CA1112929A - Use of hydroquinone esters as blocked competing developers for color transfer assemblages - Google Patents
Use of hydroquinone esters as blocked competing developers for color transfer assemblagesInfo
- Publication number
- CA1112929A CA1112929A CA312,741A CA312741A CA1112929A CA 1112929 A CA1112929 A CA 1112929A CA 312741 A CA312741 A CA 312741A CA 1112929 A CA1112929 A CA 1112929A
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- Prior art keywords
- layer
- carbon atoms
- assemblage
- timing
- silver halide
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/32—Development processes or agents therefor
- G03C8/36—Developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/42—Structural details
- G03C8/52—Bases or auxiliary layers; Substances therefor
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Hydroquinone esters are incorporated in or behind a timing layer with a high activation energy to release a competing developer upon contact with a proces-sing composition.
Hydroquinone esters are incorporated in or behind a timing layer with a high activation energy to release a competing developer upon contact with a proces-sing composition.
Description
~1 29Z9 This invention relates to photography, and more particularly to photographic assemblages for color diffu-sion transfer photography wherein a hydroquinone ester is employed in or behind a timing layer having a high activa-tion energy to release a competing developer upon contact with a processing composition.
Various formats for color integral transfer ele-ments are described in the prior art, such as U.S. Patents 3,415,6~4; 3,415,645; 3,415,646; 3,647,437; 3,635,707;
: lo 3,756,815 and Canadian Patents 928,559 and 674,082. In these formats, the image-receiving layer containing the photographic image for viewing can remain permanently attached and integral with the image generating and ancillary layers present in the structure when a transparent support is employed on the viewing side of the assemblage. The image is formed by dyes, produced in the image generating units, diffusing through the layers of the structure to the dye image-receiving layer. After exposure of the assemblage, an alkaline processing composition permeates the various layers 20 to initiate development of the exposed photosensitive silver halide emulsion layers. The emulsion layers are developed in proportion to the extent of the respective exposures, and the image dyes which are formed or released in the respective image generating layers begin to diffuse throughout the ~-structure. At least a portion of the imagewise distribution of diffusible dyes diffuse to the dye image-receiving layer to form an image of the original sub~ect.
Other so-called "peel-apart" formats for color d~ffusion transfer assemblages are described, for example, in U,S. Patents 2,983,606; 3,362,8Ig; and 3,362,821, ~n ~L~12~
these formats, the lmage-receiving element is separated from the photosensitive element after development and transfer of the dyes to the image-receiving layer.
U.S. Patent 3,462,266 relates to oxazines and benzoxazines which are cleaved to hydroquinones under alka-line conditions. The compounds are described as being auxiliary developer precursors in dye developer image transfer systems and may be present in various locations such as an overcoat layer, a spacer layer, a mordant layer or an acidic layer.
Competing developing agents have been used in various photographic assemblages heretofore. For example, ~ ~ -Research Disclosure 15162, November 1976, on page 79, dis-closes that combinations of certain developing agents with alkali-soluble competing developers such as hydroquinone, methylhydroquinone and t-butylhydroquinone are especially useful in achieving the desired sensitometric curve shape of the dye image in diffusion transfer assemblages, such as those employing dye releasers described therein. For example, -in diffusion transfer systems, optimum development tempera-tures are not always obtainable. At high temperatures, such as 32 to 35C, there is faster development with more dye being released, causing a significant loss in speed, an increase in DmaX and an increase in Dmin. The presence of a competing developing agent in the processing composition in the right concentration will help to alleviate the problem somewhat, since it will develop silver but will not cause any dye to be released. The Dmin can be lowered in this manner, but the speed loss is still there. The increase in DmaX is also still there, but is not as noticeable to the eye.
lZ9~9 Another problem wlth employing a competing devel-oper in the processing composition concerns the variability of the developer layer thickness, or DLT, in a given film unit. In cameras where the operator hand cranks the film units out of the camera, the speed at which he operates the crank will affect the DLT -- e.g., a fast cranking motion will provide a relatively low DLT. In cameras having a motor drive, the DLT varies with the viscosity of the proces-sing composition, the temperature of processing, etc. This variable DLT, in turn, magnifies the variability of a competing developer employed in the processing composition, since it is employed at a relatively low concentration.
In accordance with my invention, I have found that competing developing agents may be utilized in such a way as to significantly reduce the speed loss attendant with high temperature development described above, as well as elimina-ting the variability of their concentration with variability in DLT. I have found that employing certain hydroquinone esters in or behind a timing layer with a high activation energy 20 will provide these advantages. Employing such compounds in -or behind a timing layer provides a time delay before the material becomes operative. During processing, the processing composition penetrates through all or a part of the timing layer until it contacts the hydroquinone ester. The ester groups then hydrolyze and the resulting hydroquinone is free to diffuse to the photosensitive layers to take part in development. By employing the hydroquinone in its "blocked"
or water-insoluble ester form, it can be easily and advan-tageously incorporated into an organic solvent-coated poly-3 meric layer underlying the timing layer, in a preferred ~LlZ~9 embodiment, and it remalns stable upon incubatlon.
The timing layer employed in this invention has a high activation energy of penetration by aqueous alkali.
It rapidly "breaks down" or "opens up" at a temperature above about 30C. Below that temperature, its penetration by the processing composition is relatively slow. However, this enables the hydroquinone esters to be incorporated in relatively large amounts. During processing at 32C when dye release would ordinarily be excessive, this timing layer breaks down rapidly and allows a large amount of competing developer to diffuse to the developing silver. The result is a large amount of silver development, but the dye release is approximately the same as it would be at lower temperatures.
The speed loss which would otherwise be obtained is, therefore, significantly reduced. Incorporation of larger amounts of competing developer in the processing composition would not provide the same effect, since it would significantly lower dye release at all temperatures, My invention thus provides a means for significantly controlling the effects of high temperature overdevelopment which would ordinarily result in dark images of high dye density.
A photographic assemblage according to my invention comprises:
a) a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
b) a dye image-receiving layer;
c~ an alkaline processing composition and means for dis-charging same within the assemblage;
.' ' I ~ . .- .
~z~z9 d) a neutralizing layer for neutrallzlng the alkaline processing composition; and e) a timing layer disposed between the neutrallzing layer and the photosensitive silver halide emulsion layer so that the processing composition must first permeate the timing layer before contacting the neutrallzing layer;
the assemblage containing a silver halide developing agent, and wherein the assemblage contains a hydroqulnone ester either (1) in the timing layer, or (2) in a layer which is ad~acent thereto and is so located with respect to the timing layer that the processing composition must first permeate the timing layer before contacting the ad~acent layer, the hydroquinone ester having the following formula:
OR
I * G
t OR' wherein R is hydrogen or an acyl (including substituted acyl) group having 1 to about 20 carbon atoms, R is an acyl (includ-ing substituted acyl~ group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl (including substituted alkyl) group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein the timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
In the above formula, G can be hydrogen, an alkyl group of 1 to about 6 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, etc, or an aryl group having 6 to about 8 .' ~ L2~29 carbon atoms, such as phenyl, _-tolyl, _-methoxyphenyl, etc, as long as the compound will diffuse at a sufficient rate when the acyl group or groups are hydrolyzed. In a similar manner, when each of R and R in the formula is an acyl group, any such group such as acetyl, propionyl, benzoyl, ethoxycarbonyl, ethoxalyl, etc, can be employed, so long as it can be hydrolyzed to the corresponding hydroquinone.
The hydroquinone esters can be employed according to my invention at any concentration effective for the intended purpose. Good results have been obtained at a concentration of from about 0.054 g/m2 to about 0.54 g/m2, and especially good results have been obtained at a concentration of from about 0.10 g/m2 to about 0.45 g/m2.
Examples of hydroquinone esters useful in my inven-tion include the following:
(1) Hydroquinone diacetate O
I ~
t O-C--CH
o
Various formats for color integral transfer ele-ments are described in the prior art, such as U.S. Patents 3,415,6~4; 3,415,645; 3,415,646; 3,647,437; 3,635,707;
: lo 3,756,815 and Canadian Patents 928,559 and 674,082. In these formats, the image-receiving layer containing the photographic image for viewing can remain permanently attached and integral with the image generating and ancillary layers present in the structure when a transparent support is employed on the viewing side of the assemblage. The image is formed by dyes, produced in the image generating units, diffusing through the layers of the structure to the dye image-receiving layer. After exposure of the assemblage, an alkaline processing composition permeates the various layers 20 to initiate development of the exposed photosensitive silver halide emulsion layers. The emulsion layers are developed in proportion to the extent of the respective exposures, and the image dyes which are formed or released in the respective image generating layers begin to diffuse throughout the ~-structure. At least a portion of the imagewise distribution of diffusible dyes diffuse to the dye image-receiving layer to form an image of the original sub~ect.
Other so-called "peel-apart" formats for color d~ffusion transfer assemblages are described, for example, in U,S. Patents 2,983,606; 3,362,8Ig; and 3,362,821, ~n ~L~12~
these formats, the lmage-receiving element is separated from the photosensitive element after development and transfer of the dyes to the image-receiving layer.
U.S. Patent 3,462,266 relates to oxazines and benzoxazines which are cleaved to hydroquinones under alka-line conditions. The compounds are described as being auxiliary developer precursors in dye developer image transfer systems and may be present in various locations such as an overcoat layer, a spacer layer, a mordant layer or an acidic layer.
Competing developing agents have been used in various photographic assemblages heretofore. For example, ~ ~ -Research Disclosure 15162, November 1976, on page 79, dis-closes that combinations of certain developing agents with alkali-soluble competing developers such as hydroquinone, methylhydroquinone and t-butylhydroquinone are especially useful in achieving the desired sensitometric curve shape of the dye image in diffusion transfer assemblages, such as those employing dye releasers described therein. For example, -in diffusion transfer systems, optimum development tempera-tures are not always obtainable. At high temperatures, such as 32 to 35C, there is faster development with more dye being released, causing a significant loss in speed, an increase in DmaX and an increase in Dmin. The presence of a competing developing agent in the processing composition in the right concentration will help to alleviate the problem somewhat, since it will develop silver but will not cause any dye to be released. The Dmin can be lowered in this manner, but the speed loss is still there. The increase in DmaX is also still there, but is not as noticeable to the eye.
lZ9~9 Another problem wlth employing a competing devel-oper in the processing composition concerns the variability of the developer layer thickness, or DLT, in a given film unit. In cameras where the operator hand cranks the film units out of the camera, the speed at which he operates the crank will affect the DLT -- e.g., a fast cranking motion will provide a relatively low DLT. In cameras having a motor drive, the DLT varies with the viscosity of the proces-sing composition, the temperature of processing, etc. This variable DLT, in turn, magnifies the variability of a competing developer employed in the processing composition, since it is employed at a relatively low concentration.
