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Publication numberUS3666478 A
Publication typeGrant
Publication dateMay 30, 1972
Filing dateSep 18, 1969
Priority dateSep 24, 1968
Also published asDE1942665A1
Publication numberUS 3666478 A, US 3666478A, US-A-3666478, US3666478 A, US3666478A
InventorsGroh Margit, Oetiker Alfred
Original AssigneeCiba Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic material containing aliphatic perfluoro compounds
US 3666478 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Ufli id States Patent fice US. Cl. 96-1145 3 Claims ABSTRACT OF THE DISCLOSURE Photographic material, preferably for the silver dyestutf bleaching method, is provided which contains in at least one gelatine-containing layer as a wetting agent a watersoluble, surface-active perfluoro compound. With these wetting agents a "very good uniformity of the applied gelatine layers is achieved.

The present invention relates to a light-sensitive photographic material and to a process for its manufacture. It especially relates to the use of surface-active substances as auxiliary agents when coating films and papers with gelatine-containing light-sensitive layers and gelatine-containiny auxiliary layers. Possible light-sensitive layers are preferably silver halide-containing layers, whilst possible auxiliary layers are backing layers, substrata, intermediate layers, covering layers, filter layers and transfer layers.

It is usual to add surface-active substances to photographic gelatine solutions in order to assist the uniform wetting of film, paper or layers which already cover these supports. The wetting of the finished cast layers by processing baths is also intended to be assisted by surfaceactive substances in the layers. Numerous surface-active agents have already been proposed as additives to the casting solution, such as, for example, saponin and also a large number of synthetic anionic, cationic and nonionic substances.

The demands made on surface-active substances are very diverse. They must be obtainable in a quality which always remains constant, which is not the case for natural products such as saponin. They must be photographically harmless and must not have any disadvantageous effect on-the sensitivity, gradation, haze and storage life of the photographic emulsions. They must be compatible with emulsion additives, for example, hardeners, sensitisers, coupling agents and dyestutfs. Furthermore they must improve the physical properties of the casting solutions'to a sufiicient extent in order to fulfil their purpose;

.that'is to say, they must make uniform castings possible,

which are free from streaks, repelled material (comets) and foam (small bubbles), and which adhere well to the substrate. At the present time especially high demands are madeof such surface-active compounds since thinner layers and higher casting speeds are constantlybeing adopted, with a further aim being to cast layers without waiting for the drying of the previouslypcast layers. In particular,'the manufacture of uniform layers for the silver dyestuff bleaching process presents difiiculties,

since the/casting solutions contain water-soluble azo dyestuffs which undergo mutual interactions with the gelatine and hence unfavourably influence the flow properties of the casting solutions.

The present invention is based on the observation that perfluorinated aliphatic compounds of non-ionic or anioniccharacter can advantagesously be employed as wetting agents in photographic, gelatine-containing, casting solutions, with a much better uniformity. of the applied 3,666,478 Patented May 30,1972

layers being attainable than is possible with the wetting agents usually employed in photographic processes. Thewherein R represents a perfluorinated alkyl residue and Z represents an optionally further-substituted carboxylic acid or sulphonic acid residue. Thus the perfluoro compounds are preferably perfluorinated aliphatic carboxylic acids, sulphonic acids, carboxylic acid-amidocarboxylic acids, sulphonic acid-amidocarboxylic acids or the salts of these acids, or sulphonic acid amides, carboxylic acid amides, carboxylic acid esters or urethanes. Further possibilities are also perfluorophosphoric acid esters. By perlluoro compounds there are to be understood compounds which are fluorinated as completely as possible, that is to say, especially compounds which apart from an optionally further-substituted functional group exclusively contain fluorine atoms as substituents. Compounds which are not completely fluorinated however also fall under this concept, such as, for example, compounds which possess a terminal hydrogen atom, a so-called w-H, in the fluorinc-containing residue. ISuch compounds are also called w-H-perfluorinated compounds.

Anionic or anion-active perfluoro compounds for example correspond to the formulae Bra-C O-III-Ih-C OOX R: and above all R2 R represents an alkyl residue which is perfluorinated in the manner indicated, R represents an alkylene residue, R represents a hydrogen atom or an alkyl residue and X represents a hydrogen atom or an alkali metal atom.

