JPS5931695B2 - photosensitive recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photography, and more particularly, to the use of hydroquinone esters within or behind a timing layer with high activation energy to provide a competitive developer after contact with a processing composition. The present invention relates to a photosensitive recording material (or photographic assemblage) for use in color diffusion transfer photography.

Various forms of integrated color transfer elements are known in the art. These known forms are disclosed, for example, in US Pat. No. 3,415,644 and US Pat.
No. 5645, No. 3415646, No. 364743
7, Canadian Patent No. 3635707 and Canadian Patent No. 3756815, and Canadian Patent No. 928559 and Canadian Patent No. 6740.
It is described in No. 82.

According to these forms, an image-receiving layer carrying a photographic image (the image to be observed) is present in the assemblage structure when a transparent support is used on the viewing side of the assemblage. It can be permanently bonded to and integrated with the imaging and auxiliary layers contained therein. The image is formed by dye created in the image-forming unit, which then diffuses through each layer of the structure to the dye-image-receiving layer. After exposure of the assemblage is complete, an alkaline processing composition can be passed through the various layers to begin development of the exposed light-sensitive silver halide emulsion layers. The silver halide emulsion layers are developed in proportion to their respective exposures, and the image dyes formed or released in the respective imaging layers begin to diffuse into the structure. At least a portion of the imagewise distributed diffusible dye diffuses into the dye image-receiving layer, thus forming an image corresponding to the original (subject). Another form of color diffusion transfer assembly, the so-called peel-apart system, is described, for example, in U.S. Pat. No. 2,983,606.
No. 3362819 and No. 3362821.

These systems allow the image-receiving element to be peeled off from the photosensitive element after development and dye transfer (transfer to the image-receiving layer) is complete. US Pat. No. 3,462,266 discloses oxazines and benzoxazines that are decomposed to hydroquinones under alkaline conditions. These compounds are described in the above-mentioned patent specification as being auxiliary developer precursors in dye developer image transfer systems, and are also present in various locations, such as in overcoat layers, as spacers. It can be present in the layer, in the mordant layer or in the acidic layer. Conventionally, competitive developers are used in many photographic assemblages.

For example, ResearchDisclOsurell5
162, November 1976, p. 79, states that mixtures of certain developers with alkali-soluble auxiliary developers, such as hydroquinone, methylhydroquinone, and t-butylhydroquinone, can be used in diffusion transfer assemblies, such as those described. It is disclosed that the present invention is particularly useful for achieving dye images having a desired sensitometric characteristic curve when using dye emitters such as dye emitters. Note that, for example, in a diffusion transfer system, it is not always possible to obtain the optimum development temperature. At higher temperatures, such as 32-35 DEG C., development occurs at a relatively faster rate and more dye is released, thus resulting in significant speed losses, Dmax. and Dnlin. This causes an increase in By the way, the presence of a competing developer in the processing composition may help alleviate problems such as those described above, since the competing developer will develop the silver but will not release any dye. Dew. Drrlin.
can be reduced in this way, but the speed loss remains and cannot be resolved. Furthermore, Dmax. Although the increase in the number of cases is still unresolved, this is not significant enough to be visible to the naked eye. Here, "speed" is a measure of sensitivity, as recognized in this field. Another problem that arises when using competing developers in processing compositions is the variation in developer layer thickness (hereinafter referred to as "DLT") for a given film unit.
It is. For example, in a camera where the user rotates a crank by hand to feed the film unit out of the camera body, the speed at which the user moves the crank is directly the DLT.
For example, if the crank rotation speed is increased, a relatively small DLT will be obtained. For cameras with a built-in motor drive, DL may vary depending on the viscosity of the processing composition, processing temperature, etc.
T will vary. Such variable DLT is
Ultimately, this increases the variability of competing developers used in processing compositions (because competing developers are used at relatively low concentrations). By the way, according to the present invention, competitive development has been developed in a direction that significantly reduces the speed loss associated with high-temperature development as described above, and at the same time eliminates the variation in competitive developer concentration that accompanies variation in DLT. It has been found that the agent can be used.

