US3573916A - Method for preparing color elements providing mottle-free dye images - Google Patents

Method for preparing color elements providing mottle-free dye images Download PDF

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US3573916A
US3573916A US719689A US3573916DA US3573916A US 3573916 A US3573916 A US 3573916A US 719689 A US719689 A US 719689A US 3573916D A US3573916D A US 3573916DA US 3573916 A US3573916 A US 3573916A
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dye
emulsion
mottle
coated
electron
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Richard G Yost
Irving S Willison
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/102—Organic substances dyes other than methine dyes
    • 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
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/915—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means using mechanical or physical means therefor, e.g. corona
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/138—Corona discharge process

Definitions

  • This invention relates to a method for preparing photographic elements, and more particularly to a method for preparing spectrally sensitized photographic elements which are coated on hydrophobic surfaces.
  • photographic silver halide emulsions can be coated on supports having a hydrophobic surface.
  • One highly useful photographic support is polyolefin coated paper, the polyolefin being the hydrophobic surface.
  • Such supports offer considerable advantages over prior art paper supports in that the polyolefin acts as an emcient barrier between the emulsion and various contaminants or materials which can be contained in the paper. The polyolefin prohibits such contaminants from exerting adverse effects on the emulsion.
  • paper supports which have polyolefin coatings on both sides are effectively waterproofed.
  • Photographic substrates having a hydrophobic surface require some treatment in order to obtain suflicient adhesion between the hydrophobic surface and the photographic silver halide emulsion.
  • One of the most convenient techniques for obtaining sufficient adhesion is to electron bombard the hydrophobic surface. Electron bombardment is also known as corona discharge treatment. Processes for electron bombarding hydrophobic surfaces are described in Alsup and Venor British Patents 971,058 and 1,060,526 (polyolefin surfaces); Carroll et al. US. Patent 3,220,842, issued Nov. 30, 1965 [poly(ethy1ene terephthalate)]; and Crawford et al. US. Patent 3,117,865, issued Jan. 14, 1964 (paper coated with chromium halide complex, such as sterato chromic chloride).
  • One object of this invention is to provide a novel process for preparing light sensitive photographic elements.
  • Another object of this invention is to provide a novel process for preparing light sensitive photographic elements which have a Spectrally sensitized photographic silver halide emulsion layer containing color former coated on an electron bombarded hydrophobic surface.
  • a further object of this invention is to provide a method for coating spectrally sensitized silver halide emulsions containing color former on an electron bombarded hydrophobic surface whereby mottle-free dye images can be obtained.
  • Still another object of this invention is to provide a method for coating spectrally sensitized light sensitive silver halide emulsions containing color former onto an electron bombarded hydrophobic surface without undue photographic speed loss.
  • Spectral sensitization of photographic silver halide emulsions with a sulfo substituted methine dye allows the preparation of photographic elements by coating an emulsion containing color former onto a hydrophobic surface substantially immediately after it has been electron bombarded.
  • Photographic elements prepared in accordance with this invention are free from mottle.
  • the process of this invention can be carried out by Spectrally sensitizing photographic silver halide emulsions with a methine dye of the type used to Spectrally sensitize silver halide emulsions, which methine dye contains a sulfo group.
  • cyanine includes simple cyanine dyes and higher homologs, e.g., carbocyanine, dicarbocyanine and tricarbocyanine dyes.
  • cyanine dyes feature the amidinium-ion chromophore system. In cyanine dyes, each nitrogen atom of the amidinium-ion system is contained in a heterocyclic ring. See Mees and James, The Theory of Photographic Process, third edition, 1966, at pages 201 and 202.
  • cyanine dye containing a sulfo group can be used in the practice of this invention.
  • the most useful cyanine dyes are those wherein at least one of the nitrogen atoms of the amidinium-ion system in the dye contains a sulfoalkyl group, such as sulfomethyl, sulfopropyl, sulfobutyl, etc.
