye imaging compound in a weight ratio of about 0.25 to about 4 to a hydrophilic film-forming natural or synthetic polymeric binder, such as gelatin, polyvinyl alcohol, etc., suitable to be penetrated by the aqueous alkaline processing composition. By using a coating composition containing a dye-imaging compound, the dye-imaging compound can be applied suspended in the layers. Generally, a large number of silver halide developers can be used for developing silver halide emulsions in the photographic elements of this invention.

The developer described above can be used in photographic elements to be activated with alkaline processing compositions. Specific examples of developers that can be used in the present invention are as follows. Hydroquinone, N-methylaminophenol, phenidone (1
-phenyl-3-pyrazolidone), dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidone), aminophenol, N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl- p-phenylenediamine, N,N,NζN'-tetramethyl-p-phenylenediamine, 4-hydroxymethyl-4-methyl-
1-phenyl-3-pyrazolidone, etc.

In the present invention, when using a redox dye releaser compound, diffusible dye image formation occurs as a result of development of the silver halide emulsion.

If the silver halide emulsion used forms a directly positive silver image that is developable in the unexposed areas, such as a direct reversal internal image emulsion or a highly exposed emulsion, a redox releaser that releases the oxidized dye is used. When used, a positive-tone image is obtained on the dye image-receiving layer. After the film unit is exposed, the alkaline processing composition permeates each layer and development begins in the exposed light-sensitive silver halide emulsion layer. The developer present in the film unit develops each unexposed silver halide emulsion layer (since the silver halide emulsion is direct positive). In this way, the developer
In image form, the unexposed areas of the direct positive silver halide emulsion layer are oxidized. The oxidized developer then cross-oxidizes the redox direleasing compound, the oxidized form of which is released as a result of the imagewise exposure of the respective silver halide emulsion layer, either by direct emission or through base catalytic reaction. The previously formed dye or dye precursor is released in an imagewise manner. At least a portion of the imagewise distributed diffusible dye or dye precursor diffuses into the image-receiving layer to form a positive image of the original object. The internal image type silver halide emulsion useful in the above embodiment is a direct positive type emulsion that forms a latent image mainly on the inside of the silver halide grains, and the silver halide grains that form a latent image mainly on the surface of the grain. It is a different kind of thing.

Such internally imaged emulsions are described in Davey et al., US Pat. No. 2,592,250, issued April 8, 1952, and other publications. Other useful emulsions are described in US Pat. No. 3,761,276, US Pat. No. 3,761,266 and US Pat. Internally imaged silver halide emulsions are
This is clearly illustrated by the fact that the maximum density obtained when developing a negative-working silver image with an internal type developer is further increased compared to that obtained when it is developed with a surface type developer. can be explained. A suitable internally imaged emulsion is prepared by coating a sample portion of the silver halide emulsion on a transparent support, exposing it to a light intensity scale for a period of time from 0.01 to 1 second;
and 2 in the following developer AC internal type 1 developer).
When the maximum density is determined according to conventional photographic techniques by developing for 3 minutes at a temperature of 0°C,
At least 5 times the maximum density obtained when a silver halide emulsion exposed in the same manner is developed in developer B (a 6-surface type 1 developer) as described below at a temperature of 20° C. for 4 minutes. such that it has a maximum concentration of Preferably, the maximum concentration in developer A is at least 0.5 concentration units greater than that in developer B. When an internally imaged silver halide emulsion is processed in the presence of a fogging agent or a nucleating agent, the emulsion directly gives a positive working silver image.

Such emulsions are particularly effective in the embodiments described above. Suitable fogging agents include Ives U.S. Pat. No. 2,588,982 (issued March 11, 1952);
and hydrazine, Whit-MOre, disclosed in No. 2563785 (published August 7, 1951).
hydrazides and hydrazones disclosed in U.S. Pat. No. 3,227,552 (issued January 4, 1966), UK Pat.
Hydrazone 4th salt described in No. 15, US Pat. No. 37184
The hydrazone-containing polymethine dyes described in No. 70, acrylhydrazinophenylthiouria, or mixtures thereof are included. The amount of fogging agent used can vary widely depending on the desired results. The concentration of the fogging agent is generally from about 0.4 to about 89 moles of silver contained in the photosensitive layer in the photosensitive element; otherwise, if the fogging agent is included in the developer, from about 0.1 to about 29 for liquid 11. However, U.S. Pat.
The fogging agents described in No. 615,615 and No. 3,718,470 contain 50 to
It is desirable to use it at a concentration of 400. A typical effective direct positive emulsion is WhitmOre, U.S. Pat. No. 3,227,552 (issued January 4, 1966).
, Evans No. 3761276 (published September 25, 1973), Gilman et al. No. 3761267, MiltOn No. 3761266, MOtter
There are those disclosed in the same No. 3703584'.