Thus, it has been discovered that the use of certain hydroquinone esters within or after the timing layer, which has a high activation energy, may provide the advantages described above. The use of compounds such as those described above within or after the timing layer can provide a time delay before the resulting material is ready for use. During processing, the processing composition passes through all or a portion of the timing layer until the composition contacts the hydroquinone ester.
Subsequently, the ester groups are hydrolyzed and the resulting hydroquinone can freely diffuse into the photosensitive layer and participate in the development. By using hydroquinone in its unprotected state or in the form of a water-insoluble ester, a timing layer (in a preferred embodiment) with an organic solvent-coated polymer layer as an undercoat can be obtained.
The hydroquinone can be easily and advantageously incorporated into the hydroquinone and remains stable upon incubation. The timing layer used in the present invention has a high aqueous alkali permeation activation energy for aqueous alkali permeation.

The timing layer of the present invention rapidly "decomposes or otherwise cleaves" at temperatures above about 30.degree. If the applied temperature is below 30°C, the permeation of the treatment composition will be relatively slow. However, in this case, it becomes possible to incorporate a relatively large amount of hydroquinone ester. If processing were carried out at a temperature of 32°C, where the amount of dye release would normally be excessive, the timing layer would rapidly decompose during processing, thus leaving a large amount of competing developer in the developed silver. It is forced to spread. As a result, although there is a large amount of silver development, the amount of dye released is approximately the same as that obtained when lower temperatures are applied. The speed loss that would have been recognized under the alternative law is
Therefore, it can be significantly reduced. Note that if a large amount of competitive developer is mixed in the processing composition, the same effect as in the above case cannot be expected (because
No matter what temperature is applied, the amount of dye released will be significantly less). Thus, the present invention can provide a means to advantageously control the effects of high temperature overdevelopment, which typically results in dark images with high dye densities. A photographic assemblage according to the present invention comprises: (a) a support and at least one light-sensitive silver halide emulsion layer applied over the support, which emulsion layer is associated with a dye image; (b) a dye image-receiving layer; (c) an alkaline processing composition and means for delivering the processing composition into the assembly; (d) said dye image-receiving layer. (e) a neutralizing layer disposed on one side of the timing layer furthest from the base, and (e) such that the treatment composition must first pass through the timing layer prior to contacting the neutralizing layer. a timing layer disposed intermediate the neutralizing layer and the photosensitive silver halide emulsion layer, and the assembly also contains a silver halide developer.

Additionally, the assemblies of the present invention contain a hydroquinone ester silver halide developer either (1) in the timing layer or (2) in an adjacent layer next to the timing layer;
The adjacent layer is positioned with respect to the timing layer such that the treatment composition first passes through the timing layer prior to contacting the adjacent layer, and the timing layer has a concentration of less than 18 kcal/mol. The aqueous alkaline treatment solution (herein also simply referred to as aqueous alkaline solution) has a large permeation activation energy.

Here, the hydroquinone ester can be represented by the following general formula. (In the above formula, G is hydrogen, -COR or -SO2R, and G' is
-COR or -SO2R, and the above formula: -COR and -
R in SO2R is an alkyl group or substituted alkyl group having 1 to 20 carbon atoms or an aryl group or substituted aryl group having 6 to 12 carbon atoms, and z is hydrogen, 1 is an alkyl group (including substituted alkyl groups) having ~6 carbon atoms, an alkoxy group (including substituted alkoxy groups) having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms ).

In the above general formula, Z is generally a methyl group, ethyl group, isopropyl group, t-butyl group, or 6
Aryl groups having ~8 carbon atoms, such as phenyl, m-tolyl, p-methoxyphenyl, etc. (if one or more acyl or sulfonyl groups are hydrolyzed) The condition is that the compound of the above formula can diffuse at a sufficient rate).