  • a highly useful class of sulfoalkyl substituted cyanine dyes is represented in Formula I below:
  • Z and Z each represents the nonmetallic atoms required to complete a heterocyclic nucleus of the type used in cyanine dyes, typically containing from to 6 atoms in the heterocyclic ring, which ring can contain a second hetero atom such as oxygen, sulfur, selenium or a second nitrogen atom, such as quaternary salts formed from nuclei of the thiazole series (e.g., thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-di phenylthiazole, 4-(2-thienyl)-thiazole, benzothiazole, 4- chlorobenzothiazole, 5-ehlorobenzothiazole, 6-chlorobenzothiazole, 7-ch
  • sulfopropoxy e.g., 3 (sulfopropoxy)ethyl, (4 sulfobutoxy)ethyl, and (3-sulfobutoxy)propyl, at least one of Z, Z R and R including a sulfo group; at and e each represents an integer of from 1 to 2; n represents an integer of from 1 to 3; and X represents an acid anion, which can be a sulfo group combined with R or R or an acid anion such as chloride, bromide, iodide, thiocyanate, sulfonate, perchlorate, p-toluenesulfonate, methyl sulfate, ethyl sulfate and so forth.
  • At least one of R and R represents a sulfoalkyl group, the alkyl group advantageously containing from 1 to 4 carbon atoms.
  • the N-sulfoalkyl substituted cyanine dyes containing a benzoxazole nucleus the N,N'-disulfoalky1 substituted oxacarbocyanines being particularly useful.
  • Methine dyes having the amidic chromophore system are referred to herein, and in the art, as merocyanine dyes. Any mercocyanine dye containing a sulfo group can be employed in the practice of this invention.
  • Z has a meaning selected from those given for Z, and Z above, R represents an alkyl or aryl group selected from those described for R and R above; L and L each represents a methine group as described for L -L above; a represents an integer of from 1 to 2; m represents an integer of from 1 to 3; and Q represents the non-metallic atoms required to complete a to 6 membered heterocyclic nucleus of the type used in merocyanine dyes, typically containing a hetero atom selected from nitrogen, sulfur and oxygen, such as a 2-pyrazolin-5-one nucleus, e.g., 1-phenyl-3-(2-sulfopropyl)-2-pyrazolin-5-one, 1-(4- sulfophenyl)-2-pyrazolin-5-one, etc., an isoxazolone nucleus (e.g., 3-(4-sulfophenyl)-5(4H)-isoxazolone, 3-(4
  • l,3-di(sulfoall yl group e.g., 1,3-di- (2 sulfoethyl); 1,3-di-(3-sulfopropyl); l,3-di-(4-sulfocy clohexyl); [(4-sulfobutoxy)ethyl], etc., or 1,3-di-(sulfoaryl); e.g., 1,3-di-(4-sulfophenyl); etc., or l-sulfoaryl, e.g., l-(4-sulfophenyl); etc.; a sulfo-substituted rhodanine nucleus (i.e., Z-thio-2,4-thiazolidinedione series), such as 3- sulfoalkylrhodanines, e.g., 3-(2-sulfoethyl
  • ketomethylene nucleus of the type used in merocyanine dyes at least one of Q, Z and R containing a sulfo group.
  • Q represents a sulfosubstituted heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom, and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.
  • Preferred merocyanine dyes are those in which Q includes a heterocyclic nitrogen atom which has attached thereto a sulfoalkyl (preferably alkyl groups of from 1 to 4 carbon atoms) or a sulfoaryl group, such as a psulfophenyl group.
  • Q includes a heterocyclic nitrogen atom which has attached thereto a sulfoalkyl (preferably alkyl groups of from 1 to 4 carbon atoms) or a sulfoaryl group, such as a psulfophenyl group.
  • Specific useful merocyanine dyes of this invention include the following:
  • photographic silver halide emulsions containing color former are coated on hydrophobic surfaces.
  • color formers includes any of those compounds which react or couple with the oxidation product of primary aromatic amino developing agents (e.g., a paraphenylenediamine) on photographic color development to form a dye, and are non-diffusible in photographic silver halide emulsions.
