|Publication number||US3312549 A|
|Publication date||4 Apr 1967|
|Filing date||12 Dec 1962|
|Priority date||12 Dec 1962|
|Publication number||US 3312549 A, US 3312549A, US-A-3312549, US3312549 A, US3312549A|
|Inventors||Wilho M Salminen, John H Van Campen|
|Original Assignee||Eastman Kodak Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (8), Referenced by (5), Classifications (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
pril 4, 1967 w. M. SALMINEN ET AL 3,312,549
I RECEIVLNG SHEET FOR PHOTOGRAPHIC DYES Filed Dec. 12, 1962 /DYE MORDANT 11v HYDROPHILIC COLLOID "POLYETHYLENE 104C PAPER SUPPORT DYE MOR DANT IN HYDROPHILIC COLLOID PO LYE TH YLE N E B A RYTA PA PER SUPPORT POLYETHYLENE 36 I TOPCOAT PROTECTIVE LAYER N/BLUE-SENSITIVE EMULSION+ 35 f; YELLOW-FORMING COUPLER INTERLAYER wvf-j GREEN-SENSITIVE EMULSION+ m IMAGENTA-FORMING COUPLER 'INTERLAYER RED -SENSIT'IVE EMULSION CYAN FORMING COUPLER s u P P o R T H YDROQU/NONE DERIVATIVE LAYER BLUE-'SENSITIVE EMULSION LAYER YELLOW DYE DEVELOPER LAYER INTERLA YER GREENSENSITIVE EMULSION LAYER MAGENTA DYE DEVELOPER LAYER INTERLAYER RED-SENSITIVE EMULSION LAYER CYAN DYE DEVELOPER LAYER SUPPORT \IViiiw J0 BY FM gwfifujz United States Patent 3,312,549 RECEIVlNG SEEET FOR PHDTOGRAPHIC DYES Wilho M. Salminen and John H. Van Campen, Rochester,
N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Dec. 12, 1962, Ser. No. 244,103 17 Claims. (Cl. 96-29) The present application concerns the photographic art. More particularly, the present invention concerns receiving sheets for photographic dyes, and preferably, receiving sheets for use in photographic color diffusion transfer processes.
Photographic color diffusion transfer systems for transferring dye images to receiving sheets are well known in the art. Conventional film supports such as cellulose acetate and the like have been utilized for receiving such transferred dye images. Less costly paper supports, such as baryta-coated paper, have also been utilized. However, such paper supports are not entirely satisfactory because of support staining by processing solution components, surface roughness, nonuniform penetration by processing solutions, low color density, mottled color images and other undesirable features.
Accordingly, it is an object of this invention to provide a new sheet for receiving photographic dyes.
It is another object of this invention to provide a novel receiving sheet for photographic dyes particularly adapted for use in photographic color diffusion transfer processes.
It is another object of this invention to provide a novel receiving sheet for photographic dyes that results in high D color transfer images when utilized in photographic color diffusion transfer processes.
It is likewise an object of this invention to provide a novel sheet for receiving photographic acid dye images suitable for use with photographic color diffusion transfer processes.
' It is also an object of this invention to provide a new receiving sheet for receiving dye developer images resulting from photographic color diffusion transfer processes.
These and other objects of the invention are accomplished with receiving sheets for photographic dyes comprising a paper support having thereon a polyethylene coating, and coated thereover a coating of a mordant for dyes in a hydrophilic organic colloid.
The paper support can be any of the conventional high alpha-cellulose supports including those prepared from cotton, linen and wood (e.g., sulfate and sulfite pulped), and which supports are typically about 5 to 60 lbs. per 1000 square feet papers.
In accordance with the invention, polyethylene is coated over the paper support as a sublayer for conventional mordanting compositions. The polyethylene layer is typically about .3 to 5 mils in thickness. A wide variety of normally solid, resinous polyethylenes can be utilized as the polyethylene layer of the invention. Such polyethylenes are well known in commerce and generally have average molecular weights of at least 15,000 and more generally 20,000.
The polyethylene layer is preferably treated on its surface to facilitate the adherence of hydrophilic organic colloidal substrates containing the mordant. Typical surface treatments for polyethylene include treatments with a flame, the use of oxidizing agents such as nitric acid, sodium hypochlorate, hydrogen peroxide, sulfuric acid and potassium chromate, electron bombardment, radiation by ultraviolet light, etc.
We prefer to treat the surface of the polyethylene utilized in our receiving sheets by electron bombardment. A corona discharge can be used to obtain the high level of electron bombardment utilized in treating the present polyethylene surfaces and can be obtained by varying the electrical conditions with respect to frequency, voltage, number of electrodes, and similar variables. Apparatus disclosed in Rothacker patents, U.S. 2,864,755 and 2,864,756, can be utilized. The level of electron bombardment can be measured by the contact angle obtained when a drop of distilled water is placed on a level sample of the polyethylene coating. By projecting the image of the drop and sample on a suitable screen, and measuring the angle of a line tangent to the drop image at the point the drop touches the polyethylene sample, a contact angle is obtained which can be measured and utilized to determine the degree of electron bombardment. Generally, untreated polyethylene-coated paper gives a contact angle of about 90. We prefer that this contact angle for the polyethylene coatings utilized in the dye receiving sheets of the invention be between about and 75. Such a technique of electron bombardment of polyethylene layers to make then more desirable subbing layers for hydrophilic colloidal materials is described in copending application, Alsup et a1. U.S. Ser. No. 191,711, filed May 2, 1962, now abandoned.
