JPS6017099B2 - silver diffusion transfer film unit - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Additive color reproduction involves exposing a light-sensitive silver halide silver emulsion through an additive color screen having filter media screen elements each of which is a discrete additive color, such as red, green, or blue. and by making the inverted deposit of the formed silver image visible by transferring it to a transparent receiving element through the same or similar screen, suitably superimposing the inverted positive image carried by the receiving layer. sell.

Examples of suitable film structures for use in additive photography include U.S. Pat.
No. 154, No. 2944894, No. 3536488
No. 3615427, No. 3615428, No. 3615429, No. 3615426, No. 9
No. 4871 and No. 3364482. Patent Application No. 697,104, filed June 17, 1978, and Patent Application No. 649,201, filed January 14, 1976, also describe a diffusion transfer photographic film unit for use in additive color photography. .

Patent Application No. 383 under examination filed on July 27, 1973
No. 261 relates to an additive diffusion transfer film unit comprising a transparent support, an additive multicolor screen, a light-sensitive halogenated emulsion layer, and a layer released as a result of contact of this layer with a photographic processing composition. The coating includes a layer containing an antihalation dye that has passed through the coating.

U.S. Patent No. 370,412, issued November 28, 1972
No. 6 describes the silver diffusion transfer photography method and film units, and is titled “
A patent has been requested.

In this patent, the noble metal in the film unit is less reactive than silver. In other words, the electromotive force sequence of the element (E18
cumotiveForceseriesofEle
Positive silver images with increased stability are provided by the use of noble metal compounds that are subordinate to silver in silver. In a preferred embodiment, the noble metal compound is substantially water-impregnable and soluble in alkaline solutions, and in particular has the formula M-x, where M is a less reactive noble metal than silver, and X is The complexing organic group preferably produces a substantially water-insoluble complex compound). No. 3,704,126 is incorporated herein by reference in its entirety. In the film unit used in the additive diffusion transfer process described above, the noble metal compound is deposited in a treatment composition permeable layer terminal to the support. That is, the noble metal compound-containing layer is often located next to and adjacent to the photosensitive silver halide layer. however,
It has been found that the use of such noble metal compounds in the case of silver diffusion transfer film units can result in some desensitization of the silver halide emulsion.

While not wishing to be bound by theory, it is believed that the organic moiety of the noble metal compound may contribute to the desensitizing effect seen in the silver halide emulsion layer by distributing the optical sensitizer onto the silver halide grains. Although this is thought to be the case, the exact mechanism is unknown. The present invention consists of a transparent support, a nucleus-containing layer for silver precipitation, a photosensitive silver halide emulsion layer, a water-insoluble inorganic silver salt, and elements lower in the electromotive force series than silver (i.e.,
and a substantially water-insoluble noble metal compound containing a noble metal (more noble than silver), in this order.

Preferably, the film unit of the invention comprises an additive color screen. The accompanying figures 1, 2 and 3 show the red, green and blue density characteristic curves of the neutral columns of the additive transparencies obtained according to the examples.

It has been found that in the film units of the present invention, enhanced storage stability with respect to the photosensitivity of the silver halide emulsion layer is obtained by using a water-insoluble inorganic silver salt in combination with an organometallic stabilizer compound. .

The photosensitivity of any water-insoluble silver teeth used is too low for image formation during exposure. The use of a particular water-insoluble silver salt is not a critical condition.

However, care should be taken to avoid using anions that can be photographically harmful to this system. In a preferred embodiment, silver chloride is used. The silver salt may be fogged or unfogged. An effective amount of water-insoluble silver salt is used.

Preferably, an amount of iron is used that is sufficient to constrain the foundations from the noble metal compound to minimize or eliminate any appreciable desensitization of the silver halide emulsion. More particularly, about 0. It should be understood that a smaller amount may be used to obtain a reduced effect.
Excessive amounts should be avoided in order to protect the silver from increasing oxidation or acting as a nucleating agent. The effectiveness of the water-insoluble silver salt is also demonstrated by examining the H&D curves of film units that differ only in the presence or absence of this salt.

If a water-insoluble silver salt is not used, the image will be grainy;
The H&D curve shows a sharp protrusion. When a water-insoluble silver salt is used, the granularity of the image is fine and the H&○ curve shows a more desirable footprint. The following examples are non-limiting examples illustrating the novel film units of this invention.