In accordance with my invention, I have found that competing developing agents may be utilized in such a way as to significantly reduce the speed loss attendant with high temperature development described above, as well as elimina-ting the variability of their concentration with variability in DLT. I have found that employing certain hydroquinone esters in or behind a timing layer with a high activation energy 20 will provide these advantages. Employing such compounds in -or behind a timing layer provides a time delay before the material becomes operative. During processing, the processing composition penetrates through all or a part of the timing layer until it contacts the hydroquinone ester. The ester groups then hydrolyze and the resulting hydroquinone is free to diffuse to the photosensitive layers to take part in development. By employing the hydroquinone in its "blocked"
or water-insoluble ester form, it can be easily and advan-tageously incorporated into an organic solvent-coated poly-3 meric layer underlying the timing layer, in a preferred ~LlZ~9 embodiment, and it remalns stable upon incubatlon.
The timing layer employed in this invention has a high activation energy of penetration by aqueous alkali.
It rapidly "breaks down" or "opens up" at a temperature above about 30C. Below that temperature, its penetration by the processing composition is relatively slow. However, this enables the hydroquinone esters to be incorporated in relatively large amounts. During processing at 32C when dye release would ordinarily be excessive, this timing layer breaks down rapidly and allows a large amount of competing developer to diffuse to the developing silver. The result is a large amount of silver development, but the dye release is approximately the same as it would be at lower temperatures.
The speed loss which would otherwise be obtained is, therefore, significantly reduced. Incorporation of larger amounts of competing developer in the processing composition would not provide the same effect, since it would significantly lower dye release at all temperatures, My invention thus provides a means for significantly controlling the effects of high temperature overdevelopment which would ordinarily result in dark images of high dye density.
A photographic assemblage according to my invention comprises:
a) a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
b) a dye image-receiving layer;
c~ an alkaline processing composition and means for dis-charging same within the assemblage;
.' ' I ~ . .- .
~z~z9 d) a neutralizing layer for neutrallzlng the alkaline processing composition; and e) a timing layer disposed between the neutrallzing layer and the photosensitive silver halide emulsion layer so that the processing composition must first permeate the timing layer before contacting the neutrallzing layer;
the assemblage containing a silver halide developing agent, and wherein the assemblage contains a hydroqulnone ester either (1) in the timing layer, or (2) in a layer which is ad~acent thereto and is so located with respect to the timing layer that the processing composition must first permeate the timing layer before contacting the ad~acent layer, the hydroquinone ester having the following formula:
OR
I * G
t OR' wherein R is hydrogen or an acyl (including substituted acyl) group having 1 to about 20 carbon atoms, R is an acyl (includ-ing substituted acyl~ group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl (including substituted alkyl) group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein the timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
In the above formula, G can be hydrogen, an alkyl group of 1 to about 6 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, etc, or an aryl group having 6 to about 8 .' ~ L2~29 carbon atoms, such as phenyl, _-tolyl, _-methoxyphenyl, etc, as long as the compound will diffuse at a sufficient rate when the acyl group or groups are hydrolyzed. In a similar manner, when each of R and R in the formula is an acyl group, any such group such as acetyl, propionyl, benzoyl, ethoxycarbonyl, ethoxalyl, etc, can be employed, so long as it can be hydrolyzed to the corresponding hydroquinone.
The hydroquinone esters can be employed according to my invention at any concentration effective for the intended purpose. Good results have been obtained at a concentration of from about 0.054 g/m2 to about 0.54 g/m2, and especially good results have been obtained at a concentration of from about 0.10 g/m2 to about 0.45 g/m2.
Examples of hydroquinone esters useful in my inven-tion include the following:
(1) Hydroquinone diacetate O
I ~
t O-C--CH
o
(2) Hydroquinone monohexanoate o C CsH~ ~ n I~ ~
OH
~z~29
OH
~z~29
(3) 3-t-butyl-4-hydroxyphenyl acetate O
O--C-CH
t C--CH3
O--C-CH
t C--CH3
(4) Hydroquinone monoacetate O
OH
OH
(5) Hydroquinone monobenzoate O
O- C--C H
OH
O- C--C H
OH
(6) 4-Hydroxy-3-tolyl benzoate O
O--C--C H
OH
292~
As noted above, the hydroqulnone esters employed ln this lnvention can be employed elther ln or behlnd the timing layer with respect to the side of appllcatlon of the processing composltion. Preferably, lt ls lncorporated ln the timing layer so that the release of the competing developer occurs after a finite time. When a longer delay is deslred, the compound ls merely incorporated ln an ad~acent layer, behind the timing layer and farther away from the developing silver halide layers. This layer can be contiguous to the timing layer or can be located in an ad~acent layer several layers away from the timing layer, depending upon the results desired.
Particularly preferred timing layers useful in thls invention comprise a polymeric latex having an activation energy of penetration of the layer by an aqueous alkallne solution of greater than 18 kcal/mole. Such latex tlming layers result from a coalescence or partial coalesence of polymeric particles from an aqueous latex. Preferred latex timlng layers are described, along with their method of 20 synthesis, inCdn. Application Serial No.275~94l of Hannie, filed Apri~ 12, 1977.
These timing layers delay the neutralization of the alkaline processlng compositlon by the acid layer so that production of a hlgh quallty dye lmage ls more reproducible over a large temperature range.
The activation energy of penetration of polymeric layers by aqueous alkaline solutions can be determined by the following simple test.
A thymolphthalein dye or cresol red dye indicator 3~ is coated on a polyethylene terephthalate film support at 210 mg/m2 with 6.6 g/m2 gelatin in the case of thymolphthalein or 2.2 g/m2 ln the case of cresol red.
_ g _ 'B
. , 1 z9 A processing composition comprising a pod which contains about o.84 N potassium hydroxide and about 5 percent carboxymethyl cellulose in water, along with other conven-tional developer ingredients, is spread between the element containing the indicator dye and a sample of a cover sheet by passing the "sandwich" between a pair of ~uxtaposed pressure rollers so that the developer layer thickness is 0.1 mm.
The cover sheet comprises a polyethylene terephthalate support containing a first layer of a 30/70 (by weight) copolymer of poly(butyl acrylate-co-acrylic acid), a second layer of 50/50 (mole ratio) polymer of poly(styrene-co-maleic anhydride) at 2.2 g/m2 and the outer layer being the polymer for which the activation energy is to be determined.
The time required to reduce the pH of a unit to pH
10 as measured by the color change of the thymolphthalein dye from blue to colorless or to pH 8 as measured by the change of the cresol red dye from red to yellow is measured at various temperatures within the range of 13 to 54C. The time in seconds is plotted on a logarithmic scale against the recip-rocal of the temperature expressed in K. The activationenergy in kcal/mole is determined from the slope of the straight line portion of the curve according to the formula:
~Ea (activation energy) = 0.00458 X log Y2/Y
l/T2 l/Tl where T2 is the higher temperature and Tl is the lower temperature and Y2 is the time at T2 and Yl is the time at Tl. The thickness of the acid layer and the polymer layer is not critical to the proper determination of activation energy.
A discussion of activation energy calculations can be found in Kinetics and Mechanism, second edition, New York, John Wiley and Sons, 1961, pages 22 through 25.
Latex polymers having an activation energy to penetration by aqueous alkaline solution of greater than 18 kcal/mole include poly(methyl acrylate-co-ltaconic acid-co-vinylidene chloride) and the like.
Preferred polymeric latexes having an activation energy of penetration to aqueous alkaline solution of greater than 18 kcal/mole are terpolymers of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of poly-merized ethylenically unsaturated carboxylic acid and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
Any ethylenically unsaturated monomer which is different from the other monomers in the polymeric latex can be used to prepare the terpolymer including alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate and the like; vinyl esters, amides, nitriles, ketones, halides, ethers, olefins, diolefins and the like as exemplified by acrylonitrile, methacrylonitrile, styrene, alpha-methyl styrene, acrylamide, methacrylamide, vinyl chloride, methyl vinyl ketone, fumaric, maleic and itaconic esters, 2-chloroethylvinyl ether, dimethyl-aminoethyl methacrylate, 2-hydroxyethyl methacrylate, N-vinyl-succinamide, N-vinylphthalimide, N-vinylpyrrolidone, butadiene, ethylene and the like. Preferred monomers are methyl acrylate and acrylonitrile.
~29~29 Examples of ethylenlcally unsaturated carboxylic acids which can be lncluded in the polymer lnclude acryllc acid, methacrylic acid, itaconlc acid, fumarlc acid, maleic acid, their anhydrides, and the like. The preferred carboxylic acids are acrylic acid and itaconic acid.
A preferred terpolymer useful in the invention comprises 15 weight percent methyl acrylate, 83 weight percent vinylidene chloride and 2 weight percent ltaconic acid. Further examples of latex polymers useful herein can be ~ound ln U.S.
Patents 3,271,345; 2,627,088; 2,491,023; 2,779,684; 3,437,484;
2,943,937 and 3,143,421.
The latex timing layer can generally be employed over a broad range of coverages. Preferred coverage for the layer ranges from about 1.0 g/m2 to 6.0 g/m2 and more pre~erably from about 1 to 3 g/m2.
In a preferred embodlment of my lnventlon, the hydro-quinone esters are incorporated in an ad~acent layer comprlsing a timing layer, which layer, in turn is coated with the latex timing layer having a high activation energy described above. In this "doublet' timing layer embodiment, the first timing layer in which the hydroquinone esters are employed comprising a polymeric latex having an activation energy of penetratlon to aqueous alkaline solution of less than 18 kcal/mole. The second timing layer ls as described above and comprises a polymeric latex havlng an actlvatlon energy of penetration to aqueous alkallne solutlon of greater than 18 kcal/mole. This "double" timing layer system ls described more fully in Cdn. Applicatlon Serial No.275,941 of ~annie and Ducharme, filed April 12, 1977.
