CA1109711A - Image receiving elements containing an additive colour screen and a layer of noble metal silver precipitating nuclei and polymer - Google Patents

Abstract

Abstract of the Invention A receiving element for use in an additive color photographic diffusion transfer process which comprises a transparent support carrying an additive color screen and a layer comprising noble metal silver precipitating nuclei and a polymer; wherein said nuclei are present in a level of about 0.1 - 0.3 mgs/ft2, and said polymer is present at a level of from about 0.5 to 5 times the coverage of said nuclei. preferably, the noble metal is obtained by reduction of a noble metal salt or complex, and more preferably, the noble metal is palladium.

Description

97~

Background of the Invention Procedures for preparing photographic images in silver by diffusion transfer principles are well known in the art. For the formation of the positive silver images, a latent image contained in an exposed phc1_osensitive silver halide emulsion is developed and almost concurrently there-with, a soluble silver complex is obtained by reaction of a silver halide solvent with the unexposed and undeveloped silver halide of said emulsion. Preferably, the photosensi-tive silver halide emulsion is developed with a processingcomposition in a viscous condition which is spread between the photosensitive element comprising the silver halide emulsion and a print-receiving element comprising, preferably, a suitable silver precipitating layer. The processing com-position effects development of the latent image in theemulsion and, substantially contemporaneously rherewith, forms a soluble silver complex, for example, a thiosulfate or thiocvanate, with undeveloped silver halide. This soluble silver complex is, at least in part, transported in the direction of the print-receiving element and the silver thereof is largely precipitated in the silver precipitatin~
element to form a positive image thereon. Procedures of this description are disclosed, for example, in U. S. Patent No. 2,543,181 issued to Edwin H. Land. See, alsc, Edwin H.
Land, One Step Photography, Photographic Journal, Section A, pp. 7-15, January 1950.
Additive color reproduction may be produced by exposing a photosensitive silver halide emulsion through an additive color screen having filter media or screen elements each of an individual additive color, such as red or green 9~

or ~lue, and by viewinq the reversed or positive silver image formed by transfer to a transparent print-receiving element through the same or a similar scree~ which is suitably registered with the reversed positi~e image carried by the print-receiving layer.
As examples of suitable film structures for employment in additive color photography, mention may be made of ~. S. Patent Nos. 2,861,885i 2,726,154; 2,g44,894; 3,536,488;
3,615,427; 3,615,428; 3,615,429; 3,615,426; and 3,894,871.

The image-receiving elements of l:he present invention are particularly suited for use in diffusion / transfer film units wherein there is contained a positive transfer image and a negative silver image, the two images being in separate layers on a common, transparent support and viewed as a single, positive image. Such positive images may be referred to for convenience as "integral positive-negative images", and more particularly as "integral positive-negative transparencies." Examples of film units which provide such integral positive-negative transparencies are set forth, for example, in the above-indicated U.S.
Patents Nos. 3,536,488; 3,894,871; 3,615,426; 3,615,427;

3,615,428; and 3,615,429.

In general, silver precipitating nuclei comprise a specific class of adjuncts well known in the art as adapted to effect catalytic reduction of solubilized silver halide specifically including heavy metals and heavy metal compounds such as the metals of ~roups IB, IIB, IVA, VIA and VIII and the reaction products of Groups IB, IIB, IVA and VIII metals with elements of Group VIA.