Similarly, when G and G' in the above formula are each an acyl group or a sulfonyl group, insofar as the compound of the above formula can be hydrolyzed to the corresponding hydroquinone, for example, an acetyl group, a propionyl group, a benzoyl group, an ethoxy carbonyl group, ethoxalyl group, methylsulfonyl group,
Groups such as tolylsulfonyl groups can optionally be used as G and G. Hydroquinone esters can be used in accordance with the present invention at any concentration effective for the intended purpose.

Good results have been obtained when a concentration of about 0.054 to about 0.54 y/M2 is applied; Also, about 0.10 to about 0.4
Particularly good results were obtained when a concentration of 5t/i was applied. Examples of hydroquinone esters useful in the present invention are listed below.

(1) Hydroquinone Diacetate The hydroquinone esters used in the present invention, as described above, can be used within the timing layer or at the rear of the timing layer with respect to the side to which the treatment composition is applied, as discussed above.

These hydroquinone esters are advantageously incorporated within the timing layer in order to ensure that competitive developer release takes place after a limited period of time. If a relatively long time delay is desired, the compound can simply be incorporated into an adjacent layer behind the timing layer and further away from the silver halide layer to be developed. good. This layer may be adjacent to the timing layer or within an adjacent layer several layers apart from the timing layer, depending on the desired result. In the case of the present invention, any material can be used as the timing layer as long as it has the above-mentioned high alkaline aqueous solution permeation activation energy.

Particularly preferred timing layers useful in the present invention are:
It contains a polymer latex having an alkaline aqueous solution permeation activation energy greater than 18 kcal/mol.

Such a latex timing layer can be obtained through coalescence or partial coalescence of polymer particles from an aqueous latex. Preferred latex timing layers, along with methods of synthesizing those layers, are described in U.S. Patent Application No. 67,694.
No. 5 (Applicant: Hanniel, Application date: April 14, 1976).

These timing layers retard the neutralization of the alkaline processing composition by the acidic layer, thus making the formation of dye images with high quality more reproducible over a wide temperature range. The thickness of the acidic layer and the thickness of the polymeric layer are not critical for properly measuring the activation energy.

For example, the explanation regarding the calculation of activation energy is Kin
etics and Mechanism 2nd edition, Publisher: New York, JOllrlWileyandSON
sll96l, pp. 22-25.

Latex polymers having an alkali aqueous solution permeation activation energy greater than 18 kcal/mol include, for example, poly(methyl acrylate toko itaconic acid monomonovinylidene chloride).

Preferred polymer latexes having an aqueous alkaline permeation activation energy greater than 18 kcal/mole contain from about 5 to about 35% by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10% by weight. of polymerized ethylenically unsaturated carboxylic acid and about 55 to about 85 weight percent of polymerized vinylidene chloride.

To prepare these three-component copolymers, any ethylenically unsaturated monomer that is different from the other monomers in the polymer latex can be used, such as: alkyl acrylates and Alkyl methacrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate; and vinyl esters, amides, nitriles, ketones, halides, ethers, olefins, diolefins For example, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, acrylamide, methacrylamide, vinyl chloride, methyl vinyl ketone, fumaric acid, esters of maleic acid and itaconic acid, 2-chloroethyl vinyl ether, dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, N-vinyl succinamide,
N-vinyl phthalimide, N-vinylpyrrolidone, butadiene, ethylene, etc.

Preferred monomers are methyl acrylate and acrylonitrile. Ethylenically unsaturated carboxylic acids that can be incorporated into the polymers as mentioned above are, for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, anhydrides of these acids, and others. Preferred carboxylic acids are acrylic acid and itaconic acid. A preferred three-component copolymer useful in the present invention is 15
Contains by weight % methyl acrylate, 83% vinylidene chloride and 2% itaconic acid.

Examples of other latex polymers useful in the present invention include, for example, U.S. Pat.
No. 8, No. 2491023, No. 2779684,
It can be found in the same No. 3437484, the same No. 2943937 and the same No. 3143421.