Reference is also made to Traver, U.S. Patent 3,018,189 for methods for treating the surface of polyethylene with electrostatic discharges to change the surface properties of the polyethylene with respect to adhesion of materials coated thereon.
Over the polyethylene coatings of the present receiving sheets are coated mordanting compositions. A wide variety of conventional mordants in hydrophilic organic colloids can be utilized. Typical hydrophilic colloidal materials useful as the substrate for dispersing the mordant include gelatin and its water-soluble derivatives, polyvinyl alcoholand its water-soluble derivatives and copolymers, polyacrylamide, imidized polyacrylamide, water-soluble cellulose derivatives-such as ethanolamine cellulose acetate, and related water-soluble film-forming materials that form water-permeable coatings.
A wide variety of mordants for photographic dy'es can be utilized in the present invention. Such materials are well known to those skilled in the art. Mordants that are opposite in charge to the dye being mordanted are utilized in accordance with usual practice. As most of the useful photographic dyes have acidic properties, we more generally utilize cationic mordants. Typical mordants are organic quaternary phosphonium salts, organic ternary sulfonium salts and organic quaternary ammonium salts. Suitable mordants include polymers of amino guanidine derivatives of vinyl methyl ketone described in Minsk, U.S. Patent 2,882,156. Other suitable mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate, poly 4-vinylpyridine, thorium salts and similar compounds described in Sprague et al., U.S. Patent 2,484,430.
A particularly useful class of mordanting compositions is disclosed in copending Bush application, U.S. Ser. No. 211,094, filed July 19, 1962, now U.S. Patent 3,271,147. The Bush mordanting compositions comprise at least one hydrophilic organic colloid containing a finely-divided uniform dispersion of particles of a salt of an organic acidic composition containing free acid moieties and a.
cationic, .nonpolyme-ric, organic dye mordant for acid dyes. Generally, the salts in such dispersions are in particles less than about 30 microns in diameter. In preparing the Bush mordanting compositions containing such salts or coacervates, any of the conventional cationic mordant compounds, either water-soluble or water-insoluble, are combined with an organic acidic composition (e.g., having free acid groups such as carboxy and sulfonic acid groups) including gelatin that has been reacted with an a-haloacetic acid or acylated with a dicarboxylic acid such as phthalic', malonic, succinic, maleic, glutaric, suberic, and the like acids. Other organic acidic com-position include polymers containing such moieties as organic acid composition is sufiiciently ballasted to render the resulting salt hydrophobic in the protective hydrophilic colloid in which it is dispersed.
Basic or cationic, nonpolymeric mordant compounds useful in preparing the dye mordanting compositions of the Bush application included quaternary ammonium and phosphonium, and ternary sulfonic compositions in which there is linked to the N, P or S onium atom at least one hydrophobic ballast group, such as long-chain alkyl or substituted alkyl groups. The onium atom can be part of an open-chain or of a heterocyclic ring and there can 'be more than one onium ring in the molecule. When referring to the nonpolymeric nature of the mordant compounds of such mordanting compositions, we mean that the cationic or the basic mordant does not have regularly occurring units containing the cationic. group beyond the dimer structures. However, the ballast group attached to the quaternary or ternary atom of the cation group can contain repeating groups .such as tetraethoxy, polymethylene, etc.
Another useful class of mordanting compositions that can be coated over the polyethylene-coated paper supports of the invention comprises at least one hydrophilic organic colloid containing a finely-divided uniform dispersion of droplets or globules of a high-boiling water-immiscible organic solvent in which is dissolved a high concentration of a cationic nonpolymeric organic dye-mordanting compound for acid dyes. The droplets of the water-immiscible solvent are typically prepared to be less than 5 microns in size, and more generally in the range of .5 to 5 microns in size. Such mordanting compositions are disclosed in Knechel et al., copending application, U.S. Ser. No. 211,095, filed July 19, 19.62, now U.S. Patent 3,271,- 148.
The cationic, nonpolymeric organic mordant compounds useful in the mordanting compositions described in the Knechel et al. application are of the type that are capable of entering into salt-forming reactions, e.g., quaternary ammonium group, and at least one hydrophobic group, which prevents wandering of a long-chain aliphatic group such as disclosed in the Bush application described above.