~1~9~

Widely used as silver precipitating agents have been those disclosed in U.S. Patent No. 2,6~,237 and specifically the metallic sulfides and selenides, there detailed, these terms being understood to include the 5 selenosulfides, the polysulfides, and the polyselenides.
It has been preferred to employ sulfides whose solubility products in an aqueous medium at approximate.ly 20 C.
vary between 10 23 and lO 49, and especially rhe salts of zinc. Also particularly suitable as precipitati.ng agents 10 heavy metals such as silver, gold, platinum, palladium, etc., and in this category the noble metals illuctrated are preferred and are generally provided in a silica matrix as colloidal particles.
The nucleation layers in the art rlave generally 15 been found to be in excess of the 1 micron range (about 93 mgs/ft ). See, for example, U.S. Patents Nos. 3,220,837 and 3,709,687.
U.S. Patent No. 3,647,440, issued March 7, 1972 discloses receiving layers comprising finely divided non-20 silver noble metal nuclei obtained by reducing a noblemetal salt in the presence of a colloid or binder material with a reducing agent having a standard potential more negative than -0.30~ It is the thrust of the patent that a reducing agent having a standard potential more negative than -0.30 25 must be used in order to obtain nuclei of a specific, usable size range. It is further illustrated that stannous chloride, which does not fall within the standard potential range, does not produce useful nuclei. The b:irlder materials disclosed include gelatin, polyvinyl pyrrolidore, polymeric 30 latices such a copoly (2-chloroethylmethacrylate~acrylic acid), a mixture of polyvinyl alcohol and the interpolymer of n-butyl acrylate, 3-acryloyloxypropane-l-sulfonic acid, sodium i. 1l~)~71! 1 salt and 2-acetoacetoxyethyl methacrylate, polyethylene latex, and colloidal silica. The amount of colloid binder employed ranges from about 5 to 500 mgs/ft2 with the nuclei ranging from 1 to 200 micrograms/ft2.
A novel silver precipitating nuclei system has now been found which possesses advantages not found in the prior art, which system has particular value in silver transfer colour lmage s .
Summary of the Invention In a first embodiment, the present invention is directed to a receiving element for use in an additive colour diffusion transfer process and comprises a transparent support carrying an additive colour screen and a layer of noble metal nuclei and a polymer. The nuclei are present in a range of about 0.1 to 0.3 mgs/ft2, the polymer is present at a coverage of about 0.5 to 5 times that of the nuclei. Thus, the total of the nuclei and polymer together is not greater than about

2 mgs/ft .
In a preferred embodiment, the noble metal nuclei comprise palladium nuclei. In a particularly preferred embodi-ment the noble metal nuclei are prepared by reducing a noble metal salt or complex; and, more preferably, reducing with a first metal capable of two valence states.
In a second embodiment, the present invention is directed toward a method for preparing an image receiving element for use in an additive colour photographic diffusion transfer process which comprises the steps of:
(a) reducing a noble metal salt or complex in a solution of a polymer; and (b) coating said noble metal and polymer on a transparent 7~:~