Latex timing layers can generally be used in a wide range of coverages. The preferred coating weight of the latex timing layer is about 1.0 to 6.07 t/Rrl, more preferably about 1 to 3 t/Rrl. In another preferred embodiment of the invention, the timing layer has a permeation activation energy greater than 181 cca1/mol.
The following components: (1) 5-85% by weight vinylidene chloride, 5-35% by weight ethylenically unsaturated monomer (see above) and O-20% by weight ethylenically unsaturated carboxylic acid (
5 to 95% by weight of a three-component copolymer consisting of
and (2) a mixture of 95-5% by weight high molecular weight carboxyester lactones.

The lactone component as described above can have the following structural units. In the above formula, R1 is an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R2 and R3 are each hydrogen or a methyl group.

In another preferred embodiment of the invention, the lactone component as described above may have the following structural units.

In the above formula, n is an integer of 1 to 5, and R1, R2 and R3 are each as defined above.

In a preferred embodiment of the invention, an adjacent layer having a timing layer (to which is coated a latex timing layer having a high activation energy as described above) a hydroquinone ester. can be mixed.

In this "dual" timing layer configuration, the first timing layer (in which a hydroquinone ester is used)
contains a polymer latex having an aqueous alkaline permeation activation energy of less than 18 kea1/mole. The second timing layer is as described above and includes a polymeric latex having an aqueous alkaline permeation activation energy greater than 18 kcal/mole. This “dual” timing layer system
U.S. Patent Application No. 676,947 (Assignee: Hannie
and Ducharme, filed April 14, 1976). Polymers that can be used in the first timing layer as described above, having an aqueous alkali permeation activation energy of less than 18 kcal/mol, are, for example, a mixture of cellulose acetate and maleic anhydride copolymers. (5-50% by weight of this mixture)
is the above copolymer).

Such polymers are described, for example, in U.S. Patent Application No. 5212
No. 21 (Applicant: Abel. Application date: November 5, 1974). The maleic anhydride copolymer to be included in the timing layer as described above should be used at a concentration of about 2 to about 20 weight percent, depending somewhat on the other comonomer.

It has been found that it is particularly effective to use maleic anhydride copolymers in concentrations of 5 to 20% by weight. Additionally, the thickness of this timing layer should be such that a coverage of about 1 to about 57/m" is achieved. The cellulose acetate used in the timing layer as described above generally has a thickness of about It will have an acetyl content of % by weight.

When the acetyl content is 37% by weight, it is substantially more permeable than when the acetyl content is 40% by weight. Furthermore, mixed esters such as cellulose acetate propionate, cellulose acetate butyrate, etc. can also be used. The maleic anhydride copolymer can be arbitrarily selected from a variety of materials, as long as the copolymer is visible in compatibility with the cellulose acetate used to provide the transparent film. .

Particularly good results can be obtained when using poly(styrene-co-mono-maleic anhydride), poly(ethylene-co-mono-maleic anhydride) and poly(methyl vinyl ether-co-mono-maleic anhydride). Other layers containing polymers with an activation energy of less than 18 kcal/mole are, for example, polyvinyl acetate, cellulose acetate phthalate, partial acetals of polyvinyl alcohol, such as those described in US Pat. No. 3,785,815. butyl acrylate diacetone acrylamide styrene-methacrylic acid (60/30/4
/6), a mixture of polyvinyl acetate and polyvinyl alcohol, such as a polyvinyl acetate latex with a polyvinyl alcohol ratio of 78/22, as described in the aforementioned U.S. Pat. No. 5,212,221; cellulose acetate (acetate 40%) in a ratio of 95/5 to styrene-co-mono-maleic anhydride [molar ratio 50/50], and others.

One embodiment of an assemblage of transfer color elements having an integral structure and a method for forming photographic transfer images in color with which the present invention may be used is described, for example, in Canadian Patent No. 92
No. 8559.

