US3409433A - Photographic materials containing filter dyes - Google Patents

Photographic materials containing filter dyes Download PDF

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Publication number
US3409433A
US3409433A US377774A US37777464A US3409433A US 3409433 A US3409433 A US 3409433A US 377774 A US377774 A US 377774A US 37777464 A US37777464 A US 37777464A US 3409433 A US3409433 A US 3409433A
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Prior art keywords
emulsions
emulsion
dyes
color
green
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Expired - Lifetime
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US377774A
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English (en)
Inventor
Bockly Erich
Loffler Beate Elisabeth
Loffler Monika
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Agfa Gevaert NV
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Agfa AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39292—Dyes

Definitions

  • the present invention relates to silver halide emulsions and to multilayer materials for color photography, which emulsions and materials contain dyestuffs that increase the sharpness of color images.
  • Multilayer materials for color photography more especially printing materials, must meet high standards of sharpness and resolution and of color reproduction. It is known that these properties can be impaired by the scattering effect of the silver halide grains present in the layers.
  • the light-sensitive layers of these multilayer materials can contain dyes which absorb in the spectral sensitivity region of the emulsions and which can be removed again .after the exposure.
  • the harmful scattered or dispersed light is weakened more than thelight passing perpendicularly through the layers because of its longer path, so that it is possible to produce in this way an additional improvement in the sharpness.
  • the absorbing dyes particularly when used for color photography, must be practically completely decolorized or removed subsequently because even a faint stain of residual dyestui can considerably impair the quality of a color image.
  • Many dyestutfs which are decolorized by the agents used in the processing baths, e.g., by sodium sulte or potassium ferricyanide are useless because the decolorization is incomplete. It is therefore advantageous to use dyestuis which can be washed out of gelatin layers.
  • the absorbing dyes are most effective when their absorption maxima coincide with or only differ very slightly from the sensitization maxima of the emulsion layer for whlch the dye is to be used. This effect is most ditlicult to obtain with green senstive layers since the sensitivity range of such layers of multilayer printing materials for color photography is narrower than that of other exposure materials.
  • the highest lgreen sensitivity is usually 1n the range from 540- to 555 millmicrons and decreases sharply towards either side ofthis range, especially towards longer wavelengths.
  • an absorbing dye intended for use in a green sensitive layer of multilayer photographic material with an interchanged layer arrangement as referred to hereinbefore must not absorb in the blue region of the spectrum since such an absorption would cause an undesirable reduction in the light transmitted to the blue sensiive layer which is arranged below the green-sensitive ayer.
  • monoazo dyestuis of the following formula are excellently suitable for use as absorbing dyes for the green-sensitive layer of multilayer color-photographic materials:
  • R1 represents an alkoxy group, having preferably up to 5 carbon atoms, more especially a methoxy or an ethoxy group;
  • R2 represents a hydrogen atom or an alkoxy group as defined under R1;
  • R3 represents an acyl group, preferably an :acyl group originating (I) from a carboxylic acid, more preferably from an aliphatic carboxylic acid having up to 5 carbon atoms such as acetyl, propionyl, butyryl, valeryl, or the like, or (II) an organic sulfonic acid more preferably derived from a'phenyl sulphonic acid such as a toluene sulfonyl group or a benzene sulfonyl group;
  • M stands for any cation such as a hydrogen ion or generally a cation which forms a water-soluble salt, more especially a cation of an alkali metal such as sodium or potassium or an ammonium ion.
  • the dyes according to the invention can be completely (I) NH.CO.CH3
  • FIGURE 1 shows the absorption curves of the above dyestuifs II, III and IV (the line of crosses represents a third curve that is not drawn); and
  • FIGURE 2 illustrates the sensitivity spectrum of the green-sensitive layer, before (left portion of curve) and after (right portion of curve) it is sensitized with a sensitizing dye of the following formula:
  • the dyes of the present invention are added in aqueous solution, advantageously in quantities of 1 to 6 g. per 100 g, of silver, to the green-sensitive silver halide emulsion before it is cast. Because of the high water solubility and the low affinity of the dyes for gelatin, it may be advantageous for the other emulsions, in addition to the green-sensitive layer, to be colored in the same way before casting.
  • the photographic silver halide emulsions in which the absorbing dyes are to be used can be optically sensitized.
  • the usual optical sensitizing dyes for the green range of the Avisible spectrums can be used, such as cyanines, merocyanines, styryl dyes and the like.
  • the absorbing dyes can be used for silver chloride or bromide emulsions which may contain a small amount of up to mol percent of silver iodide or for emulsions containing silver chloride and silver bromide. While our invention is particularly directed to the ordinary silver halide gelatin emulsions, binding agents other than gelatin, e.g., polyvinyl alcohol or cellulose materials such as hydrolyzed cellulose acetate, carboxymethyl cellulose or.
  • binding agents other than gelatin e.g., polyvinyl alcohol or cellulose materials such as hydrolyzed cellulose acetate, carboxymethyl cellulose or.
  • emulsions prepared in accordance with our invention can be coated in the usual manner upon any suitable support of, e.g., a cellulose ester such as cellulose acetate, polycarbonate especially of bis-hydroxyphenyl alkanes, polystyrene, a polyester in particular polyethylene terephthalate, etc.
  • a cellulose ester such as cellulose acetate
