US3705038A - Spectral sensitization of silver halide lippmann emulsions - Google Patents

Spectral sensitization of silver halide lippmann emulsions Download PDF

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Publication number
US3705038A
US3705038A US78936A US3705038DA US3705038A US 3705038 A US3705038 A US 3705038A US 78936 A US78936 A US 78936A US 3705038D A US3705038D A US 3705038DA US 3705038 A US3705038 A US 3705038A
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group
emulsions
dye
silver halide
emulsion
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US78936A
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Herman Adelbert Philippaerts
Theofiel Hubert Ghys
Henri Depoorter
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups

Definitions

  • Z represents the atoms necessary to close a pyrroline nucleus or a tetrazole nucleus
  • R represents hydrogen, an aliphatic group or an aryl group
  • each of R and R stands for an aliphatic group or an aryl group, one of R and R comprising a sulpho group, a carboxy group, a sulphato group, a phosphone group or a sulphamoyl or sulphonyl-carbamoyl group.
  • These dyes have an excellent sensitizing action in the green region of the spectrum and can be used in high concentrations without leaving residual stain in the emulsion after processing and without producing fog.
  • the present invention relates to the spectral sensitization of light-sensitive silver halide emulsions of the Lippmanntype.
  • Lippmann emulsions are of particular importance for the preparation of photographic plates used as masks in the production of micro-electronic integrated circuits.
  • drawings are made on highly enlarged scale of the various successive circuits necessary to produce one integrated circuit whereupon the drawings are reduced, and reproduced on a photographic plate forming thereby the mask ready for use.
  • Lippmann-emulsions for micro-electronic mask making should have a high resolving power in order to allow a correct reproduction of the dimensions of the images.
  • high concentrations of spectral sensitizers are required in the emulsions. These high concentrations enhance the risk of residual stain being left in the material upon processing and the speed of the material being lowered by desensitization.
  • Lippmann-emulsions for microelectronic mask-making should be orthochromatically sensitized since the spectral region of the exposure light used in the production of the microelectronic mask is situated near 545 nm. A strong orthochromatic sensitization is required so that processing of the material with fairly bright darkroom safelight illumination is possible.
  • Z stands for the atoms necessary to close a pyrroline nucleus or a tetrazole nucleus
  • R stands for hydrogen, an aliphatic group including a saturated aliphatic group, an unsaturated aliphatic group and a cycloaliphatic group for example alkyl e.g. methyl and ethyl, aralkyl e.g. benzyl and cycloalkyl e.g. cyclohexyl or an aryl group such as phenyl, which groups may carry further substituents, and
  • each of R and R stands for an aliphatic group including a saturated aliphatic group, an unsaturated aliphatic group and a cycloaliphatic group for example C -C alkyl, allyl, benzyl, and cycloalkyl or an aryl group, which groups may carry substituents, one of R and R comprising a sulpho group in acid or salt form, a carboxy group in acid or salt form, a sulphato group in acid or salt form, a phosphono group in acid or salt form or a sulphamoyl or sulphonylcarbarnoyl group in acid or salt form for instance one of R and R being carboxylalkyl e.g.
  • each of W and V represents carbonyl, sulphonyl or a single bond, at least one of W and V being sulphonyl
  • A represents an alkylene group e.g. a C -C alkylene group
  • B represents hydrogen, alkyl including substituted alkyl, amino including substituted amino, e.g.
  • acylamino, diethylamino, or dimethylamino with the proviso, however, that B does not represent hydrogen when V represents carbonyl or sulphonyl, the group --AWNH-V-B being exemplified by N-(methylsulphonyl)-carbamoyl-methyl, 'y-(acetylsulphamoyD- propyl, and 5-(acetylsulphamoyl)-butyl,
  • Lippmann-emulsions lend themselves perfectly for spectrally sensitizing Lippmann-emulsions, in that they have an excellent sensitizing action for Lippmann-emulsions in the green region of the spectrum with their main absorption comprised between 500 and 550 nm., that they can be used in high concentrations without giving rise to desensitization and without leaving residual stain in the photographic material after processing, and that they produce no fog.
  • Exemplary merocyanine dyes falling within the ambit of the above general formula and particularly suitable for the spectral sensitization of Lippmann-emulsions are listed in the following table.
  • the merocyanine dyes of use according to the present invention are partly known e.g. from United Kingdom patent specifications 654,683 filed Feb. 24, 1947 by Kodak 00., 1,090,626 filed Oct. 11, 1965 by Agfa AG and 1,120;- 047 filed Apr. 26, 1966 by Ilford. They can be prepared by methods well known to those skilled in the art e.g. by condensing:
  • Q stands for a fi-arylamino group, preferably an acylated ,B-arylamino group, e.g. fi-acetanilido, or an alkoxy group, and
  • X- stands for an anion, or is not present when R, contains an anionic group
  • R has the same significance as above:
  • Y is hydrogen or acyl
  • Ar is aryl
  • R and R have the same significane as above.
  • Dye 20 This dye was prepared in an analogous way as dye 18 starting from 1 phenyl-5-methyl-4-(4-sulpharnylbutyl) tetrazolium bromide. Yield: 34%.
  • Dye 21 This dye was prepared from 0.6 g. of the dye of preparation 5 by recrystallization from acetic anhydride. Yield: 0.3 g. Melting point: 245 C. (decomposition).
  • photographic materials comprising at least one lightsensitive silver halide emulsion of the Lippman-type con taining at least one sensitizing dye corresponding to the above general formula.
  • the ratio of hydrophilic colloid binder to silver halide in the Lippmann emulsions according to the present invention is preferably comprised between 1:5 and 15:1.
  • the thickness of the emulsion layer of a photographic material according to the present invention is generally comprised between about 3 microns and 8 microns and the average grain size of the silver halide grains is at most 0.1 micron, generally less than 0.08 micron.
  • the liydrophilic colloid used as the vehicle for the silver halide may be any of the common hydrophilic colloids employed in photographic light-sensitive emul- 6 sions, for example gelatin, agar-agar, albumine, zein, casein, collodion, alginic acid, water soluble cellulose derivatives such as carboxymethylcellulose, polyvinyl alcohol, poly-N-vinyl pyrrolidone or other hydrophilic synthetic or natural resins or polymeric compounds, gelatin being however favoured. If desired, compatible mixtures of two or more colloids may be employed for dispersing the silver halide.
  • silver salts may be used as the light-sensitive salt such as silver chloride, silver bromide, silver iodide or mixed silver halides such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
  • Silver bromide emulsions having an average grain size of at most 0.1 micron and an iodide content comprised between 0 and 8 mole percent are favoured.
  • Sensitization of Lippmann emulsions by means of the sensitizing dyes according to the above general formula occurs by incorporating the acid dyes or their salts into the said emulsions by one of the methods customarily employed in the art. In practice, it is convenient to dissolve the dyes in water, methyl alcohol, ethyl alcohol or a mixture of one of these alcohols with water and to disperse the solution formed into the washed, finished emulsion so that the dye is uniformly distributed throughout the emulsion. It is apparent of course that the dyes can be incorporated by other methods and at any stage of emulsion preparation.
  • the concentration in the emulsion of the sensitizing dyes corresponding to the above general formula can vary between wide limits. Up to 1000 mg. and preparably from 300 mg. to 700 mg. of dye are used per mole of silver halide. The most suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art, upon making the ordinary tests and observations customary in the art of emulsion making.
  • the dyes are preferably incorporated into photographic emulsions the general sensitivity of which has been increased by chemical ripening. These emulsions may be chemically sensitized by effecting the ripening in the presence of small amounts of sulphur containing compounds such as allyl isothiocyanate, allyl thiourea, sodium thiosulphate, potassium selenocyanide, etc.
  • sulphur containing compounds such as allyl isothiocyanate, allyl thiourea, sodium thiosulphate, potassium selenocyanide, etc.
  • the emulsions may also be sensitized by means of reducing sensitizers such as tin compounds, imino-aminomethane sulphinic acids and the derivatives thereof, cadmium salts, and the salts of noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium.
  • reducing sensitizers such as tin compounds, imino-aminomethane sulphinic acids and the derivatives thereof, cadmium salts, and the salts of noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium.
  • Lippmann emulsions spectrally sensitized in accordance with the present invention may also comprise light-absorbing dyes to reduce scattering and reflection of light within the photographic material, said dyes being chosen so as to absorb light of the wavelength to which the material is exposed and may be any of the light-absorbing or filter dyes customarily employed in common photographic light-sensitive materials including oxonol dyes, arylidene dyes, styryl dyes, triarylmethane dyes, azo dyes, etc. Further details as to the use of these light-absorbing dyes in Lippmann-emulsions can be found in United Kingdom patent specification 1,139,062 filed Jan. 1, 1965 by Kodak Co. and in Belgian patent specification 742,954 filed Dec. 11, 1969 by Gevaert-Agfa N .V.
  • the emulsions may further comprise compounds restraining the growth of the silver halide crystals during precipitation so that emulsions can be prepared with an average silver halide grain-size markedly smaller than in the absence of said compounds.