  • Typical useful color for-mers include phenolic, S-pyrazolone, and open chain ketomethylene compounds, such as those described and referred to in US. Patents 2,322,027 and 2,801,171.
  • Typical useful couplers producing cyan images which can be used herein are described by Graham et al. US. Patent 3,046,129 issued July 24, 1962 at 001$. 15 and 16.
  • Typical couplers producing magenta images which can be used in this invention are described by Graham et al., supra, col. l1.
  • Couplers typical of those which can be used in this invention to produce yellow images are described by Graham et al., supra, Cols. 17 and 18.
  • Such color formers can be dispersed in any suitable coupler solvent such as one of those described in many of the following US. patents: 2,304,939; 2,322,027; 2,801,170; 2,801,171 and 2,949,360.
  • the photographic silver halide emulsions utilized in the processes hereof are preferably spectrally sensitized first with a dye of the type described herein, and then photographic color former is added to the emulsion.
  • spectral sensitizer and then color former are not essential to the practice of this invention.
  • the present invention is practiced by coating spectrally sensitized photographic silver halide emulsions containing color former onto a hydrophobic surface which has been subjected to corona discharge.
  • hydrophobic is used herein in its normal sense as inclusive of substances which do not absorb or adsorb water.
  • Typical hydroprobic surfaceswhich are advantageously electron bombarded includes any hydrophobic materials which can be electron bombarded to improve adhesion, such as continuous hydrophobic films (which may or may not be self supporting) that have an ionizable hydrogen or hydroxyl group.
  • Specific supports having hydrophobic surfaces that can be utilized in the practice of this invention include electron bombarded poly(ethylene terephthalate) films, such as those electron bombarded to have a contact angle less than 45, by the process described in Carroll et al. US. Patent 3,220,842, issued Nov. 30, 1965 (which disclosure is incorporated herein by reference); electron bombarded surfaces comprising a chromium halide complex, such as sterato chromic chloride, for example those which are electron bombarded by the process described by Crawford et al. US. Patent 3,117,865 issued Jan.
  • hydrophobic surfaces which can be electron bombarded for use in the present invention, using processes and apparatus similar to that described in the literature referred to herein, include poly-u-olefins, preferably derived from olefins having from 2 to 10 carbon atoms; polyamides; polyacetals, polycarbonates; and, cellulose esters and ethers such as cellulose triacetate, cellulose acetate butyrate, ethyl cellulose, etc.
  • the preferred hydrophobic surfaces utilized in the practice of this invention are polyolefins, polyethylene and polypropylene being especially useful.
  • the support can be composed exclusively of polyolefin. That is, self supporting polyolefin films can be electron bombarded and coated substantially immediately after electron bombardment with spectrally sensitized photographic silver halide emulsions containing color former, in accordance With this invention.
  • the invention can also be practiced when the polyolefin surface is a permanent support for the photographic emulsion, the polyolefin support being removably adhered to a suitable temporary support to form a stripping film of the type described by Goffe et al. U.S. Patent 3,359,107, issued Dec. 19', 1967.
  • Other polyolefin coated supports can also be utilized, such as polyethylene or polypropylene coated paper supports.
  • the polyolefin surface can be electron bombarded by any convenient method, such as that by Alsup and Venor in British Patents 971,058 and 1,060,526. As noted in those patents, any suitable corona discharge or electron bombardment apparatus can be employed, such as the apparatus disclosed in U.S. Patents 2,864,755 and 2,864,- 756.
  • the surface is polyethylene
  • a contact angle of less than about 54 is desirable when the polyolefin utilized is polypropylene.
  • the method for obtaining and determining the contact angle of the corona discharge treated surface is described by Alsup and Venor in British Patent 971,058
  • This invention is practiced by coating spectrally sensitized emulsions containing color former onto a hydrophobic surface substantially immediately after the hydrophobic surface has been subjected to corona discharge treatment.
  • substantially immediately after corona discharge treatment refers to a period within about 30 minutes, and is advantageously within a few seconds (from less than one second up to about 30 seconds) after the corona discharge treatment.
