US 3770439 A
A photographic product having an image pattern receiving layer which comprises a polymer of the formula:
Claims available in
Description (OCR text may contain errors)
v United States Patent [1 1 Taylor 1 3,770,439 1 Nov. 6, "1973 i 1 POLYMERIC MORDANT IN COLOR DIFFUSION TRANSFER IMAGE RECEIVING LAYER  Inventor: Lloyd D. Taylor, Lexington, Mass.
 Assignee: Polaroid Corporation, Cambridge,
221 Filed: Jan. 3, 1972 21 Appl. No.1 215,082
Primary Examiner-Norman G. Torchin Assistant Examiner-Richard L. Schilling Att0rney Brown & Mikulka 57 ABSTRACT A photographic product having an image pattern receiving layer which comprises a polymer of the formula:
Formula A vi'here each R can be the same or different s-ubstituent chosen from the group consisting of hydrogen, alkyl, alkoxy and alkanol and Xis an anion radical.
13 Claims, No Drawings BACKGROUND OF THE INVENTION 1. The Field of the Invention This invention relates to photographic products.
More precisely, the invention disclosed herein relates to photographic products especially useful in providing image patterns by way of diffusion transfer photographic processes.
2. Description of the Prior Art Diffusion transfer photographic processes and photographic products adapted for such processes are well known to the art. Essentially, such products and processes involve a photosensitive s'ystem'wliich is exposed to an image-pattern of activating radiation,- After exposure, the resultant image pattern can be developed to provide a diffusion transfer image pattern which can be transferred to an image pattern receiving layer. Details relating to some of the better known diffusion transfer photographic productsand processes can be found in U. S. Pat. Nos. 2,983,603; 3,415,644; 3,415,645; 3,415,646; 3,473,925; 3,573,042; 3,573,043; 3,573,044; 3,576,625; 3,576,626; 3,578,540; 3,579,333; 3,473,925; 3,594,164 and 3,594,165 as well as in commonly assigned U. S. Pat. application Ser. Nos. 782,056, now U.S. Pat. No. 3,672,486; 782,( )75, now abandoned, both filed Dec. 9, 1969 and U. S. Pat. application Ser. No. 65,084 filed Aug. 19,- 1970, now U.S. Pat. No. 3,672,890. All of the above patents and applications are expressly incorporated herein in their entirety by reference. I
Photosensitive systems employed in the products and processes of the type described in the above-mentioned patents and applications comprise at least oneselectively sensitized silver halide layer 'i'n'te'gratedwith a dye image-providing material. Moreoften, however, such diffusion transfer photographic products and processes include a photosensitive system which can provide multicolor diffusion transfer image patterns and photosensitive systems of this type essentially include a blue, a green and a red sensitive silverhalide layer each integrated respectively with a yellow,-a magenta and acyan dye image-providing material.
Suitable d'y'e image-providing employed in diffusion transfer photosensitive systems are those which" areeither (I) initially soluble or diffusible in the processing composition but are selectively rendered non-diffusible as a function of development; or (2) initially soluble or non-diffusible in the processing composition but are selectively rendered diffusible as a function of development. Accordingly suitable dye image-providing materials ma'y be complete dyes or dye intermediates, e.g., color couplers and especially preferred materials are those known to the art as dye developers, e.g., a dye which is also a silver halide developing agent.
I Examples of and details relating to initially soluble or diffusible materials and their application in color diffusion transfer, can be found in U. S. Pat. Nos. 2,647,049; 2,661,293; 2,698,244; 2,698,798; 2,774,668 and 2,983,606. Examples of and detials relating to diffusion transfer systemsemploying initially non-diffusible materials can be fourid in U. S. Pat. Nos. 3,443,939; 3,443,940; 3,227,550; 3,227,551; 3,227,552; 3,227,554; 3,243,294; and 3,445,228.
A known diffusion transfer particularly suitable for providing monochrome or multicolor image patterns of or comprising green, cyan and blue colors is one employing phthalocyanine dye developers of the type described in U. S. Pat. No. 3,482,972 issued to Elbert M. Idelson on Dec. 9, 1969. Dye developers of the type disclosed there are those conforming to the following formula:
FORMULA B where that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining substituents being R groups, and R comprises a group (-A),,-E; A is a divalent organic linking radical; n'is a number of from 0 1; E is an ar'yl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or' para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium-and' zinc; and each R comprises the same or a dif- .-ferent moiety selected'frofn the group consistingof monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen. Most preferred are those cyan dyes within the above formula wherein the metal moiety is copper and these dye developers may be referred to simply as copper phthalocyanine dye developers.