In another aspect of the invention, the direct positive emulsion is formed by fogging the surface of the silver halide grains either chemically or by radiation, resulting in an emulsion that develops to maximum density without exposure to light. I can do it.

Upon exposure, the exposed areas are not developed, thus providing image distinction and a positive image. Silver halide emulsions of this type are, for example, well known to those skilled in the art and are disclosed, for example, in Berriman, US Pat.
Published February 6, 1968) and IllingswOr
No. 3501305, No. 3501306, and No. 3501307 (all issued on March 17, 1970) of th. In yet another aspect of the invention, the direct positive emulsion is a direct positive emulsion, published by Me.
TheOryOftheP by s and james
hOtOgraphicPrOcess(149-16
It can be an emulsion of the type described on page 7).

The various silver halide emulsion layers of the color film assembly according to the invention can be arranged according to a conventional order.

That is, a blue-sensitive silver halide emulsion layer can be placed at a position closest to the exposure surface, followed by green-sensitive and red-sensitive silver halide emulsion layers. If necessary, a yellow dyeing layer or a yellow colloidal silver layer may be present between the blue-sensitive layer and the green-sensitive layer. This is because the blue light that can be transmitted through the blue-sensitive layer is absorbed or otherwise lost. If desired, the selectively color sensitive silver halide emulsions can be arranged in different orders. For example, with respect to the exposed surface, a blue-sensitive layer can be placed first, followed by a red-sensitive layer and a green-sensitive layer. The rupturable containers used in the present invention are, for example, U.S. Pat. No. 2,543,181;
No. 6, No. 2653732, No. 2723051, No. 3056492, No. 3056491, and No. 3152515. Generally, such containers include a rectangular sheet of material made of a liquid-impermeable and air-impermeable material that is folded longitudinally in half to form two wall sections. There is. The sheet material is sealed together along its periphery, i.e., longitudinal edges and ends, to create a cavity for containing the processing solution. In the color film unit according to the invention, each silver halide emulsion layer containing a dye-imaging material or having a dye-imaging material present in an adjacent layer may be of a material containing gelatin, calcium alginate, or Any of those disclosed in U.S. Pat. No. 3,384,483,
For example, US Patent No. 2992104, US Patent No. 30436
No. 92, No. 3044873, No. 3061428, No. 3069263, No. 3069264, No. 3121011 and No. 3427158, It can also be isolated from another silver halide emulsion layer.

Generally speaking, unless otherwise specified, the silver halide emulsion layer in the present invention comprises photosensitive silver halide dispersed in gelatin, and has a thickness of about 0.5 mm. 25 to 5 microns.

The dye imaging material is in a separate layer having a thickness of about 0.25 to 5 microns and is dispersed in a polymeric binder, such as gelatin, which is permeable to an aqueous alkaline solution. The thickness of the permeable polymeric interlayer, e.g. gelatin, is about 0.25 to 5 microns.Of course, these thicknesses are only approximate and can vary arbitrarily depending on the desired product. The alkaline solution-permeable, light-reflecting layer used in a particular form of photographic film unit can generally consist of any type of opacifying agent dispersed in a binder, so long as it has the desired properties. .

White reflective layers are particularly preferred. This is because it provides a beautiful background for the transferred dye image and has the desired optical properties of reflecting incident light. Suitable opacifying agents include titanium dioxide, barium sulfate, zinc oxide, barium stearate, silver flakes, silicates,
Opacifying agents include alumina, zirconium oxide, zirconium acetylacetate, sodium zirconium sulfate, kaolin, mica, or mixtures thereof in amounts that vary over a wide range depending on the degree of opacification desired. can be dispersed in a polymeric matrix impregnated with an alkaline solution, such as a binder such as gelatin, polyvinyl alcohol, etc.