The solvent or carrier for the ionic nonpolymeric mordant compound in the dispersed phase of the Knechel et a1. mordanting compositions is a high-boiling waterimmiscible organic liquid having a boiling point above about C. The high-boiling solvent can be used alone in forming the dispersion, or it can be admixed with some low-boiling organic solvent (e.g., boiling at least 25 C. below the boiling point of the high-boiling solvent) or a water-soluble oragnic solvent as an auxiliary solvent to facilitate the solution of the mordant material. Preferred ranges of proportions of high-boiling solvent to auxiliary solvent are 1/0 to 1/ 10 on a weight basis. Any of the high-boiling, water-immersible solvents described on page 2, col. 2, and page 3, col. 1, of U.S. Patent 2,322,027 can be utilized. Particularly useful solvents are organic carboxylic acid esters and organic phosphate esters.
Also, of course, any of the conventional mordanting materials can be dispersed directly in the hydrophilic organic colloid in accordance with usual practice to form suitable mordanting compositions.
The receiving sheets of the invention can be utilized to receive and mordant a wide variety of photographic dyes, including dye images transferred directly to such receiving sheets in photographic color diffusion transfer processes.
A typical diffusion transfer process in which the subject receiving sheets have particular utility are diffusion transfer processes utilizing dye developers (i.e., com pounds which contain in the same molecule both the chromophonic system of a dye and also a silver halide developing function) are released imagewise and diffuse to the receiving sheet which is superposed on the photographic element, such being disclosed in Rogers, U.S. Fatents 2,774,668 and 2,983,606 and Land, U.S. Patent. 2,647,049. In such color diffusion transfer processes, the element comprises a plurality of photosensitive silver halide emulsions, each of the emulsions being selectively sensitized to different regions of the spectrum. A dye developer is contiguous to the silver halide in each of such emulsions. The photoelement is processed with an alkaline solution and the latent image is developed in the negative image areas with the dye developer, this development immobilizing the dye developer in such negative image areas, and the dye developer in the unexposed areas diffuses to the surface imagewise and is mordanted in the receiving sheet to form a positive color image. When the receiving sheets of the invention having a mor danting composition coated on a polyethylene-coated paper are utilized, high-color densities are obtained in the D regions of the transferred images. Also, lowcolor densities in the D regions of the transferred images result.
Another useful photographic color diifusion transfer process that can be efficaciously carried out utilizing the receiving sheets of the invention is the process in which an element comprising a plurality of photosensitive silver halide emulsions wherein each of the emulsions are selectively sensitized to different regions of the spectrum, and wherein contiguous to the silver halide of each of these emulsions is a nondilfusible photographic color coupler which on color development in a photographic alkaline color developing solution containing a primary amino color developing agent forms a dilfusible acid dye. This dye then diffuses imagewise and is transferred to the receiving sheet transposed on the photoelement. If conventional negative-type silver halide emulsions are utilized, a negative color image results. If direct-positive silver halide emulsions, such as those having silver halide grains with substantial internal sensitivity, are utilized, a direct-positive color image results. Such color diffusion transfer processes are disclosed in British Patent 840,731 and copending Whitmore et al. application U.S. Ser. No. 222,105, filed Sept. 7, 1962, now U.S. Patent 3,227,550. The dye-releasing couplers used in the photographic elements of such processes are initially nonditfusing in the layers of the element but form dyes dilfusible in the layers of the element on reaction with oxidation product of aromatic primary amino silver halide photographic color developing agents. Such couplers include those having the formulas:
DYE-LINK- COUP-BALL) n and BALL-LINK-(COUP-SOL) wherein:
(1) DYE is a dye radical containing an acidic solubilizing radical;
(2) LINK is a connecting or linkage radical such as azo (N=N-), azoxy mercuri (Hg), oxy (O-), alkylidene (includes both CH and =CH), monothio ('-S-.-), or dithio (S1S-);
(3) COUP is a photographic color coupler radical such as a 5-py-razolone coupler radical, a phenolic coupler radical -or an open-chain ketornethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;
(4) BALL is a photo-graphically inert organic radical of such molecular size and configuration as to render the coupler nondifiusing in the element in the alkaline color developing solution;
(5) SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solu-bilizing group; and
(6) n is an integer of 1 or 2 when LINK'is an alkylidene radical, and n is always 1 when LINK is one of the other aforementioned connecting radicals, namely, azo, azoxy, mercuri, YO'XY, monothio, or dithio.
Likewise, other photographic difiusion transfer processes wherein dyes derived from such couplers can be utilized in the present process such as disclosed in Williams et al. copending application, U.S. Ser. No. 780,710, filed Dec. 16, 1958 now abandoned, and Belgian Patent No. 585,686. When the polyethylene-coated receiving sheets of the invention are utilized to receive the acid dye images resulting from such processes, good uniformity of dye images, as well as high D and low D of the dye images results.
FIG. 1 of the drawings illustrates a receiving sheet for photographic dyes of the invention. On paper support 10 is coated polyethylene layer 11, over which is coated layer 12 comprising a mordant for dyes in a hydrophilic organic colloid.
FIG. 2 of the drawings illustrates another typical receiving sheet for photographic dyes of the invention. Paper support 21 has coated on one side polyethylene layer and on the other baryta layer 22 (banium sulfate particles, e.g., .S to 1 micron, dispersed in gelatin). Over baryta layer 22 is coated polyethylene layer 23, over which is coated layer 24 comprising a mordant for dyes in a hydrophilic organic colloid.