According to this embodiment, the support for the photosensitive element is transparent and includes an image-receiving layer, a light-reflecting layer, a light-reflecting layer, an opaque layer, and a photosensitive layer (these layers include a dye image). A combination of forming material layers) is applied.
A rupturable container containing an alkaline treatment composition as described above and an opacifier such as carbon black is positioned adjacent the top layer and the transparent cover sheet. The cover sheet comprises a transparent support to which is coated a neutralizing layer and a timing layer (containing a hydroquinone ester according to the invention). To explain how to use a film unit, first, the film unit is placed in a camera, exposed to light through a transparent cover sheet, and then, when the film unit is removed from the camera, a pair of additives built into the camera are used. Guide the film unit between the pressure members. The pressure member ruptures the container and disperses the processing composition and opacifier contained therein over the imaged area of the assembly (the opacifier protects the imaged area from exposure to light). ). The processing composition develops each silver halide layer and a dye image is formed as a result of development. The dye image formed diffuses into the image-receiving layer, thus providing a positive image (viewed through the transparent support onto the opaque reflective layer, ie, the background). The neutralizing layer then neutralizes the alkaline processing composition after it has passed through the timing layer, thus completing the "shutdown" of the system. One embodiment of an assembly of transfer color elements having an integral structure and a method for forming photographic transfer images in color in which the present invention may be used is described, for example, in U.S. Pat. No. 3,415,644.

According to this embodiment, the negative has an opaque support coated with a photosensitive layer in combination with a layer of dye image-forming material. An alkaline processing composition as described above, TiO2 and an indicator dye (
A rupturable container (see US Pat. No. 3,647,437) is positioned adjacent the top layer and the transparent image receptor.

The image receptor comprises a transparent support coated with a neutralizing layer, a timing layer (containing a hydroquinone ester according to the invention) and an image receiving layer. To explain how to use a film unit, first, the film unit is placed in a camera, exposed to light through a transparent image receptor, and then, when the film unit is removed from the camera, a pair of additives built into the camera are used. Guide the film unit between the pressure members. The pressure member ruptures the container, dispersing the processing composition, TiO2, and indicator dye contained therein over the imaged area of the assembly (the TiO2 protects the imaged area from light exposure). . The processing composition develops each silver halide layer and a dye image is formed as a result of development. The dye image formed diffuses into the image receiving layer and can thus be viewed through the transparent support on a white background. As previously mentioned, the neutralization layer then neutralizes the alkaline treatment composition after it has passed through the timing layer, thus completing the "shutdown" of the system. Another embodiment of a color diffusion transfer film unit assembly in which the present invention can be used in a dye image-receiving element is described, for example, in U.S. Pat. No. 3,362,819.

The image-receiving element described in this U.S. patent includes a support (usually opaque) and a
It comprises a neutralizing layer, a timing layer (containing the hydroquinone ester of the present invention when applied to the present invention), and a dye image-receiving layer. The photosensitive elements useful in this invention can be treated with alkaline processing compositions according to any technique to effect or initiate development of the element. A preferred method for applying treatment compositions is through the use of rupturable containers or bags containing such compositions. Generally, the processing composition used in the present invention contains a developer for carrying out development. When a developer is incorporated into the photosensitive element, the alkaline processing composition acts to activate the developer incorporated into the element. Dye image-forming materials that can be used in the present invention is generally characterized by the following (1) or (2). (1) Although initially soluble in or diffusible in processing compositions, development results in selective inefficiencies in the imaged pattern. Being able to spread.

These substances are disclosed in, for example, US Pat. No. 2,647,049, US Pat. No. 2,661,293, US Pat.
No. 4668 and No. 2983606. (2) Although initially insoluble or non-diffusible in the processing composition, development results in selective diffusion in the imaged pattern. To be sexualized. These substances are described, for example, in U.S. Pat.
No. 27551, No. 3227552, No. 32275
No. 54, No. 3243294 and No. 3445228
Disclosed in the issue.