If desired, polishing agents such as stilbenes, coumarins, triazines and oxazoles can be added to the light reflective layer. When it is desired to increase the opacifying ability of the light-reflecting layer, a dark opacifying agent, such as a southern indicator dye, can be added to it, or carbon black, nigrosine dye, etc. can be applied to another layer adjacent to the light-reflecting layer. You can also do that. The neutralizing layer used in the present invention, which acts after the processing composition passes through the temporary barrier, lowers the PH value of the image layer to about 13 or 1.
4 to at least 11, preferably in the range of 5 to 8, within a short time after swelling.

For example, good results have been obtained using the polymeric acids disclosed in U.S. Pat. No. 3,362,819, or the solid acids or metal salts (zinc acetate, zinc sulfate, magnesium acetate, etc.) disclosed in U.S. Pat. No. 2,584,030. can get. Such neutralizing or precipitating material stabilizes the dye image by lowering the south of the film unit after development, terminating development and greatly reducing subsequent dye transfer. Any material can be used as the image-receiving layer in this invention so long as it achieves the desired function when mordanting or otherwise fixing the dye image.

The particular substance chosen here naturally depends, of course, on the dye to be mordanted. If acidic dyes are intended to be mordanted, the image-receiving layer may contain a basic polymeric mordant, such as Minsk U.S. Pat. No. 2,882,156 (
polymers of aminoguanidine derivatives of vinyl methyl ketone, as described in
and, for example, US Patent No. 370,969 to Cohen et al.
No. 0, No. 3625694, No. 3898088 (
(Published Aug. 5, 1975) and Burness et al., US Pat. No. 3,859,096. Other mordants useful in the present invention include poly-4-vinylpyridine, 2-vinylpyridine polymeric methyl-p-toluenesulfonate, and Sprague et al., U.S. Pat.
84430 (published October 11, 1949) and cetyltrimethylammonium bromide. Effective mordant compositions further include:
It is also described in U.S. Pat. No. 3,271,148 to Witm Ore and U.S. Pat. Other materials useful in the dye image-receiving layer include alkaline solution permeable polymer layers, such as N-methoxymethyl polyhexyl methylene adipamide, partially hydrolyzed polyvinyl acetate, and of similar character. This includes other substances that have

Generally, the image-receiving layer, preferably an alkaline solution permeable image-receiving layer, is transparent and has a thickness of about 2.5 to 5 microns.
Good results can be obtained. It goes without saying that this thickness can be modified according to the desired result. The image-receiving layer may contain UV-absorbing substances to prevent the dye image from fading due to UV light, and may also contain polishing agents such as stilbenes, coumarins, triazines, oxazole, and dye stabilizers such as chromanols and alkylphenols. You can also. The alkaline treatment compositions used in this invention are conventional aqueous solutions of alkaline substances, including, for example, sodium hydroxide, sodium carbonate, or even amines such as shell amines.

The alkaline processing compositions of this invention preferably have a pH value above 11 and preferably contain the developer described above. The solution also preferably contains viscosity increasing compounds, such as high molecular weight polymers. Examples of such compounds include water-soluble ethers inert to alkaline solutions, such as hydroxyethylcellulose, or alkali metal salts of carboxymethylcellulose, such as sodium carboxymethylcellulose. Advantageously, the concentration of the viscosity increasing compound is from about 1 to about 5% by weight of the treatment composition, so that the concentration of the viscosity increasing compound is from about 100 to about 200% by weight of the treatment composition.
,000 cp. In certain embodiments of this invention, opacifying agents such as TiO2, carbon black, PH indicator dyes, etc. may also be added to the treatment composition. Any material can be used as the support for the photographic elements of this invention so long as it does not have a deleterious effect on the photographic properties of the film unit and is dimensionally stable. Common flexible sheet materials include nitrocellulose film, acetylcellulose film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film, and poly-alpha-olefins such as polyethylene and polypropylene films. , and related films or resinous materials. The support can have a thickness of about 2-9 mils (50-255 μm). If desired, ultraviolet absorbing materials can be included in the support or formed as a separate layer on the support. Silver halide emulsions useful in the present invention are those known to those skilled in the art and include PrOductLi
sensingIndex, Volume 92, December 1971, Published 9232, Page 107, Section 1, 6 Types of Emulsion ○hu
1si0ntypes) 1.