FIG. 3 of the drawings is a typical light-sensitive photographic element or color film that can be used in conjunction with the receiving sheets of the invention to prepare photographic dye images. In processing the element of FIG. 3, the light-sensitive element can be wetted with a photographic alkaline color developing solution containing an aromatic primary amino developing agent. The mordanting composition side of the receiving sheets of the invention are pressed in contact with the emulsion side of the light-sensitive element of FIG. 3 and an image transferred thereto. Thereafter, the receiving sheet can be stripped away from the light-sensitive element, leaving a' mordanted dye image in the receiving sheet. In
6 the light-sensitive element of FIG. 3, on support is coated layer 31 comprising a red-sensitive silver halide emulsion containing a nondiffusible coupler that on color development forms a difiusible cyan dye. Over layer 31 5 is coated interlayer 32. Over layer 32 is coated layer 33 comprising a green-sensitive silver halide emulsion containing a nondiffusible coupler that on color development forms a diffusible magenta dye. Over layer 33 is coated interlayer 34. Over layer 34 is coated layer 35 compris- 10 ing a blue-sensitive silver halide emulsion containing a nondiffusible coupler that on color development forms a diffusible yellow dye. Over layer 35 is coated top coat protective layer 36.
FIG. 4 illustrates another typical light-sensitive photographic element or color film that can be utilized to produce dye images that can be transferred to the receiving sheets of the invention. The element illustrated by FIG. 4 can be utilized to prepare dye developer images of the type described above. In the photographic element of FIG. 4, on support is coated layer 41 containing a cyan dye developer. Over layer 41 is coated layer 42 which is a red-sensitive silver halide emulsion layer. Over layer 42 is coated interlayer 43. Over layer 43 is coated layer 44 comprising a magenta dye developer. Over layer 44 is coated layer 45 comprising a green-sensitive silver halide emulsion. Over layer 45 is coated interlayer 46. Over layer 46 is coated layer 47 containing a yellow dye developer. Over layer 47 is coated layer 48 comprising a blue-sensitive silver halide emulsion. Over layer 48 is coated layer 49 comprising a colorless, Water-insoluble hydroquinone.
The invention is illustrated by the following examples of preferred embodiments thereof.
EXAMPLE 1 A sheet for receiving photographic dyes of the type illustrated by FIG. 2 of the drawings was prepared. A baryta-coated support of paper stock about 10 lbs. per 1000 square feet was extrusion-coated on the baryta side with electron bombarded polyethylene containing titanium oXide pigment at' a coverage of 6 lbs. of polyethylene per 1000 square feet. The other or back side of the paper support was coated with clear polyethylene at a coverage of 2 lbs. of polyethylene per 1000 square feet. The contact angle of the surface of the electron bombarded'polyethylene layer measured with water drops was about 50. The polyethylene was plastic grade solid polyethylene having an average molecular weight greater than 15,000. Over the electron bombarded polyethylene Was coated a mordanting composition containing a coarcervate or salt prepared from the mordant, N-cetyl-N-ethyl morpholinium ethosulfate and phthaloylated gelatin at a coverage of 200 mg. per square foot of mordan-t, 750 mg.
per square foot of phthaloylated gelatin and 75 mg. per square foot of bone gelatin. The mordanting composition was prepared as follows:
Solution A was made by dissolving 1.0 g. of the mordant compound in 5 ml. of water, and 3 ml. of isopropyl alcohol. Solution B was made by adding 0.25 ml. of the gelatin hardener, bis-2,3-epoxypropoxydiethyl ether, to 35 ml. of 15% aqueous 7% phthaloylated gelatin solution (made by reacting 7 parts by weight phthalic anhydride with 100 parts by weight with bone gelatin). Thereafter, to stirred Solution B, Solution A was added in a thin stream at 85 F. The resultant mordanting dispersion contained particles that were substantially 2 to 10 microns in diameter.
Several sheets for receiving photographic dyes of the type described above were prepared and utilized to receive dye images resulting from the processing of a multicolor photographic element described in more detail below in a diffusion transfer process. For comparative purposes, several conventional baryta-coated receiving sheets containing no polyethylene coatings as supports for the mordanting composition were prepared. The color l photographic film utilized to produce the color images on the test receiving sheets had substantially the structure as shown in FIG. 3 of the drawings. The color photographic film had the following layers coated on a cellulose acetate film support.
(1) Red-sensitive layer (e.g., layer N0. 31, FIG. 3). To one mole of a melted, internal image, direct-positive, gelatino-silver bromoiodide emulsion of the type described in Davey et al., US. Patent 2,592,250 that had been red-sensitized, was added 108 g. of the cyan coupler, 1 hydroxy-4-(3-octadecylcarbamylphenylthio)-N- ethyl-3,5' dicarboxy-Z-naphthanilide, in 2500 ml. of water and enough photographic gelatin to make a total of 139 g. per mole of silver halide. This solution was then coated so as to obtain 193 mg. per square foot of gelatin, 150 mg. per square foot of coupler, and 150 mg. per square foot of silver.