Example 1 Additive color screen 3/28 (9/3500) polyvinylidene chloride polyvinyl formal protective overcoat of approximately 1500 triplets per inch of red, blue and green filter screen elements each in parallel relationship Patent application No. 64 filed on the 14th of Layer 3 197 Kuoh 1st page
No. 9201, made according to the method of Example 8, with a 0.15 9/
ft2 (1.6 9 no.) pd and 0''19 9/f
t2 (2.0 double 9/ft2)> Palladium core-containing nucleated product layer with gelatin coverage: gelatin 1.99/ft2 (2
0.4 females/ft2), acetic acid 2.3 of 9/ft2 (24.8 of 9/ft2) and oxyphenoxy polyethoxycetanol surface active agent 0.19 of 9/ft2 (2.0 of 9/ft2) 5'-dimethyl-9-ethyl-39, each of which is a red, green and blue sensitizer;
3-bis(3-sulfopropyl)thiacarpocyanine triethyl ammonium salt (0.53 female/ta Ag),
5-5-diphenyl÷9-ethylm3,3-pis-(4
-Sulfobutyl)oxacarbocyanine (9 of 0.75
/taAg), anridro-5,6-dichloro-1,3-
Diethyl-3'-(4'-sulfobutyl)-penzimidazolothiacarbocyanine hydroxide (9 of 0.7
NotaAg) and 3-(3'-sulfopropyl)-3'
-ethyl-4,5-benzothiacyanine (1.0
Panchromatically sensitized with propylene glycol alginate (about 7.1 & 9/Ag) and nonylphenol polyglycol ether (containing 9.5 moles of ethylene oxide) about 0. 73 no 9/f
Ze (7.8 9/〆) and gelatin about 91 9/f
t2 (9/2 of 979) and silver approximately 110 phosphorus/ft2 (
A film unit was made consisting of a hardened gelatinous silver bromide emulsion coated with a coverage of 1184 m9/A) and a transparent polyester film base carrying on one surface the antihalation top coat described below.

The antihalation top coating was published on July 27, 1973.
It is described in Patent Application No. 261, which is currently under examination.
A patent has been claimed. A second film unit was made that was the same as Example 1 except that the top coating did not contain silver chloride. No substantial desensitization was observed in the film units of the present invention compared to film units that did not contain silver chloride.

Film units prepared according to the above method were exposed to 18hce through an additive screen and the following treatment composition was applied between the top coat and the Polj ethylene terephrate cover sheet with a gap of 1.4 mils. Distributed and processed by mechanical lamination labrolle.

The film unit was held in place for one minute, then the cover sheet was removed and the remainder of the film unit was held together and allowed to air dry. Processing Composition FIG. 1 is a characteristic curve of a control film unit, ie, a film unit containing no silver chloride.

FIG. 2 is the characteristic curve of the film unit of Example 1, and FIG. 3 is the characteristic curve of the film unit prepared as in Example 1 except that the silver chloride was not capped. From a comparison of these curves, the images appear to be less grainy and exhibit a smoother toe shape for the processed film units of the present invention compared to the control. Additionally, this curve shows that either frosted or unfoamed silver chloride can be used. The support used in this invention is not critical.

The support or film base used may consist of any of a variety of types of transparent rigid or flexible supports, such as glass, polymer-based films, both of the synthetic type and those derived from naturally occurring products. However, particularly suitable materials are polymetallic acrylates and ethyl esters, vinyl chloride polymers, polypynylacetals, polyamides (e.g. nylon), polyesters (e.g. polymeric films derived from ethylene glycol terephthalate), polymeric cellulose. Ken conductors (e.g. cellulose acetate, triacetate)
The additive screen (a
The dditivecolor screen) can be formed by techniques well known in the art, for example by double-printing the required filter pattern by photolithography.

Additive color screens typically consist of an array of two to four differently colored castles or filter elements, each set of colored gamut being capable of transmitting visible light within a predetermined wavelength range. Color Color screens are trichromatic, with each set of color filter elements transmitting light in one of the so-called primary wavelength ranges, namely red, line and blue.Additive color screens are based on starch granules or hardened gelatin granules. A mosaic may be formed by assembling, intermixing, and interspersing microscopic dye grains, such as in a regular or random arrangement.This type of regular mosaic can be achieved by alternating embossing and the techniques described in U.S. Pat. No. 3,019,124. It can be made by a doctoring technique.