support carrying an additive colour screen; wherein said noble metal is present at a level of about 0.1-0.3 mgs/ft2 and said polymer is present at a level of about 0.5 to 5 times the coverage of said noble metal.
In a third embodiment, the present invention is directed toward an image receiving element for use in an additive colour photographic diffusion transfer process which comprises a transparent support carrying an additive colour screen and a layer comprising palladium metal silver precipit-ating nuclei and gelatin, wherein said nuclei are present at alevel of about 0.2 mgs/ft2 and said gelatin is present at a level of about 0.2 mgs/ft2; and said palladium nuclei are formed by the reduction of palladous chloride with stannous chloride.
In a fourth embodiment, the present invention is directed toward an additive colour diffusion transfer film unit which comprises a transparent support carrying, in order, an additive colour screen, a layer comprising palladium metal silver precipitating nuclei and gelatin, wherein said nuclei are present at a level of about 0.2 mgs/ft2 and said gelatin is present at a level of about 0.2 mgs/ft2; and said palladium nuclei are formed by the reduction of palladous chloride with stannous chloride; a photosensitive silver halide emulsion layer; and an antihalation layer.
Detailed Description of the Invention The silver precipitating layers employed in the novel receiving element provide positive silver transfer images at coverages heretofore not employed or taught by the prior art.
The relatively thin nucleating layer as well as the small amount of nuclei and the relatively low polymer level is not only unexpected but also unobvious in ~ -4a-view of the art. Generally, large excesses of polymer or other binder compared to nuclei are employed.
The noble metals employed in the present invention include silver, gold, palladium and platinum. However, particularly superior results are achieved at the specified coverages with palladium and, for convenience, ~he invention will be described primarily in terms of this preferred embodi-ment.
Superior photographic results are oktained employing the palladium metal nuclei in a gelatin or hydroxyethvl cellu-lose polymer, particularly with respect to silver image tone and density.
While the amount of noble metal nuc]el may range over the range indicated, particularly advantageous results are obtained at a level of about 0.15 to 0.25 mgs/ft2, and more particularly, at a level of about 0.2 mgs/ft2.
In a preferred embodiment, the polymer is employed at a level of about 0.5 to 5 times the coverage of the noble metal nuclei. It is surprising that such a reiatively small amount of pol~mer can be employed without precipitation or settling of the noble metal, while at the same time obtaining the sensitometric properties desired, particularly silver image tone. In addition, a more neutral image tone is achieved as gelatin at the lower level of the polymer range is em ~ ~cd.
The noble metal nuclei are preferably obtained by the reduction of â noble salt or complex. In a preferred embodiment, the reduction is carried out by a first or reducing metal capable of existing in two valence states. While it is not intended that we be bound by the theorv, it is believed in the art that the noble metal ion is reduced to ~he metallic ~1~97~1 state where it can function as a catalytic site for silver deposition in a diffusion transfer process. Thus, the term "noble metal nuclei" is intended to include the metallic noble metal in colloidal form as well as alloyed with other materials such as the aforementioned first metal and the terms "reduce" and "reduction" are intended to refer to the chemical reaction by which the colloidal or alloyed form of the metal is obtained. While the noble metal nuclei are substantially in the metallic or alloyed form, it should be understood that minor amounts of noble metal complexes may be present. As examples of suitable materials for use as the first metal ion, mention may be made of iron, cobalt, nickel, bismuth, lead, titanium, vanadium, chromium, copper, molybdenum, antimony, tungsten and preferably tin.
Noble metal nuclei prepared by the procedure set forth in United States Patent No. 4,025,343 may also be employed in the receiving elements of the present invention.
The term "polymer" as used therein is intended to include natural and synthetic polymers and include gelatin methyl cellulose sodium salt of carboxymethyl cellulose hydroxymethyl cellulose hydroxyethyl cellulose hydroxypropyl cellulose carboxymethyl hydroxyethyl cellulose alginic acid, sodium salt agarose polyvinyl alcohol deacetylated chitin Successive coatings of the nob e metal nucleating layers may be employed, in some cases, separated by layers of a suitable polymeric binder such as deacetylated chitin or gelatin. In a preferred embodiment, however~ a single layer of the noble metal/polymer silver precipitating layer is coated.
The novel image-receiving element of the present invention as employed in silver diffusion transfer processing forms a positive silver image therein which is frequently characterized by a uniform mirror deposit of ~.1age silver believed to be a result of the relatively thir. nuclei layer employed. The positive silver is more dense ~han that gener-ally found in prior art image-receiving elements and is similar in properties to that obtained by vacuum deposi~ted silver, which is believed to be the most compa_l: form possible.
The above-mentioned mirror effect is particularly desirable in photographic transparencies since it tends to increase the DmaX in projection images when the mirror is cn the side of the support next to the projection light. The absorption ~ of the silver transfer image is relatively neutral, i.e., similar to vacuum deposited silver. Thu~, by means of the present invention, a thin, tightly packed ma~rix of nuclei can be prepared so that the image silver deposite~ therein is similar to vacuum deposited silver.
Combinations of noble metals may be used as well as single noble metals. In a preferred embodiment, noble metals salts or complexes may be reacted with reducing metal salts from aqueous salts of the noble metals. Suitable compounds include the following:

K2PdC14 PdC12 r~ 73~1 H2PtC16 AgN03 HAuC14 The ratio of first metal salt to noble metal salt or complex may range from about 1:1 to 4:1, and preferably

3:1, said ratios based on the weight of the metals.
The following non-limiting examples ill-lstrate the novel process of the present invention:

The following solutions were prepared:
Solution A
165 cc water 0.65 g K2PdC14 85 cc 1% hydroxyethylcellulose 250 cc 0.1% alkyl phenoxypolyoxyethylene ethanol surfactant (sold under the trade name PE-120 by NOPCO Chem.
Div. of Diamond Shamrock Company) The K2PdC14 is dissolved in the water and to this solution is added the hydroxyethylcellulose and surfactant.
Solution B
165 cc water 1.0 g SnC12 85 cc 1~ hydroxyethylcellulose 250 cc 0.1% alkylphenoxypolyoxyethylene ethanol surfactant The SnC12 is added to the water and tG this mixture is added the hydroxyethylcellulose and surfactan~.
Solutions A and B are quickly mixed together, stirred for 30 to 60 minutes and coated on suitaklP supports for use as silver precipitating layers.