  • Belgian. patent specification 710,602 filed Feb. 23, 1967 by Kodak Co. and to United Kingdom patent applications 53,025/69 filed Oct. 19', 1969 and 54,539/ 69 filed Nov. 6, 1969 both by Gevaert-Agfa N.V.
  • the usual and suitable addenda such as antifoggants, stabilizers, development accelerators, plasticizers, wetting agents and hardeners are also incorporated into the emulsion in a known manner.
  • Suitable hardening agents are amongst others formaldehyde, halogen-substituted aldehydes comprising a carboxyl group such as mucobromic acid, diketones, dialdehydes, etc.
  • Compounds suitable for sensitizing the emulsions by development acceleration are e.g. compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described amongst others in US. patent specifications 2,531,832 of William Alexander Stanton, issued Nov. 28, 1950 and 2,533,990 of Ralph Kingsley Blake, issued Dec. 12, 1950, in United Kingdom patent specifications 920,637 filed May 7, 1959, 940,051 filed Nov. 1, 1961, 945,340 filed Oct. 23, 1961 all three by Gevaert Photo-Producten N.V. and 991,608 filed June 14, 1961 by Kodak Co., and in Belgian patent specification 648,710 filed June 2, 1964 by Gevaert Photo-Producten N.V. as well as onium derivatives of amino-N-oxides as described in United Kingdom patent specification 1,121,696 filed Oct. 7, 1965 by Gevaert-Agfa N.V.
  • mercury compounds such as the mercury compounds described in Belgian patent specifications 524,121 filed Nov. 7, 1953 by Kodak Co., 677,3 37 filed Mar. 4, 1966 and 707,386 filed Dec. 1, 1967 both by Gevaert-Agfa N.V., US. patent specification 3,179,520 of Yoshio Miura, Akira Kumai and Yosuke Nakajima, issued Apr. 20, 196 5, heterocyclic nitrogen containing thioxo compounds such as those described in the German patent specification 1,151,731 filed Mar.
  • Lippmann emulsions sensitized in accordance with the present invention may be coated on a wide variety of photographic emulsion supports.
  • Typical supports include cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials as well as paper and glass.
  • high-resolution plate materials for the preparation of masks for use in the electronic industry glass supports are most advantageously used in view of their high dimensional stability.
  • the following example illustrates the use of the sensitizing dyes according to the above general formula for the spectral sensitization of Lippmann-emulsions in comparison to other merocyanine dyes of closely related structure.
  • a silver bromide emulsion comprising 72 g. of silver bromide and 93 g. of gelatin was prepared by simultaneous addition of a silver nitrate solution and a potassium bromide solution to a 3% aqueous solution of gelatin. The conditions of precipitation were adjusted so that a Lippman emulsion with an average grain size of 007g was obtained. Details as to the preparation of Lippmann emulsions can be found amongst others in P. Glaf-kids Photographic Chemistry, vol. 1, 1958, Fountain Press, London. The emulsion was divided into several aliquot portions and to each portion one of the sensitizers listed in the table below were added in an amount of 0.94 millimole per mole of silver halide.
  • the emulsions were then coated on glass plates and dried so as to obtain an emulsion layer thickness of 5 microns.
  • the materials thus obtained were exposed in a sensitometer once without filter (general sensitivity) and once through a yellow filter (spectral sensitivity) the transmission of which for light of a wavelength shorter than 460 nm. is less than 0.1% and for light of a wavelength longer than 520 run. is more than 90%.
  • Photographic silver halide emulsion of the Lipprnann-type comprising a hydrophilic colloid as binder for the silver halide and a spectrally sensitizing amount of a merocyanine dye corresponding to the formula:
  • Z stands for the atoms necessary to close a pyrroline nucleus or a tetrazole nucleus
  • R stands for hydrogen, an aliphatic group or an aryl group, and each of R and R stands for an aliphatic group or an aryl group, one of R and R comprising a sulpho group in acid or salt form, a carboxy group in acid or salt form, a sulphato group in acid or salt form, a phosphono group in acid or salt form or a sulphamoyl or sulphonylcarbamoyl group in acid or salt form.
  • Photographic emulsion according to claim 1 wherein the sensitizer is present in an amount up to 1000 mg. per mole of silver halide.
  • Photographic emulsion according to claim 1, wherein the light-sensitive silver halide is silver bromoiodide, comprising at most 8 mole percent of silver iodide and having an average grain size of at most 0.08p-
  • Photographic emulsion according to claim 1 where in the ratio of hydrophilic colloid binder to silver halide is comprised between 1:5 and 15:1.
  • Photographic light-sensitive material comprising a support and a silver halide emulsion layer of the Lippmann type wherein said emulsion layer comprises a dye as defined in claim 1.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
US78936A 1970-01-20 1970-10-07 Spectral sensitization of silver halide lippmann emulsions Expired - Lifetime US3705038A (en)