SUMMARY OF THE INVENTION The present invention provides novel image receiving layers and diffusion transfer photographic products employing such layers. Essentially the image receiving layers of the present invention are water permeable, substantially water insoluble, dimensionally stable layers comprising a polymeric material including a polymer of the formula:
where each R can be the same or different substituent chosen from the group consisting of hydrogen, hydroxyl, alkyl, alkoxy or alkanol and preferably lower alkyl, alkoxy or alkanol, e.g., wherein the hydrocarbon Polymeric materials conforming to the above formula have been found to be especially effective as mordants for dye image providing materials and especially effective as mordants for the phthalocyanine dye developers mentioned before. Accordingly, photographic products containing the novel image receiving layers are particularly suitable for providing high quality, colored, diffusion transfer image patterns consisting of or comprising cyan, green or blue colors provided by phthalocyanine dye developers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS As mentioned, the image receiving layers of the present'invention essentially comprise a polymer of Formula A. More precisely, however, the image receiving. layers of the present invention comprise a polymer of Formula A copolymerized with other polymeric materials or preferably a physical blend of other polymeric materials and a polymer of Formula A. Other polymeric materials which can be included in the copolymers or in the mixtures or blends comprising the image receiving layers of the present invention are those compatable polymeric materials which can provide substantially transparent water permeable and/or swellable but substantially water insoluble, dimentionally stable layers. Specific suitable polymeric materials that can be included in the image receiving layers copolymerized with or most preferably in physical admixture with a polymeric material of Formula A include the polymers and copolymers of polyvinyl alcohol, polyacrylamide, polyvinyl pyridine and polyhydroxyalkylcellulose such .as polyhydroxymethylcellulose, polyhydroxyethylcel lulose, etc. Especially suitable receiving layers include a mixture or blend of polyacrylamide, and/or polyhydroxyalkylcellulose together with poly-4- vinylpyridine and a polymeric material of Formula A where the concentration of the polymeric material of Formula A ranges from about 8 percent by weight of the total weight of polymeric materials in the blend to about percent by weight or somewhat higher.
. Polymeric materials of Formula A as well as those that can be mixed or blended therewith to provide image receiving layers of the present invention are commercially available. The particular additional polymeric materials selected to be employed in the mixture and the respective amounts of each will be determinedprimarily by the balance of properties and characteristics desired of the layer, e.g., the strength, the swellability or moisture permeability of the layer. The molecular weight of the polymeric materials employed in the mixtures or blends'is not an especially critical feature and is subject to normal considerations such as the case of dispersion of the material in a selected dispersion medium or the compatibility of the polymeric material with other ingredients of the mixture and/or with the dispersion medium.
DESCRIPTION OF THE PREFERRED EMBODIMENT Thefollowing illustrates some of the advantages and benefits to be obtained in accordance with the practice 2. a red-sensitive gelatino silver iodobromide emulsion coated at a coverage of about l40 mgs./ft. of silver and about 50 mgs./ft. of gelatin;
3. A layer of a 60-30-4-6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic' acid and polyacrylamide coated at a coverage of about 150 mgs./ft. of the copolymer and about 5 mgs./ft. of polyacrylamide;
4. a layer of magenta dye developer dispersed in gelatin and coated at a coverage of about 100 mgs./ft. of dye and about 150 mgsJft. of gelatin;
5. a green-sensitive gelatino silver iodobromide emul sion coated at a coverage of about 120 mgs./ft. of silver and about 35 mgs./ft. of gelatin;
6. a layer containing the copolymer referred to abov'e in layer 3 and polyacrylamide coated at a coverage of about I00 mgs./ft. of copolymer and about 12 mgS./ft. of polyacrylamide;
7. a layer of yellow dye developer dispersed in gelatin and coated at a coverage of about 70 mgs./ft. of dye and about 105 mgs./ft. of gelatin;
8. a blue-sensitive gelatino silver iodobromide emulsion layer including the auxiliary developer 4- methylphenyl hydroquinone coated at a coverage of about 80 mgs./ft. of silver, about 25 mgs./ft.? of gelatin and about 15 mgs./ft. of auxiliary developer; and
9. a layer of gelatin coated at a coverage of about 50 mgs./ft. of gelatin.