These emulsions were chemically sensitized (Ch.
1 and 108-109, Section W, 6 Spectral Sensitization
These emulsions may be chemically or spectrally sensitized as described in ``Antifoggants and Stabilizers'', supra, page 107, Section V, 8 Antifoggants and Stabilizers.
By using the substances described in the tabilizers, it is possible to suppress the formation of fog and prevent loss of sensitivity during storage. These emulsions are described in Ibid.
~Page 108, Section 6, Development Control Agent (DevelOpmen)
tmOdifiers)” Section “Hardne
r) ゛ and Section ``Coating aids (COating
Development modifiers, hardeners and coating aids may be included, as described in US Pat. These emulsions, and other layers of photographic elements used in this invention, are described in "Plasticizers and Lubricants," supra, p. 108, Section M.
ub-RlOanl8) - Section, 1 Vehicle (Vehi
cles) 1 and 109, Section X, 6 AbsOrbingandfilt
It may contain plasticizers, vehicles and filter dyes as described in ERDS'2. These emulsions, and other layers of the photographic elements used in this invention, are incorporated with additives by using the techniques described in Ibid., p. 109, Section 6, Methods of Addition 1. You may. These emulsions are described in Ibid., p. 109, No. 6 Coating Procedures.
)'' can be applied by using various techniques described in .

Please note that the details of these disclosures are omitted here.
I will only clarify the literature.

Next, examples of the present invention will be described.

EXAMPLE 1 Effect of Timing Layer over a Temperature Range A treated cover sheet for a laminated integral negative receiver film unit was prepared using poly(n-butyl acrylate-CO-acrylic acid) 190 meq/m2 (A 1
(70 wt% acrylic acid), diatomaceous earth 0.44 fl/m2 and bis-vinylsulfonylpropane O. 89/m2 and an upper layer containing a polymerized hydrosol consisting of 20% solids of a terpolymer consisting of 15% by weight acrylonitrile, 79% by weight vinylidene chloride, and 6% by weight acrylic acid. ethylene acid) by coating it on a film support.

The soil layer was applied at a rate of 8.6 to 11 fl/m2 of polymer. The effectiveness of the timing layer in the cover sheet is
Sensitivity measurements were determined over a wide temperature range of laminated monolithic negative receiver elements coated on a poly(ethylene terephthalate) film support with the following sequence of layers (coating rates are in fl/m2 unless otherwise stated): ).

(1) Copoly[styrene-CO-N-vinylbenzenyl-N,N,N-hexylammonium chloride] (
2.2), poly(methyl methacrylate) beads (0.0
44) and an image-receiving layer of gelatin (2.2), (2)
a reflective layer of titanium dioxide (22) and gelatin (2.2),
(3) Carbon black (2.7) and gelatin (1
．． 7) Opaque layer, (4) a cyan image dye-forming compound (0.54) represented by the following formula, 1,4-cyclohexylene dimethylene bis(2-ethylhexanoate) (0.27) and gelatin (0.73), (5) red-sensitive internally imaged gelatin-silver chlorobromide emulsion (gelatin 1.19/I and silver 1.19/Trl1);
2-sec-octadecylhydroquinone-5-sulfonic acid (8 g/mole silver) and the nucleating agent 1-acetyl-2-{p-[5-amino-2-(2,4-di-t
-pentylphenoxy)benzamide]phenyl}hydrazine (1.59/1 mole of silver), (6) gelatin (
0.55) and 2,5-di-sec-dodecylhydroquinone (1.1); and gelatin (1.1), (8) green internal image type gelatin monochlorobromide emulsion (
gelatin 1.2 g/d and silver 1.19/M2), 2-
Sec-octadecylhydroquinone-5 sulfonic acid (1
69/silver 1m01e), and nucleating agent 1-acetyl-
2-{p-[5-amino-2-(2,4-Di-t-pentylphenoxy)benzamide]phenylene}hydrazine (1.59/silver 1m61e), (9) gelatin (0.
55) and 2,5-Di-Sec-dodecylhydroquinone (1.1), a yellow image dye-forming compound (1.1) having the formula -ethylhexanoate) and gelatin (1.1), blue-sensitive internal image gelatin monochlorobromide emulsion (gelatin 1.1 g/d and silver 1.19/M2), 2 -Sec-octadecylhydroquinone-5-sulfonic acid (89/silver 1m01e) and nucleating agent 1-acetyl-2-{p-[5-amino-2-(2,4-Di-t-pentylphenoxy) benzamide] phenyl} hydrazine (1.59/silver 1m0I
e), and (sub) gelatin overcoat (0.54) The above silver halide is a direct positive emulsion with high internal sensitivity and low surface sensitivity of the type described in U.S. Pat. No. 3,761,276. be.