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JP (1) JPS514105B1 (enrdf_load_html_response)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804634A (en) * 1971-03-20 1974-04-16 Fuji Photo Film Co Ltd Photographic supersensitized silver halide emulsion
US3869290A (en) * 1971-11-10 1975-03-04 Agfa Gevaert Nv Photographic silver halide elements of the Lippmann-type
US5338656A (en) * 1992-04-22 1994-08-16 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5464735A (en) * 1993-12-07 1995-11-07 Eastman Kodak Company Supersensitizing bis-benzothiazolocyanine dye combination for red sensitive silver halide emulsions
US5464734A (en) * 1993-06-08 1995-11-07 Fuji Photo Film Co., Ltd. Methine compounds and silver halide photographic materials containing the compound

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5652716B2 (enrdf_load_html_response) * 1972-08-30 1981-12-14

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804634A (en) * 1971-03-20 1974-04-16 Fuji Photo Film Co Ltd Photographic supersensitized silver halide emulsion
US3869290A (en) * 1971-11-10 1975-03-04 Agfa Gevaert Nv Photographic silver halide elements of the Lippmann-type
US5338656A (en) * 1992-04-22 1994-08-16 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5464734A (en) * 1993-06-08 1995-11-07 Fuji Photo Film Co., Ltd. Methine compounds and silver halide photographic materials containing the compound
US5464735A (en) * 1993-12-07 1995-11-07 Eastman Kodak Company Supersensitizing bis-benzothiazolocyanine dye combination for red sensitive silver halide emulsions

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JPS514105B1 (enrdf_load_html_response) 1976-02-09
FR2074976A5 (enrdf_load_html_response) 1971-10-08
CA979268A (en) 1975-12-09
CH567281A5 (enrdf_load_html_response) 1975-09-30
DE2101106A1 (de) 1971-07-29
SU479304A3 (ru) 1975-07-30
GB1329271A (en) 1973-09-05

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