The three developers develpers employed above were the following:
a magenta dye developer; and
a yellow dye developer.
Then a transparent 4'mil. polyethylene terephthalate film base was coated, in succession, with the following illustrative layers:
1. a polymeric acid neutralizing layer containing a 7:3 mixture, by weight, of polyethylene/maleic anhydride copolymer and 88-90 percent hydrolyzed polyvinyl acetate at a coverage of about 1,000 mgs./ft.
2. a graft copolymer'of acrylamide and diacetone acrylamide on a polyvinyl alcohol backbone in a molar ratio of 13.22] at a coverage of about 800 mgs./ft. to
provide a polymeric spacer or timing layer; and
3. a receiving layer was provided at a coverage of about 300 mgm./ft. comprising a mixture of polyacrylamide, poly-4-vinyl pyridine and an approximately equivalent mixture of polymers of Formula A of thefollowing specific structures:
H+ NH O.S Q H on, N=o CN CH: I C
on l SO2-NH-(EH H v N ([3H 01- 1r0- a l cHiN+ oH3)a' N(JuN 0H CH; I 0 g 40 Meta and para Polyvinylbenzyl trimethyl ammonium N H chlorides The ratio of each polymeric material to each other was varied in the manner set forth in the example which follows. In the controlforthe example, a mixture of polyacrylamide and poly-4-vinyl pyridine was emplayed to provide the image receiving layer.
The two components will then be laminated together to provide an integral film unit.
. A rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution was fixedly mounted on the leading edge of each of the laminates, by pressure-sensitive tapes, interconnecting the respective container and laminates so that, upon application of compressive pressure to the container to rupture the containers marginal seal, its contents may 'be distributed between' the image receiving layer and I the gelatin layer, (layer 9), of the negative component. The processing composition employed in the ruptur- O O I able container comprised the following properties of h m -CH1CHI a cyan dye developer;-
Water 100 cc. Potassium hydroxide 11.2 gms. Hydroxyethyl cellulose high viscosity) [commercially available from Hercules Powder Co., Wil., Del., under the trade name Na'trasol 250[ 3.4 gms.
N-phenethyl-a-picolinium bromide 2.7 gms. Benzotriazole 1.15 grns. Titanium dioxide 50.0 gms.
posed in known manner to form a developable image and the exposed element can then be developed by applying compressive pressure to the rupturable container in order to distribute the aqueous alkaline process composition, thereby forming a multicolor transfer image which is viewable through the transparent polyethylene terephthalate film base as a positive reflection print. As was discussed before, this development may be effected in the presence of actinic light because the negative component is suitably protected from fogging.
EXAMPLE Diffusion transfer film units were prepared in the manner described above. The image receiving layers of each of these film units comprised varying mixtures of polyacrylamide, po1y-4-viny1pyridine and the aforeof Formula A, e.g., poly quarternarys 0f the following specific structure:
Meta and para. Polyvinylbenzyl trimetliyl ammonium chlorides sold by Dow Chemical Company under the trade name E.C.R. 34
The respective ratios of the ingredients of each mixture employedin the film units are set forth in tabular form below which also describes the composition of the [.50 Film units of the foregoing description can beexmixture employed to provide an image receiving layer for a control film unit.
TABLE 1 Percent by weight 01 each material in Diffusion transfer film units of the type described above were exposed and processed at various temperatures. Examination of the resulting image patterns showed the following differential maximum densities which comprise the difference between the maximum and minimum densities recorded for the various colors of the film with a Quantalog Mac Beth Densitometer.
TABLE 11 (Processing Temperature 40F) D-MAX Red Green Blue P 2241-A 1.93 1.49 1.86 P 2241-13 1.63 1.35 1.80 P 2241-C 2.05 1.57 1.90 P 2241-D 1.88 1.51 1.85 P 2241-E 2.16 1.64 1.90 P 2241-0 1.52 1.36 1.75 (Control) TABLE 111 (Processing Temperature 74F) D-MAX Red Green Blue P 2241-A 2.29 1.93 2.07 P 2241-B 2.07 1.87 2.0 P 2241C 2.27 1.96 2.09 P 2241-D 2.17 1.89 2.03 P 2241-13 2.29 1.89 2.03 P 2241-G 1.79 1.72 1.94 (Control) TABLE IV (Processing Temperature 10291- D-MAX Red Green Blue P 224l-A 2.26 1.81 2.04 P 2241-13 2.13 1.79 2.05 P 2241-C 2.16 1.73 1.96 P 2241-D 2.15 1.67 1.99 P 2241-E 2.23 1.65 1.89 P 2241-6 1.83 1.62 1.93 (Control) mentioned approximately 1:1 mixture of. the polymers A comparison of the above data evidences the advantages in improved color reproduction to be obtained by including a polymeric merial of Formula A in mixtures of polymeric materials which can provide image receiving layers for diffusion transfer photographic products.