(2) lnterlayer (e.g., layer No. 32, FIG. 3).-To 4540 g. of a photographic gelatin solution was added 250 g. of the anti-oxidant, 2-octadecyl-4-su1fohydroquinone potassium salt, in 5000 ml. of hot water. This was coated to obtain 91 mg. per square foot of gelatin and 50 mg. per square foot of the antioxidant.
(3) Green-sensitve layer (e.g., layer N0. 33, FIG. 3).-To one mole of a melted, internal image, direct-positive emulsion of the type described in Davey et al., U.S. Patent 2,592,250, that had been green-sensitized, was added 81 g. of the magenta coupler, 1-(4-sulfopheny1)- 3-(4-sulfoanilino)-4-(2-hydroxy 4 pentadecylphenylazo)-5-pyrazolone dipotassium salt, in 3000 m1. of water and enough photographic gelatin to have a total of 162 g. per mole of silver halide. This solution was coated so as to obtain 180 mg. per square foot of gelatin, 90 mg. per square foot of coupler, and 120 mg. per square foot of silver.
(4) Interlayer (e.g., layer No. 34, FIG. 3).To 4540 g. of 10% photographic gelatin solution was added 250 g.
dium salt in 5000 ml. of water. This solution was coated to obtain 91 mg. per square foot of gelatin and 50 mg. per square foot of the ultraviolet absorbing compound.
The samples of the photographic color film were exposed in an Eastman lb sensitometer using a multicolor step wedge and then soaked for 10 second and 30 second intervals in color Developer A described below. Similarly, the various prepared receiving sheets were soaked in the color developer for 10 second and 30 second intervals. Then the receiving sheets and the color photographic films were sandwiched together for about 5 minutes at 80 F., the emulsion side of the film'being pressed against the layer of mordanting composition of the receiving sheet. Also, samples of the receiving sheets that were not dipped in the developer were similarly sandwiched together with the samples of the photographic color film that had been dipped in the developer. Color Developer A had the following composition:
Color Developer A Ascorbic acid g- 0. 4 4-arnino-N-ethyl-N- ,B-hydroxyethyl) aniline g 10.0 Benzotriazole g 0.1 4- fi-methylsul-fonamidoethyl) phenylhydrazine hydrochloride g 0.3 Sodium hydroxide -g 14.0 Water ml 300.0
(The developer ingredients were dissolved in the water, then the whole added to 700 g. of a 4% aqueous solution of alkali-soluble carboxymethylcellulose.)
After 5 minutes, the receiving sheet was stripped away from the color photographic film or negative and the densities of the three color components of the transferred image dyes in each of the receiving sheets was determined in the D and D areas. Table I below summarizes the result of this data.
TABLE I DInaX Dmin Receiving Sheet Support for Mordant Red Green Blue Red Green Blue A. Polyethylene-coated paper support (negative dipped in developer 30 sec.) 2. 20 2. 56 1. 81 17 .19 26 B. Polyethylene-coated paper support (negative and receiver dipped in developer 10 sec.) 2. 43 2. 70 2. 05 17 19 29 C. Baryta-coated paper support (negative dipped in developer 30 Sec.) 1.19 1.14 1.15 15 17 19 D. Baryta-coated paper support (negative and receiver dipped in developer 10 sec.) l. 80 2.03 1. 62 24 27 31 of the antioxidant used in layer 2 (layer No. 32, FIG.
3) in 5000 ml. of hot water and 4.0 g. of yellow Carey Lea silver as a dispersion. This solution was then coated to obtain 91 mg. per square foot of gelatin, mg. per square foot of antioxidant, and 8 mg. per square foot of Carey Lea silver.
(5) Blue-sensitive layer (e.g., layer N0. 35, FIG. 3).- To one mole of a melted, internal image, direct-positive emulsion of the type described in Davey et al., US. Patent 2,592,250, that was inherently blue light-sensitive, was added 144 g. of the yellow coupler, u-pivalyl-a-(3-octadecylcarbamylphenylthio) 4-sulfoacetanilide potassium salt, that had been dissolved in 750 ml. of ethyl alcohol and 3000 ml. of water and enough photographic gelatin to have a total of 118 g. per mole of silver halide. This solution was coated so as to obtain 161 mg. per square foot of gelatin, 200 mg. per square foot of coupler, and 150 mg. per square foot of silver.
(6) Topcoat layer (e.g., layer N0. 36, FIG. 3).--To 4540 g. ofa 10% photographic gelatin solution was added 250 g. of ultraviolet absorbing compound, 5-(4-methoxy- As can be observed from the data set out in Table I, substantially higher densities of color in the D areas resulted when the receiving sheets were the polyethylenecoated paper supports of the invention, the baryta-ooated paper supports having dye images thereon of substantially less density in the D image areas. Also, the transferred images on the polyethylene-coated paper supports had good uniformity while those on the baryta-coated paper supports were non-uniform. Further, the barytacoated paper that was dipped in the developer with the photographic color film was badly stained, such staining not being present in the polyethylene-coated paper supports.