The utility of such nuclei layers is described below.

A film unit was prepared comprising transparent polyester film base carrying on one surface an additive color screen of approximately 1000 triplets per inch of red, blue and green filter screen ele-ments in repetitive side-by-side relationship; a 4 micron polyvinylidine chloride-polyvinyl formal protective overcoat layer; nucleating material prepared according to the procedure of Example 1 was slot coated over said protective layer; a gel coat (50 mgs/ft2) prepared by adding 26 g. of a 10% inert gel solution to 72 cc of water, heating to 39C. and mixing until homogenous and then adding 3 cc of a 1% solution of octylphenoxy polyethoxy ethanol surfactant; a hardened gelatino silver iodo-chloro emulsion coated at a coverage of about 115 mgs/ft2 of gelatin and about 100 mgs/ft2 of silver with about 7.18 mgs/ft2 propylene glycol alginate and about 0.45 mgs/ft2 of sodium dioctyl sulfosuccinate panchromatically sensitized with 5,5'-dimethyl-9-ethyl 3,3'-bis-(3 sulfopropyl) thiacarbocyanine triethyl-ammonium salt; 5,5'-diphenyl-9-ethyl-3,3'-bis-(4-sulfobutyl) oxacarbocyanine; and 100 mgs/ft2 of one of the following antihalo top coats. The antihalo top coats referred to below are disclosed and claimed in Canadian Patent 1,031,204.

Top Coat A
Wt. %
Sodium bis-1,5C3-carboxy-l-(p-N-n-pentyl sulfonamido-phenyl)-2-pyrazolin-5-one]
pentamethane oxonol 0.13 Distilled Water 65.18 _g_ ~()9711 , Wt.

4-(2-chloro-4-dimethylaminohenzaldehyde-1-(p-phenyl carboxylic acid)-3-methyl pyrazalone-5 0.01 Gelatin (15% solution) 34.59 Daxad-ll*(polymerized sodium salts of alkyl naphthalene sulfonic acid) Manufactured by W. R. Grace & Co., Cambridge, Mass. 0.007 Top Coat B
Gelatin 0.02 Benzimidazole thiol gold complex 0.35 Distilled water 6.66 Pyridinium bis-1,5(1,3-diethyl-2-thiol-S-barbituric acid) pentamethine oxanol 0.22 4-(2-chloro-4-dimethylamino benzaldehyde)-l--(p-phenyl carboxylic acid)-3-methyl pyrazolone-5 0.28 Gelatin (10% solution) 92.46 ` Daxad-ll*(polymerized sodium salts of alkvl naphthalene sulfonic acid) Manufactured by W. R. Grace ~ Co., Cambridge, Mass. 0.01 The above-described film unit was given an 8 mcs exposure and was processed through mechanical lab rollers at 3,o a ~ mil gap disposing one of the processing compositions set forth below between the top coat and a gelatin cr,ated cover sheet. The film unit was held in the dark for 1 minute and the neutral column was read to white, red, green and blue light in an automatically recording densitometer.

* Trade Marks llV97~1 Processing Composition A
Wt. %
Water 79.02 Sodium hydroxide 6.97

5 Hydroxyethyl cellulose 2.70 Sodium sulfite 2.44 2-methylthiomethyl-4,6-dihydroxypyrimidine 4.06 Tetramethyl reductic acid 3.26 1,12-dodecameth~lene-bis-(pyridinium) bromide 1.70 4-amino-pvrazalo-[3.4-] pyrimidine 0.015 5-bromo-6-methyl azabenzimidazole 0.015 Thiazolidine thione 0.034 Processing Composition B
Wt. ~
Water 75.89 Sodium hydroxide 0.87 Potassium hydroxide 8.61 Hydroxyethyl cellulose 0.95 Tetramethyl reductic acid 3.86 20 Potassium sulfite 3.79 2-methylthiomethyl-4,6-dihydroxypyrimidine 5.75 1,12-dodecamethylene-bis-(pyridinium) bromide 0.82 4~amino-pyrazolo-[3,4-] pyrimidine 0.061 Film units within the scope of the present inven-tion were prepared and processed according to the procedures of Examples 1 and 2 with the indicated ratios of components, top coats and processing compositions.