  • polycarbonate especially of bis-hydroxyphenyl alkanes, polystyrene, a polyester in particular polyethylene terephthalate, etc.
  • the silver halide emulsions according to the invention can also containfsuch additives as chemical sensitizers, e.g., sulfo-sensitizers, various gold compounds, palladium compounds and the like.
  • chemical sensitizers e.g., sulfo-sensitizers, various gold compounds, palladium compounds and the like.
  • the emulsions can also be stabilized with mercury compounds such as described in U.S. Patents Nos. 2,728,663 ⁇ and 2,728,665, triazoles, and azaindenes such as disclosed by Birr in Z. Wiss. Phot, vol. 47, 1952, pp. 2 to 28.
  • the emulsions may be hardened with any suitable harderier for the binding agent, for example, formaldehyde or derivatives of formaldehyde, cyclic 1,2-diketones and the like can be used for hardening gelatin.
  • any suitable harderier for the binding agent for example, formaldehyde or derivatives of formaldehyde, cyclic 1,2-diketones and the like can be used for hardening gelatin.
  • the emulsions may further contain a coating aid such as wetting agents, for example, saponine, lauryl or oleyl monoether of polyethylene glycol, esters of glycerol and the like.
  • a coating aid such as wetting agents, for example, saponine, lauryl or oleyl monoether of polyethylene glycol, esters of glycerol and the like.
  • magenta coupler used in the emulsion of the invention is not especially critical and is selected according to the requirements of the particular reproduction process in which the emulsion is to be used. Suitable are the common types of magenta coupler such as those of the pyrazolone series as described by O. Wahl yin Angewandte Chemie, volume 64, 1952, pages 259 to 265, as well as magenta couplers of thecyanine acetyl type, indazolones, or pyrazolobenzimidazoles, such as disclosed in British Patent No. 918,128 or U.S. Patent No. 3,061,- 432.
  • Example 1 ontneemt-@ Q o (ninemsn- This emulsion also contains the usual quantities of a stabilizer such as 250 mg. of 5-methyl7hydroxy2,3,4- triazaindolizine, a hardening agent as, for example, disclosed in German Patent No 872,153 and a wetting agent such as saponine (30 ml. of a 7.5 aqueous solution of saponine per kg. of emulsion are added);
  • a stabilizer such as 250 mg. of 5-methyl7hydroxy2,3,4- triazaindolizine
  • a hardening agent as, for example, disclosed in German Patent No 872,153
  • a wetting agent such as saponine (30 ml. of a 7.5 aqueous solution of saponine per kg. of emulsion are added
  • the multi-layer materialthus prepared fand dried contains 155 mg. of absorbing dye'. per square meterAymicro'- line screen was exposed on samples of this photographic material and also on those of'a 'standard material of the same type which is prepared f orl comparison purposes and which differs only from the above material in that it does not contain any absorbing dye. These samples were processed for.. 8 minutesin a color-forming developer of the following composition:V i i After subsequent bleaching, fixing and rinsing, according to common practice, the following fogging densities, measured at the unexposed areas, were obtained:
  • Example 2 the usual quantities of stabilizing, ⁇ hardening and wetting agents'for example those described/'in Example 1, additionally containing per kg. of emulsion 6'0 ml. f'a 1% aqueous solution of the absorbing dye of Formula III; (b) A silver chlorobromide emulsion 'containing about 4 mol percent of silver bromidewhich is sensitized for light of the red region of the spectrum-and to which are added, per kg. of emulsion,l 15' g. of the cyan coupler according to Example 1, as well as the stabilizing, hardening-and wetting agentssuch as describ'ednin Example'l, and 6 (;)'ml.,v of a 1% aqueous.
  • the emulsions (a), (b) 4and (c) are coated in the above sequence onto a sheet-like support consisting of 'cellulose triacetate'.
  • the dried multilayer material which may comprise also the usual protective layers, contains :about mg. of absorbing dye according to Formula III per square meter.
  • a standard sample is prepared by using the same emulsions and additives, Ibut without the absorbing dyestuif. Microline screens are exposed onto samples of both materials, as in Example 1.
  • the evaluation of the screen exposures showed a resolution of lines per mm. for the material without dyestuif, and a resolution of lines per mm. for the material with absorbing dyestuff, with considerably improved contrast reproduction.
  • Example 3 For the formation of a three-layer positive film, the emulsions (a), (b) and (c) are prepared as described in Example 2, but (a) and (b) do not contain any absorbing dyestuff and (c) contains, per kg. of emulsion, 200 ml. of the 1% aqueous solution of thev :absorbing dye according to Formula III.
  • R1 standsv for an alkoxy group having up toi5 carbon atoms
  • R2 is amemberof'the group-consisting of hydrogen and ⁇ an alkoxy group 'havinglu'pfto 5 carbon atoms
  • R3 stnads for an a'c'yl group and M represents acation, the dye being in'readily/ rinsed-outcondition so that it is removed during processing ⁇ but :increasesthe r resolving power and contrast of the image.
  • 'ia t t 2 A photographic silver halide emulsion as defined in claim 1, wherein R3 is an acyl group of an aliphatic carboxylic acid with 1.-5 carbon atoms.
  • a photographic multilayer element comprising a sheet-like support having coated thereon the following silver halide emulsion layers:
  • R1 stands for an alkoxy group having up to 5 carbon atoms
  • R3 is a member of the groupv consisting of hydrogen and an alkoxy group having up to 5 carbon atoms
  • R3 stands for an acyl group and M represents a cation, the dye being in readily rinsedmout condition so that it is removed during processing ,bu'tincreases'th'e resolving power and con- ;-itf-ast @fue image-1' L i 5.
  • R3 ⁇ is anv acyl group of an aliphatic carboxylic ac idwith'l-S carbon atoms.
  • l (f6.
  • a photographic' multilayer element is defined in claim 4, wherein R3 is a phenyl ⁇ sulfonyl group.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US377774A 1963-07-15 1964-06-24 Photographic materials containing filter dyes Expired - Lifetime US3409433A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA43575A DE1182067B (de) 1963-07-15 1963-07-15 Farbenphotographisches Mehrschichtenmaterial mit vertauschter Schichtanordnung