EXAMPLE 2 A mordanting composition was coated on the polyethylene-coated support described in Example 1. The mordanting composition was similar to that described in Example 1, except that a coacervate or salt of two mordanting materials, namely, tridodecylmethylammonium p-toluenesulfonate and N-cetyl-N-ethyl morpholinium ethosulfate with the phthaloylated gelatin were utilized. Also, pig gelatin was used in lieu of bone gelatin. The
mordanting composition was coated on the electron bombarded polyethylene to give 200 mg. per square foot of the N-cetyl-N-ethyl morpholiniuni ethosulfate, 30 mg. per square foot of the tridodecyl methyl ammonium p-toluene l developer, 5,8 dihydroxy 1,4 bis[(;3-hydroquinonyl-amethyl)ethylamino]anthraquinone, dissolved in a mixture of N-n-butylacetanilide and 4-methylcyclohexanone, were dispersed and the mixture passed through a colloidal sulfonate, 862 mg. per square foot of the phthaloylated mill several times, coated and dried, so as to volatilize the gelatin, and 129 mg. per square foot of the pig gelatin. 4-methylcyclohexanone. The color photographic negative element described in (2) Red-sensitive emulsion layer (e.g., layer N0. 42, detail in Example 1 was dipped for seconds in the FIG. 4).A developing-out negative gelatino-silver brodeveloper described in Example 1 and then sandwiched moiodide emulsion sensitized to red light was coated. in contact with the prepared polyethylene-coated paper 10 (3) Interlayer (e.g., layer No. 43, FIG. 4).--This is mordanting compositions of the invention for 10 second a gelatin layer. intervals at 80 F. for about 5 minutes. Another sample (4) Magenta dye developer layer (e.g. layer N0. 44, of the polyethylene-coated paper receiving sheet was FIG. 4 ).This layer is similar to the cyan dye developer dipped in the color developer for 10 seconds before sandlayer except that the magenta dye developer, 2[p-(2',5- wiching with the color photographic film. The film was dihydroxyphenethy-l) phenylazo] 4 ii propoxy-lexposed in an Eastman Ib sensitometer using a multicolor naphthol, was utilized in lieu of the cyan dye developer. step wedge prior to processing as described. Table II (5) Green-sensitive emulsion layer (e.g., layer N0. 45, below summarizes the results of the color densities in the FIG. 4).This layer is similar to the red sensitive gelatino- D and D areas for the dyes transferred imagewise silver bromoiodide emulsion layer except that it is sensito the polyethylene-coated paper receiving sheets of the tized to green light. invention. (6) ImerIayer (e.g., layer No. 46, FIG. 4) .This
TABLE II Dmax Dmin Receiving Sheet Support for Mordant Red Green Blue Red Green Blue A. Polyethylene-coated paper support (negative dipped in developer 10 see.) 2. 26 2. 48 1. 76 18 19 B. Polyethylene-coated paper support (negative and receiver dipped in developer 10 sec.) 2. 52 2. 79 2.19 l7 16 23 Similar results are obtained when the mordanting comlayer is a gelatin interlayer similar to the other interlayer position is prepared by dissolving the mordant in an orof the present element. ganic solvent and dispersing the organic solvent in finely- (7) Yellow dye developer layer (e.g., layer N0. 47, divided droplets in the hydrophilic colloidal substrate. A FIG. 4 ).An aqueous gelatin solution containing the yeltypical example of such a mordanting composition can be low dye developer, 1-phenyl-3-N-n-hexylcarboxamido-4- prepared by dissolving a 0.5 g. portion of the mordant, [p-(2,5 dihydroxyphenethyl)phenylazo]-5-pyrazoloiie, N,N dimethyl-N-(fi-hydroxyethyl)-N-(y-stearamidoprodissolved in dietetrahydrof'urfuryl adipate and ethylene pyl) ammonium dihydrogen phosphoate, in 0.5 cc. of di-nglycol monobenzyl ether, the mixture passed through a butyl phthalate and 3 cc. of ethanol. The resulting solu colloidal mill several times, the resulting dispersion chilled tion is emulsified y mixing With 22 of 10% q to set, washed to remove ethylene glycol monobenzyl gelatin containing 2 cc. of a 5% aqueous solution of the ether d h ft coated d d i d surfactant, sodium diisopropylnaphthalene sulfonate. The (3) Blueensitive emulsion layer (e.g., layer No. 48, resulting oil-in-water emulsion is then passed through a FIG, 4 developing-ou,t negative gelatino silver cqllold P that the droPlets of are f f 2 bromoiodide emulsion layer that was inherently sensitive microns in S126.- The resulting mordanting composition to blue light was coated can be coated on the electron bombarded polyethylene. (9) Hydmqm-none derivative layer (ag, Layer N0 49 EXAMPLE 3 FIG. 4).Gelatin at a coverage of 120 mg. per square A receiving sheet for photographic dyes of the type set 2% and 4 flmethylhezlylhydroaunone at a covelragfi of out in FIG. 2 and described in Example 1 was prepared, per square 00 g C03 6 except that the mordanting com-position was a coating of sevral Samp 16S of t e .above'descnbed 00101: Photo'- polyvinyloxymethyl methyl morpholinium IMOIHGM sub graphic film were exposed in an Eastman 'I b sensitometer fonate at a coverage of 200 mg. per square foot and polys a llmltlcolol p W dge, and then ocessed by vinyl alcohol at a coverage of 500 mg per Square foot wetting with an aqueous solution containing 3.5% of h gh For comparative purposes, the same mordanting viscosity hydroxyethyl cellulose, 4% sodium hydrox de, position was coated on a conventional cellulose acetate 2% kfenzofnazole and 2% of l'phenethylz'plcohmum film Support These two receiving Sheets were then bromide with the above-described receiving sheets in conlized to receive the dye images produced in a phototact therewith. After about 2 minutes at 72 F., the graphic color diff i t f process The photocolor negatives and the receiving sheets were stripped graphic color film or negative utilized had substantially 0 apart and 1116 densities in The max and miii areas of the h Structure f FIG. 4 f the drawings and comprised transferred color images were determined. Table Ill bethe following layers coated on a cellulose acetate film 10W Summarizes comparative data With ffispect max Support; and D for the receiving sheet having the polyethylene- (1) Cyan dye developer layer (e.g., layer No. 41, FIG. v coated paper support of the invention with the receiving 4).An aqueous gelatin solution containing the cyan dye 75 sheet containing a cellulose acetate support.