~ - 12 -2~
Examples of polymers for the flrst timlng layer described above having an activatlon energy of penetratlon of aqueous alkaline composltion of less than 18 kcal/mole are mixtures of cellulose acetate and a maleic anhydrlde copolymer with 5 to 50 percent by weight of the mixture belng sald copolymer such as described in Cdn. Patent 1,072,800 issued March 4, 1980.
The maleic anhydride copolymer in thls timing layer should be employed in a concentration of about 2 to about 20 percent by weight, depending somewhat on the other comonomer.
A 5 to 20 percent concentration has been found to be particu-larly effective. The thickness of this tlming layer should be such as to provide a coverage of about 1 to about 5 g/m2.
The cellulose acetate employed in that layer will usually have acetyl contents of about 37 to 40 percent by weight, the 37 percent being substantially more permeable than the 40 percent acetyl. Mixed esters can also be employed, such as cellulose acetate propionate, cellulose acetate butyrate, etc.
The maleic anhydride copolymer can be selected from a wide variety of materials, so long as it ls compatible with the cellulose acetate employed to provide a clear film. Particu-larly good results are obtained with poly(styrene-co-maleic anhydride), poly(ethylene-co-maleic anhydrlde) and poly(methyl vinyl ether-co-maleic anhydride).
Examples of other layers containlng polymers havlng an activatlon energy of less than 18 kcal/mole are polyvinyl acetate, cellulose acetate phthalate, partial acetals of polyvinyl alcohol, a polymer latex of butyl acrylate-diacetone Z~
acrylamide-styrene-methacryllc acid (60/30/4/6) as described in ~.S. Patent 3,785,815, mixtures of polyvinyl acetate and polyvinyl alcohol such as polyvinyl acetate latex in 78/22 ratio with polyvinyl alcohol, cellulose acetate (40 percent acetate in 95/5 ratio with poly[styrene-co-maleic anhydride]
[50/50 mole ratio]) as described in Canadian Patent 1,072,800 and the like.
One embodiment of an assemblage Or an integral transfer color element and a process for producing a photo-graphic transfer image in color in which my invention can beemployed is disclosed in Canadian Patent 928,559. In this embodiment, the support for the photosensitive element is transparent and is coated with an image-receiving layer, a light-reflective layer, an opaque layer and photosensitive layers, having associated therewith dye image-providing material layers. A rupturable container containing the alkaline processing composition described above and an opacifier such as carbon black is positioned ad~acent the top layer and a transparent cover sheet. The cover sheet comprises a transparent support which is coated with a neutralizing layer and a timlng layer containing the hydro-quinone esters according to the invention. The film unit is placed in a camera, exposed through the transparent cover sheet and then passed through a pair of pressure-applying members in the camera as it is being removed therefrom. The pressure-applying members rupture the container and spread processlng composition and opacifier over the image-forming portion of the assemblage to protect it from -exposure. The processing compositlon develops each silver hallde layer and dye images are formed as a result of development which ~ - 14 -'~lZ~Z9 diffuse to the image-receivlng layer to provide a right-reading image which is viewed through the transparent support on the opaque reflecting layer background. The neutralizlng layer then neutrallzes the alkallne processing compositlon after the tlmlng layer has been permeated, thus "shutting down" the system. For further details concerning the format of this particular lntegral assemblage, reference is made to the above-mentioned Canadian Patent 928,559.
10Another embodiment of an assemblage of an integral transfer color element and a process for produclng a photo-graphic transfer image in color ln which my invention can be employed is described in U.S. Patent 3,415,644. In this embodiment, the negative comprises an opaque support which is coated with photosensitive layers having associated therewith dye image-providing material layers. A rupturable container containing the alkaline processing composition described above, TiO2 and an indicator dye (see U.S. Patent 3,647,437) is positioned ad~acent the top layer and a trans- ;~
parent receiver. The receiver comprises a transparent support which is coated with a neutralizing layer, a timing layer containing the hydroquinone esters according to the invention and an image-receiving layer. The film unit is placed in a camera, exposed through the transparent receiver and then passed through a pair of pressure-applying members in the camera as it is belng removed therefrom. The pressure-applylng members rupture the contalner and spread processing composltlon, TiO2 and indicator dye over the image-forming portion of the assemblage to protect it from exposure. The processing ccmposltion develops each sllver hallde layer and dye images are formed as a result of development whlch diffuse to the ~mage-receiving layer which ls viewed through the transparent support on a white background -- the lndicator dye having "shifted" to a colorless form as the alkali ls consumed by the neutralizing layer. As before, the neutral-izing layer then neutralizes the alkaline processing composi-tion after the timing layer has been permeated, thus "shutting down" the syste~. For further details concerning the format of this particular assemblage, reference is made to the above-mentioned U.S. Patent 3~415~644~
Since the image ln this embodiment is geometrically reversed, an image-reversing optlcal system such as a mirror in the camera is needed to reverse the image so that a right-reading image is vlewable in the dye image-receiving layer.
Another embodiment of an assemblage of a color diffusion transfer film unit in which this invention can be employed in a dye image-receiving element is described in U.S. Patent 3~362~819~ The image-receiving element comprises a support, which is usually opaque, having thereon a neutral-izing layer, a timing layer containing the hydroquinoneesters of the invention and a dye image-receivlng layer.
For further details concernlng the use of such an element ln color transfer assemblages, reference is made to the above-mentloned U.S. Patent 3~362~819~
Stlll other useful lntegral formats in whlch my lnventlon can be employed are descrlbed ln U.S. Patents 3~415~645; 3~415~646; 3~647~437; ~635~707~ and British Patent 1, 330~ 524 ~ \
The photosensltlve element useful in my invention can be treated with an alkaline processlng composltlon to r \ ~ 16 ~ ~ 12~29 effect or initiate development in any manner. A preferredmethod for applying processing composition is by use of a rupturable container or pod which contains the composition.
In general, the processing composition employed in my lnvention contains the developing agent for development. Where the developer is incorporated in the photosensitive element, the alkaline processing composition serves to activate the incorporated developer.
The dye image-providing materials which may be employed in my invention generally may be characterized as either (1) initially soluble or diffusible in the processing composition but are selectively rendered nondiffusible in an imagewise pattern as a function of development, such as those disclosed, for example, in U.S. Patents 2,647,049;
2,661,293; 2,698,244; 2,698,798; 2,802,735; 2,774,668; and 2,983,606; or (2) initially insoluble or nondiffusible in the processing composition but which are selectively rendered diffusible in an imagewise pattern as a function of develop-ment, such as those disclosed, for example, in U.S. Patents 3,227,550; 3,227,551; 3,227,552; 3,227,554; 3,243,294; and 3,445,228. These materials may be preformed dyes or dye precursors, e.g., color couplers, oxichromic compounds and the like.
In a preferred embodiment of my invention the dye image-providing material is a nondiffusible or ballasted redox dye releaser. Such compounds are, generally speaking, compounds which can be oxidized by oxidized developing agent, i.e., cross-oxidized, to provide a species which as a function of oxidation will release a diffusible dye, such as 30 by alkaline hydrolysis. Such dye releasers are described in U.S. Patents 3,725,062 of Anderson and Lum issued April 3, l~lZ~ 9 1973; 3,698,897 of Gompf and Lum lssued October 17, 1972;
3,443,939 and 3,443,940 Or Bloom et al lssued May 13, 1969;
3,928,312 of ~leckensteln lssued December 23, 1975; 3,929,760 of Landholm et al lssued December 20, 1975; 3,942,987 of Landholm et al issued March 9, 1976~l 3,932,380 of Krutak et al issued January 13, 1976; 3,980,479 of Fields et al issued September 14, 1976; and U.S. Publlshed Patent Appllcatlon B-351,673 of Fleckenstein et al published January 28, 1975;
German OLS 2,406,664; Canadian Patent 1,047,821Of Kxutak et al issued February 6, 1979; Canadian Patent 1,047,030 of Haase et al issued ~anuary 23, 1979; Canadian Patent 1,073,451 of ~inshaw et al issued March 11, 1980; and Canadian Application 283,408 of Chasman et al filed July 25, 1977.
In an especlally preferred embodiment of my inven-tion, the dye releasers such as those in the Fleckenstein et al patents and appllcatlons referred to above are employed.
Such compounds are ballasted sulfonamldo compounds which are alkali-cleavable upon oxldation to release a diffusible dye from the nucleus and have the formula:
Y -~-- (Ba l l ast) n- 1 wherein:
a) Col is a dye or dye precursor moiety;
b) Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic '~"3 ~12~29 groups or polymeric groups) as to render the compound nondiffusible ln the photosensitlve element durlng development ln an alkaline processing compositlon;
c) G is OR2 or NHR3 wherein R2 is hydrogen or a hydrolyzable molety and R3 ls hydrogen or a substituted or unsubsti-tuted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, secondary butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, cyclo-butyl, 4-nltroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, docosyl, benzyl, phenethyl, etc., (when R3 is an alkyl group of greater than 6 carbon atoms, it can serve as a partlal or sole Ballast group);
d) Y represents the atoms necessary to complete a benzene : nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring such as pyrazolone, pyrimidine, etc; and e) n is a positive integer of 1 to 2 and is 2 when G ls OR2 or when R3 is a hydrogen or an alkyl group of less than 8 carbon atoms.
In another preferred embodlment of my lnventlon, initially diffusible dye image-providing materials are employed such as dye developers, including metal complexed dye developers such as those described in U.S. Patents 3,453,107; 3,544,545; 3,551,406; 3,563,739; 3,597,200;
- 3,705,184; and oxichromic developers as described and claimed in my coworkers' Lestina and Bush Applicztion Canadian Patent 995,948 issued August 3, 1976.
- 19 _ ~12~29 When oxichromic developers are employed, the lmage is formed by the diffusion of the oxichromic developer to the dye image-receiving layer where it undergoes chromogenic oxida-tion to form an image dye.
The assemblage of the present invention may be used to produce positive images in single- or multicolors.
In a three-color system, each silver halide emulsion layer of the film assembly will have associated therewith a dye image-providing material possessing a predominant spectral absorption within the region of the visible spectrum to which said silver halide emulsion is sensitive, i.e., the blue-sensitive silver halide emulsion layer will have a yellow dye image-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye image-providing material associated therewith.