Non-ionic or non-ionogenic perfluoro compounds for example correspond to the formulae R represents an alkyl residue which is perfiuorinated in the manner indicated, R and R each represents a hydrogen atom or an alkyl residue and R, represents an alkyl residue. a

= The alkyl residues in Formulae 3 to 9 also rufther substituted, for examplebyiurther. functional groups;

Preferably, R represents a residue of formula wherein n represents an integer having'a value of 3 to 9.: Preferred representatives of the Formulae 2 to 5 for example correspond to the formulae wherein R R R and m have the meanings given above and 2 represents an integer having a value of at most 10.

Of especial interest are perfluorinated carboxylic acids, their alkali metal salts or esters of perfluoro-alcohols with aliphatic carboxylic acids. These perfluoro compounds correspond to the formulae wherein X, R and n have Preferably n is 7 or 8.

An especially suitable wetting agent corresponds to the formula the meanings given above.

Wetting agents of Formulae 1 to 10 and 12 to 24 are commercially available and are for example sold by Minnesota Mining and Manufacturing Company as PC- types and by I. du Pont de Nemours and Company under the name ZonylS.

The wetting agents to be ,used in accordance with the invention are employed in concentrations of 0.05 to 5.0 g. per kg. of ready-to-cast solution, preferably in amounts of from 0.2 g. to 1 g. The photographic properties such as sensitivity, gradation and haze are not influenced by the perfluorinated wetting agents.

The wetting agents to be used in accordance with the invention can also be employed together with other known .nonperfiuorinated surface-active compounds, for example saponin. Gelatine-containing solutions which contain the wetting agents to be used in accordancewith the invention are not only suitable for the application of a single layer but especially also fonthe simultaneotis applicit- -tion of several layers according to the cascade casting process, as is described in United States patent specification No. 3,005,440. Instead of a simultaneous application of several layers it is also possible to manufacture a muiti-layer laminate by applying one layer after the other onto the same support, either by usinga wet-ondry process or by using a wet-on-wet process. I v The wetting agents of the type PC or Zonyl-S usedin the examples which follow are products of- Minnesota Mining and Manufacturing Company and E. I.';du Pont de Nemours and Company, respectively. 1 j The following examples illustrate the invention:'-

EXAMPLE 1 A photographic silver halide-gelatine emulsion containing 25 g. of silver as silver bromide with 2.5 mol percent of silver iodide and' 40 g; of gelatine per kg. of emulsion is cast on a substrated transparent .cellulose triacetate substrate, with the commercial product FC 1281 of probable Formula 24 being added as the wetting agent in various amounts within the range of 0.05 g. to 3.0 g. per kg. of ready-to-cast solution. All layers are free from faults and are uniform. A sensitometric examination shows no differences in sensitivity, gradation or haze.

Similar results are obtained with the commercial products PC 126 (anionic), FC (anionic), FC 98 (anionic), FC (non-ionic), PC 176 (non-ionic) "and Zonyl S 13 (phosphoric acid esters).

EXAMPLE 2 A photographic silver halide gelatine emulsionand an aqueous gelatine solution as a protective layer are simultaneously applied to a transparent cellulose triacetate substrate with the aid of the cascade casting process, as described in United States patent specification No. 3,005,400. The silver halide-gelatine emulsion contains 0.5 g. of PC 128 of probable Formula 24, and the gelatine solution contains 2.0 g. of PC 128. per kg. of casting mixture. The resulting product is free from streaks and other casting faults.

EXAMPLE 3 A silver bromide-iodide emulsion is manufactured which contains 30 g. of gclatine, 13 g. of silver as silver bromide with 2.5 mol percent of silver iodide and 2.4 g. of a blue-green dyestulf according to British "patent specification No. 1,042,300, in 1000 g. of"solution.The silver halide is sensitised towards red "light in the'nsual manner.

One half of the emulsion is cast on a transparent cellulose triacetate substrate, with 0.3 g.v of an, alkylnaphthalenesulphonate per kg. of casting solution "being used as the wetting agent. The other half of the emulsion is cast on the same support, with the addition of 0.3 g. of PC 128 of probable Formula 24. Both layers are exposed behind a grey wedge and are developed in a p-methylaminophenolsulphate-hydroquinone developer.