TABLE III Dmux Dmin Receiving Sheet Support for Mordant Red Green Blue Red Green Blue A. Cellulose acetate support 1. 1.02 1. 16 13 l5 19 B. Polyethylene-coated paper sup port 1. 22 1. 46 1. 71 .12 19 As can be observed from the data set out in Table III, substantially improved D color densities of the transferred dye images resulted from the polyethylene-coated paper mordanting receiving sheets of the invention as compared to a receiving sheet having a conventional cellulose acetate filmsupport.
EXAMPLE 4 A receiving sheet for photographic dyes of the type illustrated by FIG. 2 of the drawings and described in Example 1 was prepared except that the following mordanting composition was coated over the electron bombarded polyethylene layer of the receiving sheet support in lieu of the one described in Example 1:
Bone gelatin 'g 2.5 Po-ly-4-vinylpyridine dissolved in 2.5 cc. glacial acetic acid g 2.5 Phenylmercapto tetrazole g 0.1 1 0% formaldehyde solution g 0.25 Distilled Water cc 100.0
ing a paper support having thereon a polyethylene coating, and having coated thereon a mordanting composition comprising a hydrophilic organic colloid containing substantially uniiormly dispersed therein finely divide'd particles of a hydrophobic salt of gelatin acylated with a dioarboxylic acid having the formula 0 0 HO i J-(Y)( }OH wherein Y is a divalent hydrocarbon radical having 1 to 10 carbon atoms and a nonpolymeric organic cationic mordant for acid dyes selected from the group consisting of quaternary ammonium mordants, quaternary phosphonium mordants and ternary sulfonium mordants.
3. A receiving sheet for photographic dyes comprising a paper support having thereon a polyethylene coating, and having coated thereon a mordanting composition comprising a hydrophilic organic colloid containing substantially uniformly dispersed therein finely-divided droplets of a water-immiscible organic solvent boiling above about 175 C., organic solvent containing dissolved therein a nonpolymeric organic cationic mordant for acid dyes selected from the group consisting of quaternary ammonium mordants, quaternary phosphonium mordants and ternary sulfonium mordants.
A receiving sheet as described in claim 2 wherein the polyethylene coating has been electron bombarded.
5. A receiving sheet as described in claim 3 wherein the polyethylene coating has been electron bombarded.
6. A sheet for photographic acid dyes comprising a paper support having thereon a polyethylene coating that has been electron bombarded, and having coated there- As can be observed from the data set out in Table IV, the receiving sheet prepared having the polyethylenecoated paper support resulted in substantially improved color density in the D areas for the transferred dye as compared to a conventional receiving sheet of the baryta-coated paper type.
The present invention thus provides a useful class of receiving sheets for photographic dyes, and which receiv-ing sheets have particular utility for receiving dyes in photographic color diffusion transfer processes.
The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
1. A sheet for receiving photographic acid dyes comprising a paper support having thereon a polyethylene coating, and coated thereover a coating of a cationic mordant for said dyes in a hydrophilic organic colloid.
2. A receiving sheet for photographic dyes comprisover a coating of a cationic mordant for dye developers in a hydrophilic organic colloid containing a mordanted multicolor image of dye developers, said dye developers being both photographic silver halide developing agents and dyes.