The dye image-providing material associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer.
The concentration of the dye image-providing materials that are employed in the present invention may be varied over a wide range depending upon the particular com-pound employed and the results which are desired. For example, the dye image-providing compounds may be coated as dispersions in layers by using coating solutions containing a ratio between about 0.25 and about 4 of the dye image-providing compound to the hydrophilic film-forming natural material or synthetic polymer binder, such as gelatin, .
polyvinyl alcohol, etc., which ls adapted to be permeated by aqueous alkaline processing composltion.
Any silver halide developing agent can be employed in my invention depending upon the particular chemistry system involved. The developer may be employed in the photosensitive element to be activated by the alkaline processing composition. Specific examples of developers which can be emplsyed in my invention include:
hydroquinone N-methylaminophenol Phenidone (l-phenyl-3-pyrazolidinone) Dimezone (l-phenyl-4,4-dimethyl-3-pyrazolidinone) aminophenols N-N-diethyl ~-phenylenediamine 3-methyl-N,N-diethyl-_-phenylenediamine N,N,N',N'-tetramethyl-~-phenylenediamine 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 4,4-bis(hydroxymethyl)-1-phenyl-3-pyrazolidinone, etc.
The black and white developing agents are preferred, however, since the color developers are generally slower, can cause stain, and can cause dermatitis if not handled properly.
In using dye releaser compounds in my invention which produce diffusible dye lmages as a function of develop-ment, either conventional negative-working or direct-positlve sllver halide emulslons may be employed. If the sllver halide emulsion employed is a direct-positive silver halide emulsion, such as an internal-image emulsion deslgned for use ln the internal lmage reversal process or a fogged, dlrect-positive emulsion such as a solarizing emulsion, which is 3 developable in unexposed areas, a positive image can be obtained in certain embodiments on the dye image-receiving layer. After exposure of the film unit, the alkaline proces-sing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The developing agent present in the film 2~9 unit develops each of the silver hallde emulsion layers ln the unexposed areas (since the silver hallde emulslons are d~rect-positive ones), thus causing the developing agent to become oxidized imagewise corresponding to the unexposed areas Or the direct-positive silver halide emulslon layers. The oxidized developlng agent then cross-oxidizes the dye-releasing compounds, and the oxidized form of the compounds then undergoes a base-catalyzed reaction to release the dyes imagewise as a function of the imagewise exposure of each of the silver halide emulsion layers. At least a portion of the lmagewlse dlstrlbutlons of diffusible dyes diffuse to the image-receiving layer to form a positive image of the original sub~ect.
Internal-image sllver halide emulsions useful in this invention are described more fully in the November 1976 edition of Research Disclosure, pages 76 through 79.
The varlous sllver halide emulsion layers of a color film assembly of the invention can be disposed in the usual order, i.e., the blue-sensitive silver hallde emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers. If desired, a yellow dye layer or a yellow colloidal silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer. If desired, the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layer flrst with 3 respect to the exposure slde, followed by the red-sensitive `~ - 22 -and green-sensitive layers.
While the alkaline processing composition used ln this invention can be applied to the assemblage by the use of rupturable contalners as described previously, other means ~or discharging the composition within the assemblage could also be used, e.g., inter~ecting the compositlons with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge.
In a color photographic assemblage according to this invention, each silver halide emulsion layer containing a dye image-providing material or having the dye image-providing material present in a contiguous layer may be separated from the other silver halide emulsion layers in the negative portion of the film unit by materials including gelatin, calcium alginate, or any of those disclosed in U.S.
Patent No. 3,384,483, polymeric materials such as polyvinyl-amides as disclosed in U.S. Patent 3,421,892, or any of those disclosed in French Patent 2,028,236 or U.S. Patents Nos. 2,992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263, 3,069,264; 3,121,011 and 3,427,158.
Generally speaking, except where noted otherwise, the silver halide emulsion layers in the invention comprise photosensitive silver halide dispersed in gelatin and are about o.6 to 6 microns in thickness; the dye image-providing materials are dlspersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 0. 2 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 0. 2 to 5 microns in thickness. Of course, these 30 ' thicknesses are approximate only and can be modified according to the product desired.
1~2S~9 Scavengers for oxldized developing agent can be employed in various lnterlayers of the photographlc elements of the invention. Suitable materials are disclosed on page 83 of the November 1976 edition Or Research Disclosure.
The alkaline solution-permeable, llght-reflectlve layer employed ln certaln embodlments of photographic assem-blages of thls invention are described more fully in the November 1976 edition of Research Disclosure, page 82, The neutralizing layer employed in my inventlon whlch becomes operative after permeation of the processing composition through the timing layer will effect a reductlon in the pH of the image layers from about 13 or 14 to at least 11 and preferably 5 to 8 within a short tlme after imblbltion. Suitable materlals and their functionlng are disclosed on pages 22 to 23 of the July 1974 edltion of Research Disclosure and pages 35 to 37 of the July 1975 edition of Research Disclosure.
The lnert timlng or spacer layer employed in my invention over the neutralizing layer "tlmes" or controls the pH reductlon as a functlon of the rate at whlch alkall dlffuses throughout the lnert spacer layer. Examples of such timing layers and their functioning are disclosed in the Research Disclosure articles mentioned in the paragraph above concerning neutralizing layers.
Any material can be employed as the image-receiving layer in this invention as long as the desired function of mordanting Gr otherwise fixing the dye images will be ~12~
obtained. The particular materlal chosen wlll, Or course, depend upon the dye to be mordanted. Sultable materlals are disclosed on pages 80 to 82 of the November 1976 editlon of Research Disclosure.
The alkaline processing composition employed ln this lnvention is the conventional aqueous solutlon Or an alkallne material, e.g., alkali metal hydroxldes or carbonates such as sodium hydroxide, sodium carbonate, or an amine such as diethylamine, possessing a pH Or at least about 11, and preferably containing a developlng agent as descrlbed pre-viously. Suitable materials and addenda frequently added to such compositions are disclosed on pages 79 to 80 of the November 1976 edition Or Research Dlsclosure.
The supports rOr the photographlc elements of thls lnventlon can be any material as long as lt does not deleter-iously effect the photographic propertles Or the film unit and is dimensionally stable. Typlcal flexlble sheet materials are descrlbed on page 85 of the November 1976 edltion of Research Dlsclosure.
The sllver hallde emulslons useful in this invention, both negative-worklng and direct-positlve ones, are well known to those skllled ln the art and are descrlbed ln Product Llcensing Index, Volume 92, December 1971, publication 9232, paragraph I, "Emulslon types", they may be chemlcally and spectrally sensltized as descrlbed on page 107, paragraph III, "Chemical sensltization", and pages 108 and 109, paragraph XV, "Spectral sensltization", of the above article; they can be protected against the production of fog and can be stablllzed against loss of sensitivity durlng keeping by employlng the materials described on page 107, paragraph V, "Antlfoggants and stabilizers", of the above article; they can contain development modifiers, hardeners, and coatlng aids as des-cribed on pages 107 through 108, paragraph IV, "Development modifiers"; paragraph VII, "Hardeners"; and paragraph XII, "Coating aids", of the above article; they and other layers in the photographic elements used in this inventlon can contain plasticizers, vehicles and filter dyes descrlbed on page 108, paragraph XI, "Plasticizers and lubricants", and paragraph VIII, "Vehicles", and page lO9, paragraph XVI, "Absorbing and filter dyes", of the above article; they and other layers in the photographic elements used in this invention may contain addenda which are incorporated by using the procedures described on page lO9, paragraph XVII, "Methods of addition", of the above article; and they can be coated by using the various techniques described on page lO9, paragraph XVIII, "Coating procedures", of the above article.
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes mater-ials that for all practical purposes do not migrate nor wander through organic colloid layers of the photographic elements of the invention in an alkaline medium, preferably when processed in a medium having a pH of ll or greater. The same meaning ls to be attached to the term "immobile". The term "diffusible"
as applied to the materials of this invention has the converse ~2~9 meaning and denotes materials having the property of diffu-sing effectively through the collold layers of the photo-graphic elements in an alkaline medium in the presence of "nondiffusing" materials. "Mobile" has the same meaning.
The term "associated therewith" as used herein is intended to mean that the materials can be in either the same or different layers so long as the materials are accessible to one another.
The following example further illustrates the invention.
EXAMPLE
(A) A control cover sheet was prepared by coating the following layers in the order received on a 0.004-inch poly-(ethylene terephthalate) film base:
(1) An acid layer comprising 15.5 g/m2 of poly(n-butyl acrylate-co-acrylic acid (30 percent acrylic acid) and o.43 g/m2 of Dicalite (trademark), Grade 103 diatomaceous earth;
(2) A timing layer comprising 1.929 g/m2 of cellulose acetate (40 percent acetyl) and 0.24 g/m2 of poly(styrene-co-maleic anhydride); and (3) A second timing layer of 2.15 g/m2 of poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (15:79:6).
(B) Another cover sheet was prepared sim~ilar to (A), except that layer 2 contained 0.22 g/m2 of hydroquinone mono-acetate.
An integral photographic element of the type des-cribed in E:lement 10 of U.S. Patent 4,030,925 of Leone et al, issued June 21, 1977, was exposed to a tungsten llght source through a graduated density multicolor test obJect.
The following processing composition was employed in a pod and spread between the exposed photosensitive ele-ment and the transparent cover sheets described above at 16C
and 38C by passing the transfer "sandwich" between a pair of ~uxtaposed rollers so that the liquid layer was about .003 inch.
The pod composition was as follows:
Distilled water 850 ml Potassium hydroxide 46.8 g Sodium sulfite (anhydrous) 1.0 g 5-methyl-1,2,3-benzotriazole3.8 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone12.0 g t-butylhydroquinone 0.3 g Carboxymethyl cellulose56.6 g Tamol SN (Trademark of Rohm and Haas Company) dispersing agent 8.8 g Carbon 171.0 g Potassium fluoride 10.0 g Methyl hydroquinone 0.1 g 1,4-cyclohexanedimethanol1.0 g Sodium hydroxide 3.4 g 4-chloro-3,5-xylenol 0.04 g The sensitometric changes observed upon processing these elements at 16C and 38C were as follows:
,9 ~al 3 0 Ir I O
I I O
* ~) ~S:~ ~D N
bO ~
OF~ o o ~ ~ I +
C~
~1 -' ~ O O ~
m I + td ~a N C~
a~ . . o ~; c o h X ~ NIr~ ~) t~ a~ o o a ~e h o o C~
C3 ~
~ ~D ~1 Q) ~ ~
m o o ~a ~ ~
Q~ .