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x ~ 9711 The following solutions were prepared:
Solution A
0.5 g. SnC12 2H2O
100 g. 1.0% acetic acid Water to make 100.5 g. total Solution B
10 g. 1% gelatin solution Solution C
0.286 g. PdC12 100 g. 2.0% acetic acid Dissolution carried out with stirring at about 40C.
The nuclei were formed by bringing 145 g. of water to a boil in a flask with a magnetic stirrer. 20 g.
of Solution A was added and, after one-half minute, 5 g. of Solution B. The mixture was allowed to come to a boil again and stirred vigorously while 20 g. of Solution C was added.
After stirring for another one-half minute, the mixture was 20 cooled to room temperature within five minutes. Sufficient -water was then added to make up a total of 190 g. As a ~s coating aid, 20 mil. of 0.1% alkyl phenoxypolyoxy-ethylene ethanol surfactant (sold under the trade name PE120 by NOPCO
Chem. Div. of Diamond Shamrock Company) was added.
In an alternative procedure the nuclei are formed at room temperature. To differentiate the variations in the procedures the nuclei formed at elevated temperature will be designated "HOT" and the nuclei formed at room temperature designated "Room Temperature".

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11~)9711 Example 9 Film units were prepared accordinq to the proce-dure of Example 2 except that the gel layer between the receiving layer and the emulsion layer was replaced with a 5 copper-chitin layer prepared as follows: .
To a solution comprising:
3300 g. distilled water 3.316 g. copper acetate 0.914 g. sodium acetate was added a solution comprising: -279.413 g. distilled water 9.065 g. acetic acid 11.522 g. deacetylated chitin The thus-formed solution was coated tc provide a layer of 7 mgs/ft2.
The above-described copper-chitin layer is claimed in United States Patent 4,056,392.

Film units within the scope of the pxes2nt inven-tion were prepared according to the procedures of Examples 8 20 and 9 and processed according to the procedure o Example 2 with the indicated ratios of components, top coats and processing compositions.

~'097~1 Processinq Composition C

Wt. %
Water o6 . 2 Sodium hydroxide 7.1 Hydroxyethyl cellulose 0.9 Tetramethyl reductic acid 11.1 Sodium sulfite 0.8 Sodium thiosulfate 12.4 N-benzyl- ~ -picolinium bromide 1.4 (50% solution) Processinq Composition D
~t.%
Water ~C.
Sodium hydroxide 7.~
Hydroxyethyl cellulose 0.9 Tetramethyl reductic acid 11.7 Sodium sulfite 2 . 2 Sodium thiosulfate 5.3 N-benzyl- ~ -picolinium bromide 1.7 (50% solution) 4-amino-pyrazolo-[3,4-] pyrimidine0.02 Bromomethyl azabenzimidazole0.03 Processinq ComPosition E
Wt.%
Water 70.4 Sodium hydroxide 7.3 Hydroxyethyl cellulose 0.6 Tetramethyl reductic acid 7.5 Potas~ium sulfite 3.6 2-methylthiomethyl-4,6-dihydroxy-pyrimidine 7.5 N-benzyl- ~ -picolinium bromide 3.0 (50% solution) 11~3g7~ ~