Another method of forming a suitable color screen is multi-track extrusion (m) in the manner described in U.S. Pat.
In this method, colored lines are arranged in parallel in one coating operation. Yet another method is disclosed in U.S. Patent No. 328,420.
It is stated in No. 8. Silver halide solvents useful for forming the desired soluble complex compounds with unexposed silver are well known and can be chosen, for example, from alkali metal thiosulfates, especially sodium or potassium thiosulfates, or alternatively halogenated The silver solvent was released on October 21, 2019 by Edwin Wich Rand.
It can be a cyclic imide, such as uracil, in combination with a nitrogenous base, as taught in U.S. Pat. Although the silver halide solvent is preferably present initially in the processing composition, it is preferable that the silver halide solvent is initially present in the layers of the film unit, preferably releasing or releasing the silver halide solvent when contacted with the alkaline processing fluid. It is also within the scope of the invention if it is present in the form of a generated precursor. The treatment composition may contain a thickening agent, such as alkali metal carboxymethyl cellulose or hydroxyethyl cellulose, in an amount and viscosity sufficient to facilitate application of the treatment composition.

The processing composition may remain on the processed film or may be removed according to known techniques, as most appropriate for the particular film used. Preferably, the necessary alkalinity, e.g. a pH of 12-14, is imparted to the treatment composition by compounds such as sodium hydroxide, potassium and/or lithium. To facilitate application of the treatment composition, it may be advantageous to include a wetting agent in the treatment composition, particularly when the treatment composition is applied as a very thin layer of a low viscosity fluid. Suitable silver halide developers can be selected from those known in the art and are initially applied to the layer of the photosensitive element and (
or) may be located in the treatment composition. Organic silver halide developers are commonly used, such as hydroquinone, tert-butylhydroquinone, toluhydroquinone, p-aminophenol, 2,6-dimethyl-4-aminophenol, 2,4,6-triaminophenol, etc. A benzene- or naphthalene-based organic compound having hydroxyl and/or amino groups in mutually para- or ortho-positions, such as, is used. Additive transparent positive painting
The silver halide developer(s) may stain the image if the color transparency is not cleaned after processing to remove unused silver halide developer, development reaction products, etc. Alternatively, it should not produce colored reaction products, either unreacted or reacted, that could have a detrimental effect on the stability and sensitometry of the final image. A particularly useful silver halide developer having good stability in alkaline solutions is published by Stanley M. Bloom and Richard D. Cramer on October 26, 1971.
Substituted reduced acids, particularly tetramethyl reduced acids, such as those described in U.S. Pat. No. 3,615,440, issued in 1973
Edwin H. Land, Stanleyem, Froome and Leonard C., dated May 1st. Q,8-enediol as described in U.S. Pat. No. 3,730,716 issued to Onard C. Famey.

[Brief explanation of drawings]

Figures 1, 2 and 3 show the red, green and blue density characteristic curves of the neutral columns of the additive transparencies obtained according to the examples. FIG. l FIG2 FIG3

Claims (1)

[Scope of Claims] 1. A layer containing silver precipitation nuclei; a photosensitive silver halide layer; and a processing composition permeable polymer, a substantially non-photosensitive water-insoluble inorganic silver halide salt and an elemental A silver diffusion transfer film unit comprising a transparent support carrying on one surface, in this order, layers comprising substantially water-insoluble noble metal compounds containing noble metals lower in the electromotive force series than silver. 2 Claim 1 in which the noble metal lower than silver is gold
Film unit of term. 3. The film unit according to claim 2, wherein the noble metal compound is a benzimidazole-2-thiol gold (Au+1) composite compound. 4. The weight ratio of silver to gold in the treatment composition-permeable polymer layer is 0.
．． The film unit according to claim 3, which has a ratio of 4 to 1. 5. The film unit of claim 1 comprising an additive color screen. 6. The film unit according to claim 1, wherein the silver precipitation core is a noble metal core. 7. The film unit according to claim 6, wherein the noble metal core is palladium. 8. The film unit according to claim 1, wherein the treatment composition permeable polymer is gelatin.