~ O O J~
+ +
S ~~ 3 ,~ ~
e~ O O
~ h c o o ~ ~ + +
~ o o , 1 o ~
m + ~
h ~d ~1 ~ e e cC J~ m a, o C) *
The above results indicate that the speed loss has been significantly reduced in Element B, especially ln the figures given for the red region.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be apparent that variations and modifications can be effected within the spirit and scope of the invention.
O--C--C H
OH
292~
As noted above, the hydroqulnone esters employed ln this lnvention can be employed elther ln or behlnd the timing layer with respect to the side of appllcatlon of the processing composltion. Preferably, lt ls lncorporated ln the timing layer so that the release of the competing developer occurs after a finite time. When a longer delay is deslred, the compound ls merely incorporated ln an ad~acent layer, behind the timing layer and farther away from the developing silver halide layers. This layer can be contiguous to the timing layer or can be located in an ad~acent layer several layers away from the timing layer, depending upon the results desired.
Particularly preferred timing layers useful in thls invention comprise a polymeric latex having an activation energy of penetration of the layer by an aqueous alkallne solution of greater than 18 kcal/mole. Such latex tlming layers result from a coalescence or partial coalesence of polymeric particles from an aqueous latex. Preferred latex timlng layers are described, along with their method of 20 synthesis, inCdn. Application Serial No.275~94l of Hannie, filed Apri~ 12, 1977.
These timing layers delay the neutralization of the alkaline processlng compositlon by the acid layer so that production of a hlgh quallty dye lmage ls more reproducible over a large temperature range.
The activation energy of penetration of polymeric layers by aqueous alkaline solutions can be determined by the following simple test.
A thymolphthalein dye or cresol red dye indicator 3~ is coated on a polyethylene terephthalate film support at 210 mg/m2 with 6.6 g/m2 gelatin in the case of thymolphthalein or 2.2 g/m2 ln the case of cresol red.
_ g _ 'B
. , 1 z9 A processing composition comprising a pod which contains about o.84 N potassium hydroxide and about 5 percent carboxymethyl cellulose in water, along with other conven-tional developer ingredients, is spread between the element containing the indicator dye and a sample of a cover sheet by passing the "sandwich" between a pair of ~uxtaposed pressure rollers so that the developer layer thickness is 0.1 mm.
The cover sheet comprises a polyethylene terephthalate support containing a first layer of a 30/70 (by weight) copolymer of poly(butyl acrylate-co-acrylic acid), a second layer of 50/50 (mole ratio) polymer of poly(styrene-co-maleic anhydride) at 2.2 g/m2 and the outer layer being the polymer for which the activation energy is to be determined.
The time required to reduce the pH of a unit to pH
10 as measured by the color change of the thymolphthalein dye from blue to colorless or to pH 8 as measured by the change of the cresol red dye from red to yellow is measured at various temperatures within the range of 13 to 54C. The time in seconds is plotted on a logarithmic scale against the recip-rocal of the temperature expressed in K. The activationenergy in kcal/mole is determined from the slope of the straight line portion of the curve according to the formula:
~Ea (activation energy) = 0.00458 X log Y2/Y
l/T2 l/Tl where T2 is the higher temperature and Tl is the lower temperature and Y2 is the time at T2 and Yl is the time at Tl. The thickness of the acid layer and the polymer layer is not critical to the proper determination of activation energy.
A discussion of activation energy calculations can be found in Kinetics and Mechanism, second edition, New York, John Wiley and Sons, 1961, pages 22 through 25.
Latex polymers having an activation energy to penetration by aqueous alkaline solution of greater than 18 kcal/mole include poly(methyl acrylate-co-ltaconic acid-co-vinylidene chloride) and the like.
Preferred polymeric latexes having an activation energy of penetration to aqueous alkaline solution of greater than 18 kcal/mole are terpolymers of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of poly-merized ethylenically unsaturated carboxylic acid and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
Any ethylenically unsaturated monomer which is different from the other monomers in the polymeric latex can be used to prepare the terpolymer including alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate and the like; vinyl esters, amides, nitriles, ketones, halides, ethers, olefins, diolefins and the like as exemplified by acrylonitrile, methacrylonitrile, styrene, alpha-methyl styrene, acrylamide, methacrylamide, vinyl chloride, methyl vinyl ketone, fumaric, maleic and itaconic esters, 2-chloroethylvinyl ether, dimethyl-aminoethyl methacrylate, 2-hydroxyethyl methacrylate, N-vinyl-succinamide, N-vinylphthalimide, N-vinylpyrrolidone, butadiene, ethylene and the like. Preferred monomers are methyl acrylate and acrylonitrile.
~29~29 Examples of ethylenlcally unsaturated carboxylic acids which can be lncluded in the polymer lnclude acryllc acid, methacrylic acid, itaconlc acid, fumarlc acid, maleic acid, their anhydrides, and the like. The preferred carboxylic acids are acrylic acid and itaconic acid.
A preferred terpolymer useful in the invention comprises 15 weight percent methyl acrylate, 83 weight percent vinylidene chloride and 2 weight percent ltaconic acid. Further examples of latex polymers useful herein can be ~ound ln U.S.
Patents 3,271,345; 2,627,088; 2,491,023; 2,779,684; 3,437,484;
2,943,937 and 3,143,421.
The latex timing layer can generally be employed over a broad range of coverages. Preferred coverage for the layer ranges from about 1.0 g/m2 to 6.0 g/m2 and more pre~erably from about 1 to 3 g/m2.
In a preferred embodlment of my lnventlon, the hydro-quinone esters are incorporated in an ad~acent layer comprlsing a timing layer, which layer, in turn is coated with the latex timing layer having a high activation energy described above. In this "doublet' timing layer embodiment, the first timing layer in which the hydroquinone esters are employed comprising a polymeric latex having an activation energy of penetratlon to aqueous alkaline solution of less than 18 kcal/mole. The second timing layer ls as described above and comprises a polymeric latex havlng an actlvatlon energy of penetration to aqueous alkallne solutlon of greater than 18 kcal/mole. This "double" timing layer system ls described more fully in Cdn. Applicatlon Serial No.275,941 of ~annie and Ducharme, filed April 12, 1977.
~ - 12 -2~
Examples of polymers for the flrst timlng layer described above having an activatlon energy of penetratlon of aqueous alkaline composltion of less than 18 kcal/mole are mixtures of cellulose acetate and a maleic anhydrlde copolymer with 5 to 50 percent by weight of the mixture belng sald copolymer such as described in Cdn. Patent 1,072,800 issued March 4, 1980.
The maleic anhydride copolymer in thls timing layer should be employed in a concentration of about 2 to about 20 percent by weight, depending somewhat on the other comonomer.
A 5 to 20 percent concentration has been found to be particu-larly effective. The thickness of this tlming layer should be such as to provide a coverage of about 1 to about 5 g/m2.
The cellulose acetate employed in that layer will usually have acetyl contents of about 37 to 40 percent by weight, the 37 percent being substantially more permeable than the 40 percent acetyl. Mixed esters can also be employed, such as cellulose acetate propionate, cellulose acetate butyrate, etc.
The maleic anhydride copolymer can be selected from a wide variety of materials, so long as it ls compatible with the cellulose acetate employed to provide a clear film. Particu-larly good results are obtained with poly(styrene-co-maleic anhydride), poly(ethylene-co-maleic anhydrlde) and poly(methyl vinyl ether-co-maleic anhydride).
Examples of other layers containlng polymers havlng an activatlon energy of less than 18 kcal/mole are polyvinyl acetate, cellulose acetate phthalate, partial acetals of polyvinyl alcohol, a polymer latex of butyl acrylate-diacetone Z~
acrylamide-styrene-methacryllc acid (60/30/4/6) as described in ~.S. Patent 3,785,815, mixtures of polyvinyl acetate and polyvinyl alcohol such as polyvinyl acetate latex in 78/22 ratio with polyvinyl alcohol, cellulose acetate (40 percent acetate in 95/5 ratio with poly[styrene-co-maleic anhydride]
[50/50 mole ratio]) as described in Canadian Patent 1,072,800 and the like.
One embodiment of an assemblage Or an integral transfer color element and a process for producing a photo-graphic transfer image in color in which my invention can beemployed is disclosed in Canadian Patent 928,559. In this embodiment, the support for the photosensitive element is transparent and is coated with an image-receiving layer, a light-reflective layer, an opaque layer and photosensitive layers, having associated therewith dye image-providing material layers. A rupturable container containing the alkaline processing composition described above and an opacifier such as carbon black is positioned ad~acent the top layer and a transparent cover sheet. The cover sheet comprises a transparent support which is coated with a neutralizing layer and a timlng layer containing the hydro-quinone esters according to the invention. The film unit is placed in a camera, exposed through the transparent cover sheet and then passed through a pair of pressure-applying members in the camera as it is being removed therefrom. The pressure-applying members rupture the container and spread processlng composition and opacifier over the image-forming portion of the assemblage to protect it from -exposure. The processing compositlon develops each silver hallde layer and dye images are formed as a result of development which ~ - 14 -'~lZ~Z9 diffuse to the image-receivlng layer to provide a right-reading image which is viewed through the transparent support on the opaque reflecting layer background. The neutralizlng layer then neutrallzes the alkallne processing compositlon after the tlmlng layer has been permeated, thus "shutting down" the system. For further details concerning the format of this particular lntegral assemblage, reference is made to the above-mentioned Canadian Patent 928,559.