The treatment composition was used as a pot (POd) and spread through the cover sheet between the laminated integral negative receiver sample and the cover sheet sample exposed to the graduated density multicolor test article. Add distilled water for a total of 1 liter. These elements were stacked for 3 hours, and the following sensitivity measurements were obtained from the image-receiving side of the stack. Example
2 Methyl methacrylate 15 weight? , a polymeric hydrosol containing 83% by weight vinylidene chloride and 2% by weight itaconic acid as an overcoat latex timing layer, 18.49/m
An emulsion oversheet was prepared similar to Example 1, except that the polymer coating was applied in an amount of 1.

The above oversheet sample was tested with elements according to Example 1 with the following sensitivity measurements.

Example 3 Penetration rate at timing 1 over a wide temperature range;
Determination of the ability of various timing layers to produce late stopping effects at low temperatures is described in U.S. Pat. No. 3,785,815 and U.S. Pat.
21 (received November 5, 1974), a polyvinyl acetate-polyvinyl alcohol latex, and a latex of the present invention.
Neutralization tests were carried out over a temperature range of .

The oversheet consists of a polyester support, a 2.29/I first layer made of a 30/70 (weight ratio) copolymer of poly(butyl acrylate-CO-acrylic acid), and a poly(styrene-CO) A 2.29/TI second subbing layer consisting of a 50/50 (mole ratio) polymer of monomaleic anhydride and an overcoat for the timing layer under test were prepared by applying a covering for each timing layer. Efficacy in sheets was determined by the time required to reduce the pH of the laminate monolithic film unit of the simulation to 10 as measured by the color change of the thymol phthalein dye from blue to colorless.

The dye was incorporated into a simulated laminated monolithic element formed by coating the following layers on a polyester film support: Poly[styrene-CO-N-benzyl-
A mordant layer of a 2:1 mixture of N,N-dimethyl-N-(3-maleimidopropyl) ammonium chloride] and gelatin, a gelatin layer, and a gelatin layer containing a thymolphthalein indicator dye. The treatment composition described in Example 1 was used in a pot and spread between the elements of the simulation, including the indicator dye and cover sheet samples.

This was done by passing the developer through a 0.0 sand Deutscher 7 between a pair of juxtaposed rollers to give the developer a thickness of 0.111. The times listed here represent the average time between the time the indicator dye begins to change color and the time until the dye completely changes color by visual observation.

As seen in the table, the latex polymer according to the invention has a much longer development time at low temperatures and a much shorter development time at high temperatures.

Example 4 Effect of Timing Layer on Sensitivity Measurements over a Wide Temperature Range The cover sheet described in Example 3 was used with the control timing layer described in Example 3 to process a multicolor laminated integral negative receiver element.

This element consists of a poly(ethylene terephthalate) film support coated with layers in the following order (unless otherwise indicated, coating weights are in g/m). (1)
Poly[styrene-CO-N-benzyl-N,N-
Dimethyl-N-vinylbenzylammonium sulfate-CO-divinylbenzene latex (2.2
) and an image-receiving layer of gelatin (2.2). (2)
Titanium dioxide (21.5) and gelatin (1.7
) reflective layer.

(3) Carbon black (2.7) and gelatin (
1.7) Opaque layer.

(4) Cyan image forming compound having the following formula (0.54)
.

Disperse in 1,4-cyclohexylene dimethylene Bis (2-ethylhexanoate) and gelatin (1.1).