It will be appreciated that the foregoing description is illustrative and the various elements of diffusion transfer film units may be arranged differently and/or may contain additional reagents providing specific, desired functions. The alternative arrangements of these elements and/or selection the selection of additional reagents will be readily apparent to those skilled in the art and per se comprise no part of this invention.
Since certain changes may be made in the above product without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed:
l. A receiving element for use in photographic diffusion transfer processes comprising a composite structure which comprises a support and an alkali permeable and dyeable polymeric layer comprising a polymer conforming to formula A below:
where each R can be the same or different substituent chosen from the group consisting of hydrogen, hydroxyl, alkyl radicals having from one to six carbon atoms, alkoxy radicals having oneto six carbon atoms or alkanol radicals having one to six carbonatorns; and X is an anion radical.
2. A receiving element of claim 1 wherein said polymeric layer comprises a mixture of a polymer of Formula A and a polymeric material chosenfrom the group consisting of the polymers of polyvinylalcohol, polyacrylamide, polyvinyl pyridine, polyhydroxyalkylcellulose and mixtures of these. i
3. A receiving element of claim 2 wherein the concentration of the polymer Formula A insaid mixture ranges from about 8 percent by weight of the total polymeric materials in the mixture to about 50 percent by weight. w
4. A receiving element of claim 3 wherein said polymeric layer comprises a mixture of a polymer of Formula A and a polymeric material chose from the group consisting of the polymers of polyacrylamide, poly-4- vinylpyridine, polyhydroxy alkylcellulose and mixtures of these.
5. A receiving element of claim 3 wherein said poly meric materials includes polyacrylamide and poly-4- vinyl pyridine.
7. A diffusion transfer photographic product having as essential elements thereof a photosensitive system comprising at least one selectively sensitized silver halide layer integrated with a dye image providing material, a processing composition which can provide a diffusion transfer image pattern after exposure of said photosensitive system and an image receiving element arranged to receive said diffusion transfer image pattern, said image receiving element comprising a composite structure which comprises a support and an al;- kali permeable and dyeable polymeric layer comprising a polymer conforming to Formula A below: A
wherein each R can be the same or different substituent chosen from the group consisting'of hydrogen, hydroxyl, alkyl radicals having from one to six carbon atoms, alkoxy radicals having from one to six carbon atoms or alkanol radicals having from'one to six carbon atoms; and X is an anion radical. I
8. -A diffusion transfer product of claim 7 wherein said photosensitive system comprises a blue, green and red sensitive silver halide layer each integrated with a yellow, a magenta and cyan dye image providing material.
9. A diffusion transfer product of claim 10 wherein Z the concentration of said'cornpound of Formula .A in
said mixture of polymeric materials comprising said dyeable layer ranges from about 8 percent by weight of said polymeric materials to about 50 percent by weight.
10. A diffusion transfer product of claim 7 wherein said polymeric layer comprises a mixture of polymer of Formula A and a polymeric material chosen from the group consisting of the polymers of polyvinylalcohol, polyacrylamide, polyvinyl pyridine, polyhydroxyalkylcellulose and mixtures of these.
ll. A diffusion transfer product of claim 10 wherein said polymeric layer comprises a mixture of a polymer of Formula A and a polymeric material chosen from the group consisting of the polymers of polyacrylamide, poly-4-vinyl pyridine, polyhydroxyalkylcellulose and mixtures of these.
12. A diffusion transfer product of claim l0 wherein saidpolymeric-material of Formula A in said dyeable layer is a polyvinylbenzyl trimethyl ammonium chloride. 7
13.'A diffusion transfer product of claim 10 wherein said polymeric material of Formula A in said dyeable layer is a polyvinyl trimethyl ammonium chloride and said mixture of polymeric materials includes polyacrylamide and poly-4-vinyl pyridine.