10Another embodiment of an assemblage of an integral transfer color element and a process for produclng a photo-graphic transfer image in color ln which my invention can be employed is described in U.S. Patent 3,415,644. In this embodiment, the negative comprises an opaque support which is coated with photosensitive layers having associated therewith dye image-providing material layers. A rupturable container containing the alkaline processing composition described above, TiO2 and an indicator dye (see U.S. Patent 3,647,437) is positioned ad~acent the top layer and a trans- ;~
parent receiver. The receiver comprises a transparent support which is coated with a neutralizing layer, a timing layer containing the hydroquinone esters according to the invention and an image-receiving layer. The film unit is placed in a camera, exposed through the transparent receiver and then passed through a pair of pressure-applying members in the camera as it is belng removed therefrom. The pressure-applylng members rupture the contalner and spread processing composltlon, TiO2 and indicator dye over the image-forming portion of the assemblage to protect it from exposure. The processing ccmposltion develops each sllver hallde layer and dye images are formed as a result of development whlch diffuse to the ~mage-receiving layer which ls viewed through the transparent support on a white background -- the lndicator dye having "shifted" to a colorless form as the alkali ls consumed by the neutralizing layer. As before, the neutral-izing layer then neutralizes the alkaline processing composi-tion after the timing layer has been permeated, thus "shutting down" the syste~. For further details concerning the format of this particular assemblage, reference is made to the above-mentioned U.S. Patent 3~415~644~
Since the image ln this embodiment is geometrically reversed, an image-reversing optlcal system such as a mirror in the camera is needed to reverse the image so that a right-reading image is vlewable in the dye image-receiving layer.
Another embodiment of an assemblage of a color diffusion transfer film unit in which this invention can be employed in a dye image-receiving element is described in U.S. Patent 3~362~819~ The image-receiving element comprises a support, which is usually opaque, having thereon a neutral-izing layer, a timing layer containing the hydroquinoneesters of the invention and a dye image-receivlng layer.
For further details concernlng the use of such an element ln color transfer assemblages, reference is made to the above-mentloned U.S. Patent 3~362~819~
Stlll other useful lntegral formats in whlch my lnventlon can be employed are descrlbed ln U.S. Patents 3~415~645; 3~415~646; 3~647~437; ~635~707~ and British Patent 1, 330~ 524 ~ \
The photosensltlve element useful in my invention can be treated with an alkaline processlng composltlon to r \ ~ 16 ~ ~ 12~29 effect or initiate development in any manner. A preferredmethod for applying processing composition is by use of a rupturable container or pod which contains the composition.
In general, the processing composition employed in my lnvention contains the developing agent for development. Where the developer is incorporated in the photosensitive element, the alkaline processing composition serves to activate the incorporated developer.
The dye image-providing materials which may be employed in my invention generally may be characterized as either (1) initially soluble or diffusible in the processing composition but are selectively rendered nondiffusible in an imagewise pattern as a function of development, such as those disclosed, for example, in U.S. Patents 2,647,049;
2,661,293; 2,698,244; 2,698,798; 2,802,735; 2,774,668; and 2,983,606; or (2) initially insoluble or nondiffusible in the processing composition but which are selectively rendered diffusible in an imagewise pattern as a function of develop-ment, such as those disclosed, for example, in U.S. Patents 3,227,550; 3,227,551; 3,227,552; 3,227,554; 3,243,294; and 3,445,228. These materials may be preformed dyes or dye precursors, e.g., color couplers, oxichromic compounds and the like.
In a preferred embodiment of my invention the dye image-providing material is a nondiffusible or ballasted redox dye releaser. Such compounds are, generally speaking, compounds which can be oxidized by oxidized developing agent, i.e., cross-oxidized, to provide a species which as a function of oxidation will release a diffusible dye, such as 30 by alkaline hydrolysis. Such dye releasers are described in U.S. Patents 3,725,062 of Anderson and Lum issued April 3, l~lZ~ 9 1973; 3,698,897 of Gompf and Lum lssued October 17, 1972;
3,443,939 and 3,443,940 Or Bloom et al lssued May 13, 1969;
3,928,312 of ~leckensteln lssued December 23, 1975; 3,929,760 of Landholm et al lssued December 20, 1975; 3,942,987 of Landholm et al issued March 9, 1976~l 3,932,380 of Krutak et al issued January 13, 1976; 3,980,479 of Fields et al issued September 14, 1976; and U.S. Publlshed Patent Appllcatlon B-351,673 of Fleckenstein et al published January 28, 1975;
German OLS 2,406,664; Canadian Patent 1,047,821Of Kxutak et al issued February 6, 1979; Canadian Patent 1,047,030 of Haase et al issued ~anuary 23, 1979; Canadian Patent 1,073,451 of ~inshaw et al issued March 11, 1980; and Canadian Application 283,408 of Chasman et al filed July 25, 1977.
In an especlally preferred embodiment of my inven-tion, the dye releasers such as those in the Fleckenstein et al patents and appllcatlons referred to above are employed.
Such compounds are ballasted sulfonamldo compounds which are alkali-cleavable upon oxldation to release a diffusible dye from the nucleus and have the formula:
Y -~-- (Ba l l ast) n- 1 wherein:
a) Col is a dye or dye precursor moiety;
b) Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic '~"3 ~12~29 groups or polymeric groups) as to render the compound nondiffusible ln the photosensitlve element durlng development ln an alkaline processing compositlon;
c) G is OR2 or NHR3 wherein R2 is hydrogen or a hydrolyzable molety and R3 ls hydrogen or a substituted or unsubsti-tuted alkyl group of 1 to 22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl, secondary butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, cyclo-butyl, 4-nltroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, docosyl, benzyl, phenethyl, etc., (when R3 is an alkyl group of greater than 6 carbon atoms, it can serve as a partlal or sole Ballast group);
d) Y represents the atoms necessary to complete a benzene : nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring such as pyrazolone, pyrimidine, etc; and e) n is a positive integer of 1 to 2 and is 2 when G ls OR2 or when R3 is a hydrogen or an alkyl group of less than 8 carbon atoms.
In another preferred embodlment of my lnventlon, initially diffusible dye image-providing materials are employed such as dye developers, including metal complexed dye developers such as those described in U.S. Patents 3,453,107; 3,544,545; 3,551,406; 3,563,739; 3,597,200;
- 3,705,184; and oxichromic developers as described and claimed in my coworkers' Lestina and Bush Applicztion Canadian Patent 995,948 issued August 3, 1976.
- 19 _ ~12~29 When oxichromic developers are employed, the lmage is formed by the diffusion of the oxichromic developer to the dye image-receiving layer where it undergoes chromogenic oxida-tion to form an image dye.
The assemblage of the present invention may be used to produce positive images in single- or multicolors.
In a three-color system, each silver halide emulsion layer of the film assembly will have associated therewith a dye image-providing material possessing a predominant spectral absorption within the region of the visible spectrum to which said silver halide emulsion is sensitive, i.e., the blue-sensitive silver halide emulsion layer will have a yellow dye image-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye image-providing material associated therewith.
The dye image-providing material associated with each silver halide emulsion layer may be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer.
The concentration of the dye image-providing materials that are employed in the present invention may be varied over a wide range depending upon the particular com-pound employed and the results which are desired. For example, the dye image-providing compounds may be coated as dispersions in layers by using coating solutions containing a ratio between about 0.25 and about 4 of the dye image-providing compound to the hydrophilic film-forming natural material or synthetic polymer binder, such as gelatin, .
polyvinyl alcohol, etc., which ls adapted to be permeated by aqueous alkaline processing composltion.
Any silver halide developing agent can be employed in my invention depending upon the particular chemistry system involved. The developer may be employed in the photosensitive element to be activated by the alkaline processing composition. Specific examples of developers which can be emplsyed in my invention include:
hydroquinone N-methylaminophenol Phenidone (l-phenyl-3-pyrazolidinone) Dimezone (l-phenyl-4,4-dimethyl-3-pyrazolidinone) aminophenols N-N-diethyl ~-phenylenediamine 3-methyl-N,N-diethyl-_-phenylenediamine N,N,N',N'-tetramethyl-~-phenylenediamine 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 4,4-bis(hydroxymethyl)-1-phenyl-3-pyrazolidinone, etc.
The black and white developing agents are preferred, however, since the color developers are generally slower, can cause stain, and can cause dermatitis if not handled properly.
In using dye releaser compounds in my invention which produce diffusible dye lmages as a function of develop-ment, either conventional negative-working or direct-positlve sllver halide emulslons may be employed. If the sllver halide emulsion employed is a direct-positive silver halide emulsion, such as an internal-image emulsion deslgned for use ln the internal lmage reversal process or a fogged, dlrect-positive emulsion such as a solarizing emulsion, which is 3 developable in unexposed areas, a positive image can be obtained in certain embodiments on the dye image-receiving layer. After exposure of the film unit, the alkaline proces-sing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The developing agent present in the film 2~9 unit develops each of the silver hallde emulsion layers ln the unexposed areas (since the silver hallde emulslons are d~rect-positive ones), thus causing the developing agent to become oxidized imagewise corresponding to the unexposed areas Or the direct-positive silver halide emulslon layers. The oxidized developlng agent then cross-oxidizes the dye-releasing compounds, and the oxidized form of the compounds then undergoes a base-catalyzed reaction to release the dyes imagewise as a function of the imagewise exposure of each of the silver halide emulsion layers. At least a portion of the lmagewlse dlstrlbutlons of diffusible dyes diffuse to the image-receiving layer to form a positive image of the original sub~ect.
Internal-image sllver halide emulsions useful in this invention are described more fully in the November 1976 edition of Research Disclosure, pages 76 through 79.
The varlous sllver halide emulsion layers of a color film assembly of the invention can be disposed in the usual order, i.e., the blue-sensitive silver hallde emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers. If desired, a yellow dye layer or a yellow colloidal silver layer can be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer. If desired, the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layer flrst with 3 respect to the exposure slde, followed by the red-sensitive `~ - 22 -and green-sensitive layers.
While the alkaline processing composition used ln this invention can be applied to the assemblage by the use of rupturable contalners as described previously, other means ~or discharging the composition within the assemblage could also be used, e.g., inter~ecting the compositlons with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge.
In a color photographic assemblage according to this invention, each silver halide emulsion layer containing a dye image-providing material or having the dye image-providing material present in a contiguous layer may be separated from the other silver halide emulsion layers in the negative portion of the film unit by materials including gelatin, calcium alginate, or any of those disclosed in U.S.
Patent No. 3,384,483, polymeric materials such as polyvinyl-amides as disclosed in U.S. Patent 3,421,892, or any of those disclosed in French Patent 2,028,236 or U.S. Patents Nos. 2,992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263, 3,069,264; 3,121,011 and 3,427,158.