(5) Interlayer of gelatin (0.54) (6) Red-sensitive, direct positive, internally imaged gelatin-silver bromide emulsion (1.2 Ag) 1.1 gelatin), 5-Sec
-octadecylhydroquinone-2-sulfonic acid (16f
I/silver 1m01e) and 1-acetyl-2-4
-[5-amino-2-(2,4-Di-t
Under an intermediate layer (8) of gelatin (1.1) and 2,5-Di-Sec-dodecylhydroquinone (1.1) A magenta image dye-forming compound of formula (0.54) is dissolved in dimethyl lauramide (0.27) and dispersed in gelatin (1.1).

(9) Green-sensitive direct positive internal image type gelatin-silver bromide emulsion (1.35Ag) 1.1 gelatin), 5-S
ec-octadecylhydroquinone-2-sulfonic acid (1
6g/AglmOle) and 1-actyl-2
-{4(5-amino-2-(2,4-D
i(t-pentylphenoxy)-benzamido]phenyl}hydrazine (4009/AglmOle), Qω gelatin (1.2) and 2,5-Di-Sec-dodecylhydroquinone (1.1), aυ yellow of the formula below Image dye-forming compound (0.86).

This material is dissolved in dimethyl lauramide (0.43) and dispersed in gelatin (1.1). a Blue-sensitive direct positive internal image type gelatin silver bromide emulsion (1.25Ag
) 1.1 gelatin), 5-Sec-octadecyl-
5-hydroquinone-2-sulfonic acid (169/Ag
lmOle) and 1-actyl-2-{4-[5-amino-2-(2,4-Di-t-pentylphenoxy)benzamide]phenyl}hydrazine (5007
! ! y/AglmOle), A, gelatin (0.54
) and 2,5-Sec-dodecylhydroquinone (0
．． 11) Top coat layer. The element was exposed to a tungsten electric light source through a polychrome test object. The treatment composition described in Example 1 was used in pots and spread between the element and the cover sheet at temperatures of 15°C and 38°C. This operation was carried out by passing a transferred "sandwich" structure through a pair of juxtaposed rollers, giving a layer thickness of 65 μm. These properties were compared to those obtained by similar tests of the timing layer of Example 3. The results are shown in the table below. As seen in the table, the timing layer according to the present invention has almost constant D at both high and low temperatures in the Dirnn band.
The mlaX band is higher at low temperatures, whereas the conventionally known ones have substantially higher Dmln and higher I)Nax at higher temperatures.

At very low temperatures the timing layer of the present invention outperforms those previously known. Examples 5-7 Various coating weights of the single latex timing layer embodiment of the present invention were compared for sensitivity measurements with the timing layer described in U.S. Pat. No. 3,785,815.

30/70 (weight ratio) poly(butyl acrylate-CO)
- acrylic acid) (19.49/A) and a second subbing layer (Subbing
A coating was prepared consisting of a structure on a polyester support containing (2.2 g/M2).

The following latex was applied to the above sample.

The cover sheet described above was used to process multicolor laminated integral negative receiver elements.

The element is a poly(ethylene terephthalate) film support carrying each layer in the following order (coating weights are given in parentheses as 9/Trl unless otherwise noted). (1
) Poly[styrene-CO-N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride-C
O-divinylbenzene] latex (2.2) and gelatin (2.2) image-receiving layer. (2) Reflective layer of titanium dioxide (21.5) and gelatin (3.2).

(3) Carbon black (2.7) and gelatin (1
．． 7) Opaque layer.

(4) Cyan dye-forming compound of Example 1 (0.54) dispersed in gelatin (1.1).

(5) Intermediate layer of gelatin (0.54).

(6) Red-sensitive direct positive internal image type gelatin/silver bromide emulsion (1.2 Bl.l gelatin), 5-SeC-octadecylhydroquinone-2-sulfonic acid (169/
Silver 1r1X) 1e), fogging agent Taki 1:1-acetyl-2
-{4-[5-amino-2-(2,4-Di-Tert
-Phenyl(phenoxy)benzamide]phenyl}hydrazine (150W9/silver 1m01e) and fogging agent.
/F62:1-[4-(2-formylhydrazino)-
phenyl]-3-phenylthiouria (6.4η/silver 1
m01e).