The following results are obtained:

' I Sensitivity Wetting agent Haze rel. log. units Gradetion With alkylnapthalenesulphonate O. 02 3. 22 0. 58 With F0 128 0. 02 3. 22 0. 58

Furthermore, a 1 metre long piece of both cast films is fixed without exposure, cutinto 35 mm. wide strips, and the colour density of these strips measured at intervals of 6' mm. at a time. The mean value of the colour density and the standard deviation are calculated With FG 128 From this it can be seen that the layer containing PC 128 is much more uniform than the layer containing alkylnaphthalenesulphonate.

Explanation Standard deviation x =mean value x=measured values n=number of measured values EXAMPLE 4 The following layers are successively applied to a transparent polyethylene terephthalate substrate:

1) A silver halide-gelatine emulsion sensitised to red light, containing a blue-green image dyestuff according to British patent specification No. 1,042,300.

(2) A gelatine layer.

(3) A silver halide-gelatine emulsion sensitised towards green light, containing a purple image dyestuiT according to British patent specification No. 914,876.

(4) A gelatine layer.

(5) An unsensitised silver halide-gelatine emulsion containing a yellow image dyestuif according to British patent specification No. 1,094,956.

0.035% of PC 128 of probable Formula 24 are in each case added as the Wetting agent to the ready-to-cast solutions.

In a comparison experiment, the same solutions using 0.035% of an alkylnaphthalenesulphonate were cast.

Samples of both materials are fixed, washed and dried. All colour densities lie between 2.5 and 2.8.

Two other samples of these materials are hazed by homogeneous exposure, developed in p-methylaminophenolsulphatehydroquinone developer, soaked, bleached in a colour bleaching bath, soaked, freed of excess silver in a bleach fixing bath, soaked and dried. A strip of 1 metre length and 35 mm. width was cut from each of these two samples and the colour densities were measured at intervals of 6 mm. The following values are thus obtained:

Standard deviations of the Mean values of the analytical colour densities It can be seen from this table that after photographic processing the material containing FC 128 is again more uniform than the material containing alkylnaphthalenesulphonate.

We claim:

1. Photographic material which comprises at least one gelatine-containing layer that contains as a wetting agent a water-soluble surface active, aliphatic perfluorosulfonic acid derivative of the formula in which R, is a perfiuorinated alkyl group containing 3 to 9 carbon atoms R is an alkylene residue containing from 1 to 6 carbon atoms R is hydrogen, methyl or ethyl and X is hydrogen or an alkali metal atom.

2. Photographic material as claimed in claim 1, wherein the gelatine-containing layer contains a water-soluble azo dyestutf as well as the perfluoro compound.

3. Photographic material as claimed in claim 2, wherein the perfluoro compound corresponds to the formula References Cited UNITED STATES PATENTS 2,732,398 1/1956 Brice et al. 25271 2,937,098 5/1960 Geen 26029.2 3,415,649 12/1968 Nishio et a1. 96114.5 3,514,293 5/1970 Knox 961l4.5 3,516,835 6/1970 Mackey et al. 96114.5

OTHER REFERENCES Surface Active Materials From Perfluorocarboxylic and Perfluorosulfonic Acids, R. A. Guenthner et al., Industrial and Engineering Chemistry, Product Research and Development, vol. 1, No. 3, pp. -169.

JOHN T. GOOLKASIAN, Primary Examiner G. W. MOXON II, Assistant Examiner US. Cl. X.R. 96-94; 106-135 ag UNI ED STATES PATENT OFFICE CERTIFICATE 9F CORRECTION Patent No. 3,666, L78 Dated May 30, 1972 Inventor(s) Margit Groh et 8.1

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 5, delete 'CIBA Limited" and substitute CIBA-GEIGY AG Signed and sealed this 23rd day of April 1971+.