Generally speaking, except where noted otherwise, the silver halide emulsion layers in the invention comprise photosensitive silver halide dispersed in gelatin and are about o.6 to 6 microns in thickness; the dye image-providing materials are dlspersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 0. 2 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 0. 2 to 5 microns in thickness. Of course, these 30 ' thicknesses are approximate only and can be modified according to the product desired.
1~2S~9 Scavengers for oxldized developing agent can be employed in various lnterlayers of the photographlc elements of the invention. Suitable materials are disclosed on page 83 of the November 1976 edition Or Research Disclosure.
The alkaline solution-permeable, llght-reflectlve layer employed ln certaln embodlments of photographic assem-blages of thls invention are described more fully in the November 1976 edition of Research Disclosure, page 82, The neutralizing layer employed in my inventlon whlch becomes operative after permeation of the processing composition through the timing layer will effect a reductlon in the pH of the image layers from about 13 or 14 to at least 11 and preferably 5 to 8 within a short tlme after imblbltion. Suitable materlals and their functionlng are disclosed on pages 22 to 23 of the July 1974 edltion of Research Disclosure and pages 35 to 37 of the July 1975 edition of Research Disclosure.
The lnert timlng or spacer layer employed in my invention over the neutralizing layer "tlmes" or controls the pH reductlon as a functlon of the rate at whlch alkall dlffuses throughout the lnert spacer layer. Examples of such timing layers and their functioning are disclosed in the Research Disclosure articles mentioned in the paragraph above concerning neutralizing layers.
Any material can be employed as the image-receiving layer in this invention as long as the desired function of mordanting Gr otherwise fixing the dye images will be ~12~
obtained. The particular materlal chosen wlll, Or course, depend upon the dye to be mordanted. Sultable materlals are disclosed on pages 80 to 82 of the November 1976 editlon of Research Disclosure.
The alkaline processing composition employed ln this lnvention is the conventional aqueous solutlon Or an alkallne material, e.g., alkali metal hydroxldes or carbonates such as sodium hydroxide, sodium carbonate, or an amine such as diethylamine, possessing a pH Or at least about 11, and preferably containing a developlng agent as descrlbed pre-viously. Suitable materials and addenda frequently added to such compositions are disclosed on pages 79 to 80 of the November 1976 edition Or Research Dlsclosure.
The supports rOr the photographlc elements of thls lnventlon can be any material as long as lt does not deleter-iously effect the photographic propertles Or the film unit and is dimensionally stable. Typlcal flexlble sheet materials are descrlbed on page 85 of the November 1976 edltion of Research Dlsclosure.
The sllver hallde emulslons useful in this invention, both negative-worklng and direct-positlve ones, are well known to those skllled ln the art and are descrlbed ln Product Llcensing Index, Volume 92, December 1971, publication 9232, paragraph I, "Emulslon types", they may be chemlcally and spectrally sensltized as descrlbed on page 107, paragraph III, "Chemical sensltization", and pages 108 and 109, paragraph XV, "Spectral sensltization", of the above article; they can be protected against the production of fog and can be stablllzed against loss of sensitivity durlng keeping by employlng the materials described on page 107, paragraph V, "Antlfoggants and stabilizers", of the above article; they can contain development modifiers, hardeners, and coatlng aids as des-cribed on pages 107 through 108, paragraph IV, "Development modifiers"; paragraph VII, "Hardeners"; and paragraph XII, "Coating aids", of the above article; they and other layers in the photographic elements used in this inventlon can contain plasticizers, vehicles and filter dyes descrlbed on page 108, paragraph XI, "Plasticizers and lubricants", and paragraph VIII, "Vehicles", and page lO9, paragraph XVI, "Absorbing and filter dyes", of the above article; they and other layers in the photographic elements used in this invention may contain addenda which are incorporated by using the procedures described on page lO9, paragraph XVII, "Methods of addition", of the above article; and they can be coated by using the various techniques described on page lO9, paragraph XVIII, "Coating procedures", of the above article.
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes mater-ials that for all practical purposes do not migrate nor wander through organic colloid layers of the photographic elements of the invention in an alkaline medium, preferably when processed in a medium having a pH of ll or greater. The same meaning ls to be attached to the term "immobile". The term "diffusible"
as applied to the materials of this invention has the converse ~2~9 meaning and denotes materials having the property of diffu-sing effectively through the collold layers of the photo-graphic elements in an alkaline medium in the presence of "nondiffusing" materials. "Mobile" has the same meaning.
The term "associated therewith" as used herein is intended to mean that the materials can be in either the same or different layers so long as the materials are accessible to one another.
The following example further illustrates the invention.
EXAMPLE
(A) A control cover sheet was prepared by coating the following layers in the order received on a 0.004-inch poly-(ethylene terephthalate) film base:
(1) An acid layer comprising 15.5 g/m2 of poly(n-butyl acrylate-co-acrylic acid (30 percent acrylic acid) and o.43 g/m2 of Dicalite (trademark), Grade 103 diatomaceous earth;
(2) A timing layer comprising 1.929 g/m2 of cellulose acetate (40 percent acetyl) and 0.24 g/m2 of poly(styrene-co-maleic anhydride); and (3) A second timing layer of 2.15 g/m2 of poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (15:79:6).
(B) Another cover sheet was prepared sim~ilar to (A), except that layer 2 contained 0.22 g/m2 of hydroquinone mono-acetate.
An integral photographic element of the type des-cribed in E:lement 10 of U.S. Patent 4,030,925 of Leone et al, issued June 21, 1977, was exposed to a tungsten llght source through a graduated density multicolor test obJect.
The following processing composition was employed in a pod and spread between the exposed photosensitive ele-ment and the transparent cover sheets described above at 16C
and 38C by passing the transfer "sandwich" between a pair of ~uxtaposed rollers so that the liquid layer was about .003 inch.
The pod composition was as follows:
Distilled water 850 ml Potassium hydroxide 46.8 g Sodium sulfite (anhydrous) 1.0 g 5-methyl-1,2,3-benzotriazole3.8 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone12.0 g t-butylhydroquinone 0.3 g Carboxymethyl cellulose56.6 g Tamol SN (Trademark of Rohm and Haas Company) dispersing agent 8.8 g Carbon 171.0 g Potassium fluoride 10.0 g Methyl hydroquinone 0.1 g 1,4-cyclohexanedimethanol1.0 g Sodium hydroxide 3.4 g 4-chloro-3,5-xylenol 0.04 g The sensitometric changes observed upon processing these elements at 16C and 38C were as follows:
,9 ~al 3 0 Ir I O
I I O
* ~) ~S:~ ~D N
bO ~
OF~ o o ~ ~ I +
C~
~1 -' ~ O O ~
m I + td ~a N C~
a~ . . o ~; c o h X ~ NIr~ ~) t~ a~ o o a ~e h o o C~
C3 ~
~ ~D ~1 Q) ~ ~
m o o ~a ~ ~
Q~ .
~ O O J~
+ +
S ~~ 3 ,~ ~
e~ O O
~ h c o o ~ ~ + +
~ o o , 1 o ~
m + ~
h ~d ~1 ~ e e cC J~ m a, o C) *
The above results indicate that the speed loss has been significantly reduced in Element B, especially ln the figures given for the red region.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be apparent that variations and modifications can be effected within the spirit and scope of the invention.
Claims (23)
1. In a photographic assemblage comprising:
a) a support having thereon at least one photosensitive silver halide emulsion layer having associated there-with a dye image-providing material;
b) a dye image-receiving layer;
c) an alkaline processing composition and means for discharging same within said assemblage;
d) a neutralizing layer for neutralizing said alkaline processing composition; and e) a timing layer disposed between said neutralizing layer and said photosensitive silver halide emulsion layer so that said processing composition must first permeate said timing layer before contacting said neutralizing layer;
said assemblage containing a silver halide developing agent, the improvement wherein said assemblage contains a hydro-quinone ester either in said timing layer or in a layer which is adjacent thereto and is so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
a) a support having thereon at least one photosensitive silver halide emulsion layer having associated there-with a dye image-providing material;
b) a dye image-receiving layer;
c) an alkaline processing composition and means for discharging same within said assemblage;
d) a neutralizing layer for neutralizing said alkaline processing composition; and e) a timing layer disposed between said neutralizing layer and said photosensitive silver halide emulsion layer so that said processing composition must first permeate said timing layer before contacting said neutralizing layer;
said assemblage containing a silver halide developing agent, the improvement wherein said assemblage contains a hydro-quinone ester either in said timing layer or in a layer which is adjacent thereto and is so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
2. The assemblage of Claim 1 wherein:
a) said dye image-receiving layer is located between said support and said silver halide emulsion layer; and b) said assemblage also includes a transparent cover sheet over the layer outermost from said support.
a) said dye image-receiving layer is located between said support and said silver halide emulsion layer; and b) said assemblage also includes a transparent cover sheet over the layer outermost from said support.
3. The assemblage of Claim 2 wherein said trans-parent cover sheet is coated with said neutralizing layer and said timing layer, respectively.
4. The assemblage of Claim 2 wherein said dis-charging means is a rupturable container containing said alkaline processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said transparent sheet and the layer outermost from said support.
5. The assemblage of Claim 1 wherein said hydro-quinone ester is hydroquinone diacetate, hydroquinone mono-acetate, hydroquinone monohexanoate, 3-t-butyl-4-hydroxy-phenyl acetate, hydroquinone monobenzoate or 4-hydroxy-3-tolyl benzoate.
6. The assemblage of Claim 1 wherein said hydro-quinone ester is present at a concentration of from about 0.054 g/m2 to about 0.54 g/m2.
7. The assemblage of Claim 1 wherein said timing layer is a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethyl-enically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
8. The assemblage of Claim 1 wherein said timing layer is a polymeric latex comprising from about 5 to about 35 percent by weight of acrylonitrile, from about 2 to about 10 percent by weight of a member selected from the group consisting of acrylic acid and itaconic acid and from about 55 to about 85 percent by weight of vinylidene chloride.
9. The assemblage of Claim 1 wherein said hydro-quinone ester is in a layer adjacent to said timing layer, said adjacent layer comprising a polymeric latex having an activation energy of penetration of the layer by an aqueous alkaline solution of less than 18 kcal/mole.