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US3409433A true US3409433A (en) 1968-11-05

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US (1) US3409433A (de)
BE (1) BE650453A (de)
CH (1) CH436983A (de)
DE (1) DE1182067B (de)
FR (1) FR1401787A (de)
GB (1) GB1045609A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3338835A1 (de) * 1982-10-27 1984-05-10 Canon K.K., Tokio/Tokyo Monoazoverbindungen und aufzeichnungsfluessigkeiten mit einem gehalt an diesen verbindungen

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0725312B1 (de) * 1995-02-01 2002-11-27 Tulalip Consultoria Comercial Sociedade Unipessoal S.A. Farbphotographische Silberhalogenidelemente
DE69528957T2 (de) * 1995-02-01 2003-09-11 Tulalip Consultoria Com Socied Farbphotographische Silberhalogenidelemente

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2697037A (en) * 1949-11-23 1954-12-14 Eastman Kodak Co Multilayer print film having incorporated coloring material
US2704710A (en) * 1950-04-18 1955-03-22 Gen Aniline & Film Corp Precipitation of azo dyes in silver halide emulsions by means of guanidine and biguanide compounds containing long alkyl chains
US2947628A (en) * 1956-10-12 1960-08-02 Eastman Kodak Co Multilayer print film having incorporated coloring material
US2956879A (en) * 1958-01-07 1960-10-18 Eastman Kodak Co Filter and absorbing dyes for use in photographic emulsions
US3177078A (en) * 1962-02-03 1965-04-06 Agfa Ag Filter and absorbing dyes for photographic emulsions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2697037A (en) * 1949-11-23 1954-12-14 Eastman Kodak Co Multilayer print film having incorporated coloring material
US2704710A (en) * 1950-04-18 1955-03-22 Gen Aniline & Film Corp Precipitation of azo dyes in silver halide emulsions by means of guanidine and biguanide compounds containing long alkyl chains
US2947628A (en) * 1956-10-12 1960-08-02 Eastman Kodak Co Multilayer print film having incorporated coloring material
US2956879A (en) * 1958-01-07 1960-10-18 Eastman Kodak Co Filter and absorbing dyes for use in photographic emulsions
US3177078A (en) * 1962-02-03 1965-04-06 Agfa Ag Filter and absorbing dyes for photographic emulsions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3338835A1 (de) * 1982-10-27 1984-05-10 Canon K.K., Tokio/Tokyo Monoazoverbindungen und aufzeichnungsfluessigkeiten mit einem gehalt an diesen verbindungen
DE3338835C3 (de) * 1982-10-27 1998-06-10 Canon Kk Aufzeichnungsflüssigkeit mit einem Gehalt an bestimmten Monoazoverbindungen in einem Gemisch aus Wasser und einem mit Wasser mischbaren organischen Lösungsmittel und Verwendung eines Gemisches aus Wasser und einer dieser Monoazoverbindungen als Aufzeichnungsflüssigkeit

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FR1401787A (fr) 1965-06-04
GB1045609A (en) 1966-10-12
DE1182067B (de) 1964-11-19
BE650453A (de) 1965-01-13
CH436983A (de) 1967-05-31

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