Top Coat C
Wt. %
Gelatin 0.03 Benzimidazole thiol gold complex 0.41 Distilled water 44.84 Pyridinium bis-1,5(1,3-diethyl-2-thiol-5-barbituric acid) pentamethine oxanol 0.13 4-(2-chloro-4-dimethylamino benzaldehyde~
(p-phenyl carboxylic acid)-3-methyl pyrazoione-5 0.16 Gelatin (10% solution) 54.41 Daxad-ll (polymerized sodium salts of alkyl naphthalene sulfonic acid) manufactured by W. R. Grace & Co., Camhridge, Mass. 0.01 Top Coat D
Wt. %
Gelatin 0.03 Benzimidazole thiol gold complex 0.41 Distilled water 45.35 Pyridinium bis-1,5(1,3-diethyl-2-thiol-5-barbituric acid) pentamethine oxanol 0.13 4-(2-chloro-4-dimethylamino benzaldehyde)-l-(p-phenyl carboxylic acid)-3-methyl pyrazolone-5 0.16 Gelatin (10% solution) 53.92 Daxad-ll (polymerized sodium salts of alkyl naphthalene sulfonic acid) manufactured by W. R. Grace & Co., Cambridge, Mass. 0.01 Top Coat E
Wt. %
Gelatin 0.03 Benzimidazole thiol gold complex 0.02 Distilled water 27.45 Pyridiunium bis-1,5(1,3-diethyl-2-thiol-5-barbituric acid) pentamethine oxanol 0.13 4-t2-chloro-4-dimethylamino benzaldehyde)-l-(p-phenyl carboxylic acid)-3-methyl pyrazolone-5 0.16 Gelatin (10~ solution) 72.02 Daxad-ll (polymerized sodium salts of alkyl naphthalene sulfonic acid) manufactured by W. R. Grace & Co., Cambridge, Mass. 0.01 _l f;_ 11~9~1 ,, ~

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The following table shows the photographic results obtained with nuclei prepared according ~o Example 8 and incorporated with film units prepared and processed according to the procedure of Example 9 with varying levels of noble metal nuclei.
Table 3 Aim Coverage ~ /D
2 max min mgs/ft Example Pd Gelatin Red Green Blue 16 0.2 0.2 3.20/0.41 3.10/0.42 2.93/0.46 17 0.07 0.07 3.11/0.41 3.09/0.39 2.94/0.41 In Examples 16 and 17 Processing Composition D
and Top Coat D were employed.
Example 18 Nuclei was prepared according to tlle procedure of Example 8 and incorporated into a film unit according to the procedure of Example 9 except that a copper-gelatin layer was substituted for the copper-chitin layer with the same quantity of materials employed. At a 0.2 mgs/ft palladium coverage and a 1:1 gelatin/palladium ratio the following transmission densities were obtained on the film units.
Red Green Blue Dmax 2.95 2.75 2.65 Dmin 0.42 0.36 0.44 Processing Composition D and Top Coat D

were employed.
Example 19 Nuclei was prepared according to the procedure of Example 8 except that potassium palladous tetra chloride was substituted for palladium chloride. The nuclei was incorporated into a film unit according to the procedure of Example 9. At a 0.2 mgs/ft palladium coverage and a -lR-11097~1 1:1 gelatin/palladium ratio the following transmission densities were obtained.
R Green Blue max .33 3.15 3.00 Dmin 0 43 0.39 0.42 Processing Composition D and Top Coat D
were employed.
Example 20 The procedure of Example 8 was modified by the substitution of 0.235 g. of sodium hypophosphite in 100 g.
of water for the stannous chloride reducing agent.
Example 21 The procedure of Example 8 was modified by the sub-stitution of 0.084 g. of sodium borohydride in 100 g. of water for the stannous chloride reducing agent. Nuclei prepared employing these reducing agents were incorporated in film units described in Example 9 and processed with the following results obtained:
Table 4 Aim Coverage mgs/ft D
Example Pd Gelatin Red Green Blue Green min 0.20 0.20 3.37 3.06 2.79 0.38 21 0.20 0.20 3.28 3.12 2.78 0.33 Processing Composition E and Top Coat E were employed.
As stated above, the preferred polyrner employed in the receiving layers of the present invention comprises gelatin. Gelatin at the low end of the nuclei-binder ratio can be employed to provide good density, neutral tone positive images in the receiving layer whereas the preferred levels of other polymers, such as hydroxyethyl cellulose are at the higher portions of the nuclei-binder range.