(SEAL) Attest:

MARSHALL DANN Commissioner of Patents EDWARD DLFLETCHERJR. G. Atesting Officer

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3775126 *Feb 29, 1972Nov 27, 1973Eastman Kodak CoLight-sensitive element comprising a coating layer containing a mixture of a cationic perfluorinated alkyl and an alkylphenoxypoly(propylene oxide)
US3850642 *Jan 21, 1974Nov 26, 1974Eastman Kodak CoMultilayer radiation sensitive element having controlled triboelectric charging characteristics
US3888678 *Oct 9, 1973Jun 10, 1975Eastman Kodak CoMethod for adjusting triboelectric charging characteristics of materials
US3948663 *Aug 27, 1974Apr 6, 1976Fuji Photo Film Co., Ltd.Multi-layer color photographic light-sensitive material
US4086178 *May 27, 1975Apr 25, 1978Rolls-Royce Motors LimitedGlass cleaning formulation
US4201586 *Nov 4, 1977May 6, 1980Fuji Photo Film Co., Ltd.Photographic light-sensitive material
US4242444 *Jun 30, 1978Dec 30, 1980Konishiroku Photo Industry Co., Ltd.Perfluoroalkenyl amine, ether, or sulfide derivatives as wetting agents for coating solutions
US4347308 *Feb 17, 1981Aug 31, 1982Fuji Photo Film Co., Ltd.Photographic materials
US4367283 *Jun 25, 1981Jan 4, 1983Fuji Photo Film Co., Ltd.Hydrophilic colloid
US4385110 *Aug 26, 1981May 24, 1983Fuji Photo Film Co., Ltd.Emulsion containing a fluoroalkyl sulfonate or sulfate anionic surfactant
US4508764 *Dec 14, 1982Apr 2, 1985E. I. Du Pont De Nemours And CompanyCoating process employs surfactants
US4806571 *May 6, 1988Feb 21, 1989The Dow Chemical CompanyOrganic composition containing a fluoroalkyl sulfonic acid salt
US4840881 *Jul 21, 1988Jun 20, 1989Konishiroku Photo Industry Co., Ltd.Incorporating oil particles in at least one layer
US5541049 *Jun 13, 1995Jul 30, 1996Minnesota Mining And Manufacturing CompanySilver halide photographic material having improved antistatic properties
US5576074 *Aug 23, 1995Nov 19, 1996Minnesota Mining And Manufacturing CompanyBinder converted to supercooled liquid upon exposure to coherent radiation, absorbing radiation with dye to heat exposure to lasers, forming patterns with toners and heating to fuse
US5674671 *Jun 27, 1995Oct 7, 1997Minnesota Mining And Manufacturing CompanyLight senitive material having improved antistatic behavior
US5866285 *Jun 12, 1997Feb 2, 1999Eastman Kodak CompanyAuxiliary layer for imaging elements containing solvent-soluble fluoropolymer
US5866312 *Jun 19, 1997Feb 2, 1999Eastman Kodak CompanyPhotographic element having surface protective layer
US5874191 *Jun 12, 1997Feb 23, 1999Eastman Kodak CompanyAuxiliary layer formed by the steps comprising coating fluoroolefin-vinyl ether copolymer latex composition on said support, drying
US5888712 *Dec 16, 1997Mar 30, 1999Eastman Kodak CompanyMultilayer imaging element
US5955250 *Dec 16, 1997Sep 21, 1999Eastman Kodak CompanyMultilayer imaging element for silver halide photographic elements
US6071688 *Jul 29, 1998Jun 6, 2000Eastman Kodak CompanyContacting coating material on a support with uniform cloud of additive vaporized by flowing carrier gas through liquid phase additive
US6699648Mar 27, 2002Mar 2, 2004Eastman Kodak CompanyComprising modified fluorochemicals
US7250202Jun 18, 1999Jul 31, 2007Ilford Imaging Ch GmbhSupport with image receiver sheet
DE3207674A1 *Mar 3, 1982Sep 30, 1982Fuji Photo Film Co LtdPhotographisches, empfindliches silberhalogenidmaterial
EP0111338A2 *Dec 10, 1983Jun 20, 1984E.I. Du Pont De Nemours And CompanyCoating process employs surfactants
EP0112162A2Dec 13, 1983Jun 27, 1984Konica CorporationLight-sensitive silver halide photographic material
Classifications
U.S. Classification430/635, 106/154.3, 430/636
International ClassificationG03C7/28, G03C1/38
Cooperative ClassificationG03C7/28, G03C1/385
European ClassificationG03C1/38F, G03C7/28