7. A sheet for photographic acid dyes com rising a paper support having thereon a polyethylene coating that has been electron bombarded, and having coated thereon a coating of a cationic mordlaut for acid dyes in 'a hydrophilic organic colloid containing a mordanted multicolor image of acid dyes, said acid dyes being formed by re acting the oxidation product of an aromatic primary amino color developing agent in a photographic alkaline color developing solution with a photographic color coupler having a formula selected from the group consisting of DYE-LINK-(COUP-BALL) and BALL-LINK-(COUP-SOL) wherein:
(l) DYE is 'a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group;
(2) LINK is a connecting radical selected from the group consisting of an .azo radical, a 'mercuri radical, an oxy radical, an alkylidene radical, a monothio radical, a dithio radical and an lazoxy radical;
(3) COUP is a coupler radical selected from the group consisting of a S-pyrazolone coupler radical, la phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;
(4) BALL is a photognaphically inert organic ballasting radical of such molecular size and configuration as to render said couplers nondifiusible during development in said alkaline color developing solution;
(5) SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and S01. is an acidic solubilizing group when said color developing agent is free of an acidic solubilizing group; and
(6) n is an integer of l to 2 when said LINK is an lalkylidene radical, and n is 1 when said LI NK is a radical selected from the group consisting of an 'azo radical, la mercun' radical, an oxy radical, a monothio radical, a dithio radical and an azoxy radical.
8. A sheet for receiving photographic dyes as described in claim 1 wherein the hydrophilic organic colloid comprises gelatin.
9. A sheet for receiving photographic dyes as described in claim 1 wherein the hydrophilic organic colloid comprises polyvinyl alcohol.
10. A sheet for receiving photographic dyes as described in claim 1 wherein the polyethylene coating has been electron bombarded to provide a contact angle of its surface measured with water of firom about 40 to 75 '11. A receiving sheet as described in claim 2 wherein the mordant comprises a salt of N-cetyl-N-ethyl morpholinium ethosulfiate land phthaloylated gelatin.
12. A receiving sheet as described in claim 2 wherein the mordlant comprises a salt of N-cetyl-N-ethyl morpholinium ethosulfate, tridodecyl methyl ammonium ptoluene sulfonate and phthaloylated gelatin.
13. A sheet for photographic dyes as described in claim 6 wherein the mor-dalnt comprises poly 4-vinylpyridine.
14. In the process of transferring photographically produced dye images to a mondanted receiving sheet, the improvement which comprises utilizing a receiving sheet comprising a paper support having thereon a polyethylene coating, and coated thereover a coating of a mordant for photographic dyes in la. hydrophilic organic colloid.
15. A sheet iior receiving photographically produced.
dye images comprising a paper support, having coated on one side of said paper support a polyethylene layer, and having coated on the other side of said paper support the following layers respectively from said paper support:
(1) a banayta layer,
(2) an electron bombarded polyethylene layer, and
(3) a layer of a hydrophilic organic colloid containing a cationic mordlant for photographic dyes.
16. A sheet for receiving photographic dyes as described in claim 1 wherein the polyethylene contains a pigment.
17. A sheet tor receiving photographic dyes as described in claim 1 wherein the polyethylene contains a titanium oxide pigment.
References Cited by the Examiner UNITED STATES PATENTS 2,773,769 12/ 1956 Goldschein 9685 2,955,953 10/1960 Graham 11747 2,983,606 5/1961 Rogers 9629 3,076,720 2/1963 Rice et a1. 117-47 3,148,061 9/ 1964 Haas 9629 3,148,062 9/ 1964 Whitmore et a1 9655 3,161,506 12/ 1964 vBecker 9629 FOREIGN PATENTS 720,916 2/ 1932 France.
NORMAN G. TOROHIN, Primary Examiner.
I. TRAVIS BROWN, Examiner.
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|US2955953 *||5 Jun 1956||11 Oct 1960||Du Pont||Process of adhering an organic coating to a polymeric substrate|
|US2983606 *||14 Jul 1958||9 May 1961||Polaroid Corp||Processes and products for forming photographic images in color|
|US3076720 *||17 Oct 1960||5 Feb 1963||Lowe Paper Co||Coated paper and polyolefin and method of coating|
|US3148061 *||22 Aug 1960||8 Sep 1964||Polaroid Corp||Photographic diffusion transfer processes employing image receiving layers containing poly-4-vinylpyridine|
|US3148062 *||6 Apr 1959||8 Sep 1964||Eastman Kodak Co||Photographic elements and processes using splittable couplers|
|US3161506 *||27 Mar 1961||15 Dec 1964||Eastman Kodak Co||Photographic multicolor diffusion transfer process using dye developers|
|FR720916A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3435761 *||10 May 1966||1 Apr 1969||Eastman Kodak Co||Premordanted imbibition dye printing blank|
|US3649265 *||6 May 1970||14 Mar 1972||Eastman Kodak Co||Diffusion transfer system comprising dye developers, a pyrazolone and an onium compound|
|US3770431 *||16 Sep 1971||6 Nov 1973||Eastman Kodak Co||Photographic elements containing ballasted resorcinols|
|US4141730 *||7 Apr 1976||27 Feb 1979||Fuji Photo Film Co., Ltd.||Multilayer color photographic materials|
|US5432043 *||17 Feb 1994||11 Jul 1995||Fuji Photo Film Co., Ltd.||Product of diffusion transfer photography with polyester coated support|
|U.S. Classification||430/213, 430/941, 430/212|
|Cooperative Classification||G03C8/52, Y10S430/142|