~1~97~1 In an alternative embodiment, the colloid formed by the reduction of the noble metal salt or complex is dialyzed before coating. The effect of the dialysis is to provide enhanced stability to the coating composition. While not intending to be bound by theory, it is believed that this enhanced stability is a result of the pH beinq raised and/or the removal of certain ions, such as Ht, K and Cl .
ïn still a further embodiment, the pH of the above-mentioned colloid is changed from acid to alkaline resulting in the precipitation of the noble metal, which r~J~s pev~
can then be separated, washed and ~d~ro~ in a polymer and coated. Any unwanted by-products or .starting materials are thereby removed.

The particle size of the silver precipitating nuclei of the present invention may vary over a relatively wide range. In a preferred embodiment, the nuclei range from about 15A to about 65A. For example, nuclei prepared according to the procedure of Example 1, on a 1000 particle count,have a mean diameter of about 20A
with 80% of the particles having a diameter bet.ween 17A and 4OA. Nuclei prepared according to Example 8, on a 1000 particle count,have a mean diameter of about 31A with 80% of the particles having a diameter between 19A and 46A.
The support employed in the present invention is not critical. The support of film base employed may comprise any of the various types of transparent rigid or flexible supports, for example, glass, polymeric films o~ both the synthetic type and those derived from naturally occurring products, etc. Especially suitable materials, 1~097~1 however, comprise flexible transparent synthetic polymers such as polymethacrylic acid, methyl and ethyl esters;
vinyl chloride polymers; polyvinyl acetals; polyamides such as nylon; polyesters such as the polymeric films derived from ethylene glycol terephthalic acid; polymer cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate-butyrate; or acetate propionate; polycarbonates; polystyrenes; and the like.
The additive color screen empioyed in the present invention may be formed by techniques well known in the art, e.g., by sequentially~printing the requisi~e filter patterns by photomechanical methods. An additive color screen comprises an array of sets of colored areas or filter elements, usually from two to four different colors, each of said sets of colored areas being capable of transmitting viqible light within a predetermined wave-length range. In the most common situations the additive color screen is trichromatic and each ~et of color filter elements transmits light within one of the so-called primary wavelengthq ranges, i.e., red, green and blue. The additive color screen may be composed of minute dyed particles, such as starch grains or hardened gelatin particles, intermixed and interspersed in a regular or random arrangement to provide a mosaic. ~ regular mosaic of this type may be made by the alternating embossing and doctoring technique described in U.S. Patent No. 3,019,124.

Another method of forming a suitable color screen comprises multi-line extrusion of the type disclosed in U.S. Patent No. 3.032,008, the colored lines being deposit~d side-by-side in a single coating operation. Still another methodis set forth in U.S. Patent No. 3,284,208. Silver halide p~

solvents useful in forming the desired soluble complex with unexposed silver are well known and, for example, may be selected from the alkali metal thiosulfates, particularly sodium or potassium thiosulfates, or the silver halide solvent may be cyclic imide, such as uracil, in combination with a nitrogenous base as taught in U.S. Patent No. 2,857,274 issued October 21, 1958, to Edwin H. Land~ While the silver halide solvent is preferably initially present in the processing composition, it is within this invention to initially position the silver halide solvent in a layer of the film unit, preferably in the form of a precursor which releases or generates the silver halide solvent upon contact with an alkaline processing fluid.
The processing composition may contain a thickening agent, such as an alkali metal carboxymethyl cellulose or hydroxyethyl cellulose, in a quantity and viscosity grade adapted to facilitate application of the processing composition. The processing composition may be left on the processed film or removed, in accordance with known techniques, as is most appropriate for the particular film use. The requisite alkalinity, e.g., a pH of 12-14, is preferably imparted to the processing composition, such as sodium, potassium and/or lithium hydroxide. A wetting agent may be advantageously included in the processing composition to facilitate application thereof, particularly where the processing composition is applied in a very thin layer cf low viscosity fluid.
Suitable silver halide developing agents may be selected from amongst those known in the art, and may be initially positioned in a layer of the photosensitive 7~1 element and/or in the processing composition. Organic silver halide developing agents are generally used, e.g., organic compounds of the benzene or naphthalene series containing hydroxyl and/or amino groups in the para- or ortho-positions with respect to each other, such as hydroquinone, tert-butyl hydroquinone, toluhydroquinone, p-aminophenol, 2,6-dimethyl-4-aminophenol, 2,4,6-triaminophenol, etc. If the additive color transparency is one which is not washed after processing to remove unused silver halide developing agent, development reaction products, etc., the silver halide developing agent~s) should not give rise to colored reaction products which might stain the image or which, either unreac~ed or reacted, might adversely affect the stability and sensitometric properties of the final image. Particularly useful silver halide developing agents having good stability in alkaline solution are substituted reductic acids, particularly tetramethyl reductic acid, as disclosed in U.S. Patent No. 3,615,440 issued October 26, 1971 to Stanley M. Bloom and Richard D. Cramer, and ~ enediols as disclosed in U.S. Patent No. 3,730,716 issued to Edwin H. Land, Stanley M. Bloom and Leonard C. Farney on May 1, 1973.