(7) Gelatin (1.1) and 2,5-Di-SeC
- Interlayer of dodecylhydroquinone (1.1). (8) Diethyl lauramide (
Magenta image dye-releasing compounds of the examples in 0.27) (
0.54).

(9) Green-sensitive direct positive internal image gelatin/silver bromide emulsion (1.35 Bl.l gelatin), 5-Sec-octadecylhydroquinone-2-sulfonic acid (169/Agl
mOle), and fogging agent Taki 1 (240TI1f/A
glmOIe) and fogging agent A2 (4.87!1f/
AglmOle).

Examples 8 and 9 below further demonstrate the improvements obtained using the two-layer embodiment of the temporary barrier according to the present invention.

Example 8 A combination of timing layers of the present invention was compared to a single timing layer as described in French Patent No. 2,290,698 in an image transfer element as follows.

*(Serial) Gelatin (1.2) and 2,5-Di-Se
Interlayer of c-dodecylhydroquinone (1.1).

(10 Yellow one-image dye-releasing compound (0.86)
Present in diellulauramide (0.43) dispersed in gelatin (1.1).

◎ Blue-sensitive direct positive internal image type gelatin/silver bromide emulsion (
1.25 Tao Bl. gelatin), 5-SeC-octadecyl-5-hydroquinone-2-sulfonic acid (16 g/A
glmOle), and Foggant Falls 2 (117!1f/
AglmOIe).

(auto)gelatin (0.54) and 2,5-Di-Se
Overcoat layer of c-dodecylhydroquinone (0.11).

The element was exposed to a tungsten electric light source through a multicolored test object.

The Z treated composition as used in Example 1 was used as a pot and spread between the element and the cover sheet at temperatures of 16°C and 38°C. This operation was carried out by passing the sandwich structure between a pair of juxtaposed rollers to a thickness of 75 μm. After spreading the treatment composition,
The above temperature was maintained for 2 minutes. Reflection density analysis of the transparent support was performed for at least 3 hours after lamination to obtain a sensitivity curve for the mordant dye on the image receiving layer. The results are shown in Table 5.

4.49/M2.

Acid layer poly(n-butyl acrylate-CO-acrylic acid) 19
0meq/Trlsbis-vinylsulfonylpropane 0.89/M2 and 0.44g/M2 diatomaceous earth 0.44
9/Transparent poly(ethylene terephthalate) support 2.2
Layer timing layer poly(acrylonitrile-CO vinylidene monochloride-CO
-acrylic acid) (15/79/6) 1.19/Trl and 0.02 g/M2 of methyl methacrylate beads.

89% acetyl cellulose (40% acetyl) and 1
1% poly(styrene-CO monomaleic anhydride) (approximately 50
% hydrolysis) mixture 2.2g/Iric acid layer poly(n-butyl-alkylate-CO-acrylic acid 220meq/Mlb
is-vinylsulfonylpropane 0.8g/M2 and diatomaceous earth 0.44f! To test the efficacy of the /M2 clear poly(ethylene terephthalate) support timing layer, pots containing various treatment compositions were ruptured and laminated integrally with each of the above coversheet layers as described in Example 1. The image receiving element was spread between exposed samples.

The following photosensitivity measurement results were obtained. Example 9 One single timing layer and one two timing layers according to the present invention were prepared by coating the following layers on a poly(ethylene terephthalate) film support in the order listed: Two cover sheets were prepared containing:

(1) 15.5 g/M2 acid layer of poly(n-butyl acrylate-CO-acrylic acid) (acrylic acid 70% by weight)
and (2) 5-(2-cyanoethylthio)-1-phenyltetrazole (0.119/M2), acetyl cellulose (40
% acetino(ha) (4.319/M2) and poly(styrene-CO monomaleic anhydride) (0.119/d).

(3) Poly(acrylonitrile-CO vinylidene monochloride-CO-acrylic acid) (2,159/M2).

A multicolor laminated integral negative receiver element was processed using a cover sheet. This element was prepared by coating the following layers in the order listed on a transparent poly(ethylene terephthalate) film support (coating weights are given as 9/M2 unless otherwise noted). (1) Copoly [styrene-C
Image-receiving layer of latex of O-N-vinylbenzyl-NN-dimethylammonium sulfate-CO-divinylbenzene] (2.2) and gelatin. (2) A light-reflecting layer of titanium dioxide (22) and gelatin (2.2).