These arostrum contain pre-prepared pigments or pigment precursors (
(precursor substances), such as color couplers, oxychromic compounds, and others.

In a preferred embodiment of the invention, the dye image-forming material is a non-diffusible or stabilized redox dye releaser. Generally speaking, such compounds can be oxidized (i.e., cross-oxidized) by an oxidized developer and, as a result of the oxidation, e.g., by alkaline hydrolysis, become diffusible. It is a compound capable of producing a component capable of releasing a dye. Such di-releasers are disclosed in, for example, US Pat. No. 3,725,062 and US Pat. No. 3,698.
No. 897, No. 3443939, No. 3443940
No. 3928312, No. 3929760, No. 3942987, No. 3932380, No. 39
No. 80479, U.S. Patent Application Publication No. B-35167
3 and German Patent Application No. 2406664. In one particularly preferred embodiment of the invention, the direleasing agents are stabilized sulfonamide compounds that can be oxidized and alkaline cleaved to release the diffusible dye from the core.

Note that the stabilized sulfonamide compound can be represented by the following general formula. In the above formula: (a) COI is a dye or dye precursor component; and (b) Ballast is a non-diffusible component of the compound in the photosensitive element during development of the photosensitive element in an alkaline processing composition. (c) G is 0R2 or NHR3, where R2 is hydrogen or a hydrolyzable group, and R3 in the formula is hydrogen or a substituted or unsubstituted alkyl group (having 1 to 22 carbon atoms), such as a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, a butyl group, S
ec. -butyl group, Tert. -butyl group, cyclopropyl group, 4-chlorobutyl group, cyclobutyl group, 4-nitroamyl group, hexyl group, cyclohexynole group, octyl group, decyl group, octadecyl group, docosyl group, benzyl group, phenethyl group, etc. (in the formula (d) Y represents a group of atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocycle, such as pyrazolone, pyrimidine, and (e) n represents an integer of 1 to 2, and , 2 when G in the formula is 0R2 or R3 in the formula is a hydrogen atom or an alkyl group having 8 or less carbon atoms.

According to another preferred embodiment of the invention, a dye image-forming material having diffusive properties at an early stage, such as a dye developer (e.g., U.S. Pat. No. 3,453,107;
No. 544545, No. 3551406, No. 3563
No. 739, No. 3597200 and No. 370518
No. 4) and oxychromic developers, such as those described in U.S. Pat.
80658 can be used.

When an oxychromic developer is used, the oxychromic developer is diffused into the dye image-receiving layer, where it undergoes chromogenic oxidation to form the image dye, thus forming the image. can be done. The assemblies of the present invention can be used to form positive-tone images in monochrome or multicolor.

In the case of three-color color photography, each silver halide emulsion layer of the film assembly has a predominant spectral absorption in the region of the visible spectrum to which the silver halide emulsion associated with that emulsion layer is sensitive. It will contain such a dye image-forming material.

That is, the blue-sensitive silver halide emulsion layer has a yellow dye image-forming material associated therewith, the green-sensitive silver halide emulsion layer has a magenta dye image-forming material associated therewith, and , the red-sensitive silver halide emulsion layer will have a cyan dye image-forming material associated therewith. The dye image-forming materials to be associated with each silver halide emulsion layer may be contained within the silver halide emulsion layer itself or in a layer adjacent to the silver halide emulsion layer. The concentration of the dye image-forming materials used in this invention can vary over a wide range, depending on the nature of the compounds used and the desired results.

For example, a dye image-forming compound and a hydrophilic film-forming natural or synthetic polymeric binder, such as gelatin, polyvinyl alcohol, etc., may be used in a ratio of about 0.25 to about 4 to allow the aqueous alkaline processing composition to pass through. The dye image-forming material may be applied in the form of a dispersion by using a coating solution containing a fluorine-containing material (e.g. Any silver halide developer can be used in the present invention depending on the particular chemical system involved.