Claims (23)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An image receiving element for use in additive color photographic diffusion transfer process which comprises a trans-parent support carrying an additive color screen and a layer comprising noble metal silver precipitating nuclei and a polymer;
wherein said nuclei are present in a level of about 0.1-0.3 mgs/ft2; and said polymer is present at a level of from about 0.5 to 5 times the coverage of said nuclei.

2. The product of claim 1 wherein said nuclei are obtained by the reduction of a noble metal salt or complex.

3. The product of claim 2 wherein said reduction is effected by a reducing metal capable of two valences.

4. The product of claim 1 wherein said nuclei are present at a level of about 0.2 mgs/ft2.

5. The product of claim 1 wherein said polymer is gelatin.

6. The product of claim 1 wherein said polymer is hydroxyethyl cellulose.

7. The product of claim 1 wherein said polymer is present at a level of about 1 times that of the nuclei.

8. The product of claim 5 wherein said nuclei is present at a level of about 0.2 mgs/ft2.

9. The product as defined in claim 1 wherein said noble metal is palladium.

10. The product as defined in claim 3 wherein said reducing metal is tin.

11. The product as defined in claim 3 wherein said noble metal salt is palladous chloride and said reducing metal is provided by stannous chloride.

12. A method for preparing an image receiving element for use in an additive color photographic diffusion transfer process which comprises the steps of:
(a) reducing a noble metal salt or complex in a solution of a polymer; and (b) coating said noble metal and polymer on a trans-parent support carrying an additive color screen; wherein said noble metal is present at a level of about 0.1-0.3 mgs/ft2 and said polymer is present at a level of about 0.5 to 5 times the coverage of said noble metal.

13. The method of claim 12 wherein said reduction is effected by a reducing metal capable of two valence states.

14. The method of claim 12 wherein said nuclei is present on said support at a level of about 0.2 mgs/ft2.

15. The method of claim 12 wherein said polymer is gelatin.

16. The method of claim 12 wherein said polymer is hydroxyethyl cellulose.

17. The method of claim 12 wherein said polymer is present at a level of about 1 times that of the nuclei.

18. The method of claim 15 wherein said nuclei is present at a level of about 0.2 mgs/ft2.

19. The method as defined in claim 12 wherein said noble metal is palladium.

20. The method as defined in claim 13 wherein said reducing metal is tin.

21. The method as defined in claim 13 wherein said noble metal salt is palladous chloride and said reducing metal is provided by stannous chloride.

22. An image receiving element for use in an additive color photographic diffusion transfer process which comprises a transparent support carrying an additive color screen and a layer comprising palladium metal silver precipitating nuclei and gelatin, wherein said nuclei are present at a level of about 0.2 mgs/ft2 and said gelatin is present at a level of about 0,2 mgs/ft2; and said palladium nuclei are formed by the reduction of palladous chloride with stannous chloride.

23. An additive color diffusion transfer film unit which comprises a transparent support carrying, in order, an additive color screen, a layer comprising palladium metal silver precipitating nuclei and gelatin, wherein said nuclei are present at a level of about 0.2 mgs/ft2 and said gelatin is present at a level of about 0.2 mgs/ft2; and said palladium nuclei are formed by the reduction of palladous chloride with stannous chloride;
a photosensitive silver halide emulsion layer; and an antihalation layer.