10. The assemblage of Claim 9 wherein said adjacent layer comprises a mixture of cellulose acetate and a maleic anhydride copolymer, said mixture comprising about 5 to about 50 percent by weight of said copolymer.
11. The assemblage of Claim 1 wherein said dye image-providing material is a ballasted sulfonamido compound which is alkali-cleavable upon oxidation to release a diffu-sible color-providing moiety from a benzene nucleus, said compound having the formula:
wherein:
a) Col is a dye or dye precursor moiety;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
c) G is OR2 or NHR3 wherein R2 is hydrogen or a hydrolyzable moiety and R3 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring; and e) n is a positive integer of 1 to 2 and is 2 when G is OR2 or when R3 is hydrogen or an alkyl group of less than 8 carbon atoms.
wherein:
a) Col is a dye or dye precursor moiety;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
c) G is OR2 or NHR3 wherein R2 is hydrogen or a hydrolyzable moiety and R3 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring; and e) n is a positive integer of 1 to 2 and is 2 when G is OR2 or when R3 is hydrogen or an alkyl group of less than 8 carbon atoms.
12. An integral photographic assemblage com-prising:
a) a photosensitive element comprising a transparent support having thereon the following layers in sequence:
a dye image-receiving layer; an alkaline solution-permeable, light-reflective layer; an alkaline solution-permeable, opaque layer; a red-sensitive, direct positive silver halide emulsion layer having a ballasted redox cyan dye releaser associated therewith; a green-sensitive, direct positive silver halide emulsion layer having a ballasted redox magenta dye releaser associated therewith;
and a blue-sensitive, direct positive silver halide emulsion layer having a ballasted redox yellow dye releaser associated therewith;
b) a transparent sheet superposed over said blue-sensitive silver halide emulsion layer and comprising a transparent support coated with, in sequence, a neutralizing layer and a timing layer; and c) a rupturable container containing an alkaline processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said trans-parent sheet and said blue-sensitive silver halide emulsion layer;
said assemblage containing a silver halide developing agent, the improvement wherein said assemblage contains a hydro-quinone ester either in said timing layer or in a layer which is adjacent thereto and is so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
a) a photosensitive element comprising a transparent support having thereon the following layers in sequence:
a dye image-receiving layer; an alkaline solution-permeable, light-reflective layer; an alkaline solution-permeable, opaque layer; a red-sensitive, direct positive silver halide emulsion layer having a ballasted redox cyan dye releaser associated therewith; a green-sensitive, direct positive silver halide emulsion layer having a ballasted redox magenta dye releaser associated therewith;
and a blue-sensitive, direct positive silver halide emulsion layer having a ballasted redox yellow dye releaser associated therewith;
b) a transparent sheet superposed over said blue-sensitive silver halide emulsion layer and comprising a transparent support coated with, in sequence, a neutralizing layer and a timing layer; and c) a rupturable container containing an alkaline processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said trans-parent sheet and said blue-sensitive silver halide emulsion layer;
said assemblage containing a silver halide developing agent, the improvement wherein said assemblage contains a hydro-quinone ester either in said timing layer or in a layer which is adjacent thereto and is so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
13. The assemblage of Claim 12 wherein each said redox dye releaser is a ballasted sulfonamido compound which is alkali-cleavable upon oxidation to release a diffusible color-providing moiety from a benzene nucleus, said compound having the formula:
wherein:
a) Col is a dye or dye precursor moiety;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
c) G is OR2 or NHR3 wherein R2 is hydrogen or a hydrolyzable moiety and R3 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring; and e) n is a positive integer of 1 to 2 and is 2 when G is OR2 or when R3 is hydrogen or an alkyl group of less than 8 carbon atoms;
and wherein said hydroquinone ester is in a layer adjacent to said timing layer, said adjacent layer comprising a polymeric latex having an activation energy of penetration of the layer by an aqueous alkaline solution of less than 18 kcal/mole.
wherein:
a) Col is a dye or dye precursor moiety;
b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
c) G is OR2 or NHR3 wherein R2 is hydrogen or a hydrolyzable moiety and R3 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring; and e) n is a positive integer of 1 to 2 and is 2 when G is OR2 or when R3 is hydrogen or an alkyl group of less than 8 carbon atoms;
and wherein said hydroquinone ester is in a layer adjacent to said timing layer, said adjacent layer comprising a polymeric latex having an activation energy of penetration of the layer by an aqueous alkaline solution of less than 18 kcal/mole.
14. The assemblage of Claim 13 wherein each said silver halide emulsion is an internal-image silver halide emulsion, said timing layer comprises a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride, and said adjacent layer comprises a mixture of cellulose acetate and a maleic anhydride copolymer, said mixture comprising about 5 to about 50 percent by weight of said copolymer.
15. In a process for producing a photographic transfer image in color from an imagewise-exposed photosensi-tive element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material, said process comprising treating said element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each of said exposed silver halide emulsion layers, said processing composition contacting said emulsion layer prior to contacting a neutralizing layer; whereby an imagewise distribution of dye image-providing material is formed as a function of development and at least a portion of it diffuses to a dye image-receiving layer to provide said transfer image, whereby a timing layer associated with said neutralizing layer is permeated by said alkaline processing composition after a predetermined time, said timing layer being disposed between said neutralizing layer and said photosensitive silver halide emulsion layer so that said processing composition must first permeate said timing layer before contacting said neutralizing layer; whereby said alkaline processing composi-tion is neutralized by means of said neutralizing layer associated with said photographic element after said predeter-mined time; the improvement wherein a hydroquinone ester is employed either in said timing layer or in a layer adjacent thereto and is so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydro-quinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
16. The process of Claim 15 wherein said hydro-quinone ester is hydroquinone diacetate, hydroquinone mono-acetate, hydroquinone monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydroquinone monobenzoate or 4-hydroxy-3-tolyl benzoate.
17. The process of Claim 15 wherein said hydro-quinone ester is present at a concentration of from about 0.054 g/m2 to about 0.54 g/m2.
18. The process of Claim 15 wherein said timing layer is a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethyl-enically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
19. The process of Claim 15 wherein said hydro-quinone ester is in a layer adjacent to said timing layer, said adjacent layer comprising a polymeric latex having an activation energy of penetration of the layer by an aqueous alkaline solution of less than 18 kcal/mole.
20. The process of Claim 19 wherein said adjacent layer comprises a mixture of cellulose acetate and a maleic anhydride copolymer, said mixture comprising about 5 to about 50 percent by weight of said copolymer.
21. In a dye image-receiving element comprising a support having thereon, in sequence, a neutralizing layer, a timing layer and a dye image-receiving layer, the improve-ment wherein a hydroquinone ester is employed in a layer between said dye image-receiving layer and said support, said hydroquinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
22. In a cover sheet comprising a transparent support having thereon, in sequence, a neutralizing layer and a timing layer, the improvement wherein said cover sheet contains a hydroquinone ester having the following formula:
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
wherein R is hydrogen or an acyl group having 1 to about 20 carbon atoms, R' is an acyl group having 1 to about 20 carbon atoms, and G is hydrogen, an alkyl group having 1 to about 6 carbon atoms or an aryl group having 6 to about 8 carbon atoms, and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
23. The cover sheet of Claim 22 wherein said hydro-quinone ester is in a separate layer between said neutralizing layer and said timing layer, said separate layer comprising a polymeric latex having an activation energy of penetration of the layer by an aqueous alkaline solution of less than 18 kcal/mole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84806177A | 1977-11-03 | 1977-11-03 | |
| US848,061 | 1977-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112929A true CA1112929A (en) | 1981-11-24 |
Family
ID=25302227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA312,741A Expired CA1112929A (en) | 1977-11-03 | 1978-10-05 | Use of hydroquinone esters as blocked competing developers for color transfer assemblages |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5931695B2 (en) |
| CA (1) | CA1112929A (en) |
| DE (1) | DE2847637A1 (en) |
| FR (1) | FR2408162A1 (en) |
| GB (1) | GB2007862B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5674247A (en) * | 1979-11-22 | 1981-06-19 | Konishiroku Photo Ind Co Ltd | Method for continuously processing silver halide photographic material |
| US4314020A (en) | 1980-08-04 | 1982-02-02 | Eastman Kodak Company | Color transfers assemblages with two timing layers and a neutralizing layer |
| EP0049685B1 (en) * | 1980-10-02 | 1984-07-18 | Ciba-Geigy Ag | Hydroquinone derivatives and their preparation and use in photographic materials |
| US4446216A (en) * | 1981-12-10 | 1984-05-01 | Smith Norman A | Photographic material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3243294A (en) * | 1963-11-06 | 1966-03-29 | Eastman Kodak Co | Photographic direct-positive color process |
| US3375253A (en) * | 1964-05-20 | 1968-03-26 | Eastman Kodak Co | Azonia salts |
| US3462266A (en) * | 1967-09-05 | 1969-08-19 | Eastman Kodak Co | Photographic color diffusion transfer processes and elements |
| GB1258924A (en) * | 1968-06-10 | 1971-12-30 | ||
| US3816126A (en) * | 1972-09-11 | 1974-06-11 | Polaroid Corp | Novel photographic products and processes |
| US4056394A (en) * | 1976-04-14 | 1977-11-01 | Eastman Kodak Company | Timing layer for color transfer film units comprising copolymer with activation energy to penetration greater than 18 kcal/mole |
-
1978
- 1978-10-05 CA CA312,741A patent/CA1112929A/en not_active Expired
- 1978-11-02 DE DE19782847637 patent/DE2847637A1/en not_active Withdrawn
- 1978-11-03 GB GB7843126A patent/GB2007862B/en not_active Expired
- 1978-11-03 FR FR7831100A patent/FR2408162A1/en active Granted
- 1978-11-04 JP JP13517678A patent/JPS5931695B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2007862A (en) | 1979-05-23 |
| GB2007862B (en) | 1982-03-03 |
| JPS5931695B2 (en) | 1984-08-03 |
| DE2847637A1 (en) | 1979-05-10 |
| FR2408162A1 (en) | 1979-06-01 |
| JPS5474744A (en) | 1979-06-15 |
| FR2408162B1 (en) | 1982-06-25 |
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