For example, a developer may be used within the photosensitive element to be activated by an alkaline processing composition.
Particular examples of developers that can be used in the present invention are as follows. Hydroquinone, N-methylaminophenol, phenidone (1-phenyl-3-pyrazolidinone), dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidinone), aminophenol, N-N-diethyl-p-phenylenediamine , 3-methyl-N-N-diethyl-p-phenylenediamine, N-
N-N'・N! -Tetramethyl-p-phenylenediamine, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, 4,4-bis(hydroxymethyl)-1-phenyl-3-pyrazolidinone, and others.

However, preferred are black and white developers.

This is because color developers (color developers) generally have low sensitivity and may cause contamination.
If not handled properly, the inhaler may develop dermatitis himself. When a dye releaser compound which forms a diffusive dye image as a result of development is used in the present invention, either a conventional negative-working silver halide emulsion or a direct positive-working silver halide emulsion may be used. good. The silver halide used may be a direct positive silver halide emulsion, such as an internal image emulsion made for use in internal image reversal processes, or a clouded direct positive emulsion, such as a supersensitized emulsion. If the emulsion is developable in the unexposed areas, a positive-working image can be obtained in certain embodiments (dye image on one receiving layer). After exposure of the film unit is complete, an alkaline processing composition is passed through the various layers to permit development of the exposed light-sensitive silver halide emulsion layers.
The developer present in the film unit develops each of the silver halide emulsion layers contained in the unexposed area (
This is because the silver halide emulsion here is a direct positive type), therefore the developer itself is also a direct positive type.
・It is oxidized imagewise corresponding to the unexposed areas of the silver halide emulsion layer. The oxidized developer then cross-oxidizes the dye-one-releasing compound, and the dye-one-releasing compound in the oxidized state then undergoes a base-catalyzed reaction, thus producing silver halide. As a result of the imagewise exposure of each emulsion layer, dye is released imagewise. The imagewise distributed diffusible dye diffuses at least in part into the image-receiving layer, thus forming a positive image corresponding to the original (subject). Internal image silver halide emulsions useful in the present invention include, for example, Zuzu Research D
isclOsure-November 1976 edition, 76-7
It is explained in detail on page 9.

The various silver halide emulsion layers making up the color film assembly of this invention can be arranged in any conventional order.

That is, a blue-sensitive silver halide emulsion layer is placed closest to the exposure side, followed by a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order. I can do it. If necessary, a yellow dye layer or a yellow colloidal silver layer is provided between the blue-sensitive layer and the green-sensitive layer to absorb the blue light that can pass through the blue-sensitive layer or else cause gloss. It may be allowed to exist. If desired, the selectively sensitized silver halide emulsion layers may be arranged in a different order than above, for example, the blue-sensitive layer is arranged closest to the exposure side; A red-sensitive layer and a green-sensitive layer may be arranged behind it. Although the alkaline treatment composition used in the present invention can be applied to the assemblage by using a rupturable container, as described above, there is no need to use a rupturable container to release the composition into the assemblage. Other means can also be used.

For example, such delivery means may include injecting the composition using a communication member (similar to a hypodermic syringe) attached to either the camera or the camera cartridge. In the color photographic assemblage according to the invention, each silver halide emulsion layer containing a dye image-forming material or having a dye image-forming material in an adjacent layer is separated from another silver halide emulsion layer. It may be isolated from the emulsion layer in the negative part of the film unit.