(3) Carbon black (2.7) and gelatin (1
．． 7) Opaque layer〇(4) Cyan image dye forming compound represented by the following formula (0.54) This is mixed with 1,4-cyclohexylene dimethylene Bis (2-ethylhexanoate)
and dispersed in gelatin (1.1).

(5) Red-sensitive internally imaged gelatin/silver bromide emulsion (1.1
silver, 1.1gelatin), 2-octadecylhydroquinone-5-sulfonate (169/silver 11NOl)
e) and the nucleating agent 1-acetyl-2-{4-[5-amino-2-(2,4-Di-t-pentylphenoxy)
benzamide]phenyl}-hydrazine and 1-p-formylhydrazinophenyl-3-phenyl-2-thiourea (150η and 6711f/m01 silver, respectively)
e).

(6) Gelatin (1.6) and 2,5-Di-Sec
- Interlayer of dodecylhydroquinone (1.3). (7) A magenta image dye-forming compound represented by the following formula (0.54
).

Disperse in diethyl lauramide and gelatin (1.2). (8) Green-sensitive internally imaged gelatin/silver bromide emulsion (1.25 silver, 1.3 gelatin), potassium 2-octadecylhydroquinone-5-sulfonate (169/silver 1m01e) and the former 1-acetyl-2 -{4-
[5-Amino-2-(2,4-Di-t-pentylphenoxy)benzamide]phenyl}hydrazine and 1-
Formylhydrazinophenyl-3-phenyl-2-thiourea (1201f1f! I and 2.5 w/silver 1m01e
).

(9) Gelatin (1.6) and 2,5-Di-Sec
- Interlayer of dodecylhydroquinone (1.3). A yellow image dye-forming compound having the formula AI.

Disperse in 1,4-cyclohexylene dimethylene Bis (2-ethylhexanoate) and gelatin (1.1).

00 blue-sensitive internally imaged gelatin/silver bromide emulsion (1.25
silver 1.3 gelatin), potassium 5-octadecylhydroquinone-2-sulfonate (169/silver 1m01e)
and the nucleating agent 1-p-formylhydrazinophenyl-3-phenyl-2-thiourea (5.5Tn9/silver 1m
01e) and (auto)gelatin (0,9) and 2,5
- Overcoat of didodecylhydroquinone (0.11).

The photosensitive element prepared as described above was exposed to a multicolor test object of certified density. The processing composition described below was applied in a pot and spread between a photosensitive material and an opaque acetylcellulose sheet by passing the six-sandwich structure between a pair of juxtaposed rollers. Table 7 shows the sensitivity measurement results.

Example 10 The timing layer combination of Example 8 was tested by testing all cover sheets as described in Example 8 and US Pat.
No. 3,645, as well as a single timing layer and polyvinyl acetate-polyvinyl alcohol latex as described in French Patent No. 2,290,698.

Claims (1)

Claims: 1. A photographic element for color diffusion transfer processes comprising a temporary barrier layer between two alkali-permeable layers, said barrier layer comprising:
It has activation energy for permeation of alkaline aqueous solution of 18 Kcal/mol or more and is 5 to 35% based on weight.
a ternary copolymer latex consisting of a polymerized ethylenically unsaturated monomer, 2 to 10% of a polymerized ethylenically unsaturated carboxylic acid or its anhydride, and 55 to 85% of a polymerized vinylidene chloride. A photographic element featuring. 2 Photographic elements for color diffusion transfer processes comprising a temporary barrier layer between two alkali-permeable layers, said barrier layer comprising two alkali-permeable layers.
a combination of two layers, in which the layer to which the aqueous alkaline solution is first contacted has an activation energy for penetration of the aqueous alkaline solution of 18 Kcal/mol or more, and
Consisting, by weight, of 5-35% polymerized ethylenically unsaturated monomer, 2-10% polymerized ethylenically unsaturated carboxylic acid or its anhydride, and 55-85% polymerized vinylidene chloride. A photographic element comprising a ternary copolymer latex, the second layer comprising a polymer having an activation energy of aqueous alkaline penetration of 18 Kcal/mole or less.