Such isolation of silver halide emulsion layers can be accomplished by using a variety of materials, such as gelatin, calcium alginate, and those disclosed in U.S. Pat. No. 3,384,483. ,
Polymeric materials such as polyvinylamide as disclosed in US Pat. No. 3,421,892 or French Patent No. 2,028,236 or US Pat. No. 306
No. 9264, No. 3121011 and No. 34271
Examples include those disclosed in No. 58.
Generally speaking, unless otherwise specified, the silver halide emulsion layer in the present invention can have photosensitive silver halide dispersed in gelatin; The thickness of the emulsion layer is about 0.6~
It is 6 microns. The dye image-forming material is dispersed as a separate layer (approximately 0.2 to 7 microns thick) in a polymer binder permeable to an aqueous alkaline solution, such as gelatin; The polymeric interlayer, such as gelatin, has a thickness of about 0.2 to 5 microns. Of course, these thicknesses are only approximate, and can be arbitrarily changed depending on the desired product. As used herein, the term "non-diffusible" has the meaning generally accepted in the field of photographic terminology, i.e., the term "non-diffusible" refers to such properties. No matter what practical purpose the substance is used for, if the treatment is carried out in an alkaline catalyst, preferably in a medium with a pH value of 11 or more,
It refers to materials that do not micrate or become suspended within the organic colloid layer of the photographic elements of this invention. It may also be added that the term ``immobility'' has the same meaning. Furthermore, the term "diffusible" has a completely opposite meaning when applied to the substance of the present invention.
That is, the term refers to a material that has the property of effectively diffusing into the colloidal layer of a photographic element in an alkaline medium and in the presence of a "non-diffusible" material. The term "mobility" also has the same meaning as above.
The term ゛ in combination with ``...'' refers to cases in which two or more materials have mutual accessibility, in which case such materials can be placed either in the same layer or in different layers. It means that it can be made to exist.

The invention will now be explained in more detail with the following examples.

Examples: (A) A cover sheet (control) was prepared by applying the following layers in sequence onto a 0.004 inch poly(ethylene terephthalate) film substrate.

(1) Poly(n-butyl acrylate-acrylic acid) (30% acrylic acid) of 15.57/I and 0.4
37/m” Dicalte (trade name), Grade 1
Acidic layer having diatomaceous earth of 03, (2) 1.92
97/d cellulose acetate (40% acetyl) and 0.97/d.
a timing layer having poly(styrene-co-mono-maleic anhydride) of 247/M; and (3) 2.15y/M.
a second timing layer consisting of poly(acrylonitrile-vinylidene-monochloride-acrylic acid) (15:79:6);

(B) Another cover sheet was prepared in the same manner as above.

In this example, layer (2) also contained 0.22 y/m'' of hydroquinone monoacetate.

'ElementlO' of U.S. Patent No. 4,030,925
An embossed photographic element of the type described in Section 1 was exposed to a tungsten light source (using a multicolor est chart with increasing density).

A processing composition as described below was used in a bag, and the processing composition was then sprinkled between the exposed photosensitive element and the transparent cover sheet as described above (temperature: 16°C). and 38°C).

When spraying the composition, the thickness of the liquid layer is approximately 0.00.
A transparent ``sandwich structure'' was passed between a pair of juxtaposed rollers to achieve a thickness of 3 inches. The compositions contained in the bag were as follows.

The table below summarizes the changes in sensitometric properties observed after processing these elements at temperatures of 16°C and 38°C.

The above results show that the speed loss is significantly reduced in element B (see especially the numbers listed for the red range).

Claims (1)

[Claims] Hydroquinone ester silver halide developer represented by the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, G is hydrogen, -COR or -SO_2R, and G' is -COR or -SO_2R, and R in the above formula: -COR and -SO_2R is an alkyl group or substituted alkyl group having 1 to 20 carbon atoms, or 6 to
an aryl group or substituted aryl group having 12 carbon atoms, and Z is hydrogen, an alkyl group (including substituted alkyl groups) having 1 to 6 carbon atoms, having 1 to 6 carbon atoms an alkoxy group (including substituted alkoxy groups) or an aryl group having 6 to 8 carbon atoms) is present in the timing layer or in an adjacent layer next to the timing layer; wherein the treatment composition is positioned such that the treatment composition first passes through the timing layer prior to contact with the adjacent layer, and the timing layer has an aqueous alkaline treatment solution permeation activation of greater than 18 kcal/mol. A photosensitive recording material for color diffusion transfer photography that contains energy.