  • a web having a hydrophobic surface is continuously passed by a first station where the hydrophobic surface is electron bombarded, and then to a second station where a spectrally sensitized emulsion containing color-former is coated onto the electron bombarded hydrophobic surface. Utilizing such techniques, the interval between electron bombardment and coating the emulsion is generally less than a few seconds, and can be a fraction of a second, depending upon the speed selected for operation.
  • This invention may be satisfactorily utilized when a spectrally sensitized emulsion containing color former is coated as a single layer upon a support of the type described herein, or when a plurality of emulsion coatings are applied to such support.
  • a plurality of coatings are applied to the support, suitable multiple coating techniques of the type heretofore utilized in photographic processes can be employed.
  • multiple emulsion coatings are applied over a corona discharge treated hydrophobic surface, the most serious problems of mottle appear in the two emulsion layers closest the hydrophobic surface. The problem of mottle has generally not been too severe with emulsions coated further from the support than two emulsion layers.
  • the present invention is especially well suited to the preparation of multicolor photographic elements having light sensitive layers of the general type described in Knott et al. Belgian Patent 641,414, issued Jan. 16, 1964, and corresponding U.S. Patent No. 3,434,837 issued Mar. 25, 1969.
  • a support having a hydrophobic surface such as a polyethylene or polypropylene coated paper support
  • a blue sensitive photographic silver halide emulsion layer containing a yellow coupler an optional interlayer comprising a hydrophilic colloid such as gelatin
  • a green sensitive photographic silver halide emulsion layer containing a magenta coupler an optional hydrophillic colloid layer such as gelatin
  • a red sensitive photographic silver halide emulsion layer containing a cyan coupler When such photographic silver halide emulsions are coated on an electron bombarded hydrophobic surface, mottle is most severe in the magenta dye image produced by green sensitive silver halide emulsion layer.
  • the blue sensitive layer contains a spectral sensitizer other than one of the type described herein, mottle is severe in the yellow dye image.
  • the cyan dye image formed by the red sensitive layer does not appear to be seriously susceptible to mottle.
  • the red sensitive emulsion layer is coated adjacent the polyolefin surface, with the green and blue sensitive emulsion layers thereover, the most serious mottle appears in the cyan and magenta dye images produced by the spectrally sensitized red and green sensitive emulsions.
  • mottle is used herein as a word of art which describes a defect occurring when a light sensitive silver halide emulsion layer containing color former is subjected to an overall even exposure, color developed to provide a dye image, and the dye image, which should have even dye density throughout, instead exhibits finger or lightning marks which are areas having distinctly higher dye density than that of the remaining areas of the dye image.
  • the areas having the higher dye density exhibit greater density than would be expected or predicted from the photographic speed of the particular system.
  • Mottle is also frequently accompanied by a lower speed than would be predicted in areas outside the finger or lightning marks. Frequently, the speed loss is about .1 Log E over that which would be predicted from the results obtained with a mottle free element corresponding to the test element.
  • EXAMPLE 1 A photographic silver bromoiodide emulsion is spectrally sensitized with 149 mg. per mole of silver of the dye anhydro-5-chloro-9-ethyl-5 -phenyl-3 3-sulfobutyl) 3-(3-sulfopropyl)oxacarbocyanine hydroxide, sodium salt.
  • a coupler is added to form a magenta image, the coupler being a pyrazolone coupler of the type described in Loria et al. U.S.
  • Patent 2,600,788, dated June 17, 1952 e.g., 3- ⁇ 3 2",4"-di-tert-amylphenoxy) acetamido benzoamido ⁇ - 1-(2,4,6-trichlorophenyl)-5-pyrazolone
  • a suitable coupler solvent such as dibutyl phthalate.
  • a polyethylene coated paper support is electron bombarded with a corona discharge by the process described in Alsup and Venor British Patent 971,058, the polyethylene surface passing the corona discharge station at the rate of about 500 feet per minute.
  • the polyethylene has a contact angle of less than 76.
  • the spectrally sensitized silver chlorobromide gelatin emulsion containing magenta coupler is coated onto the support, at a concentration of about mg. silver per square foot, about mg. gelatin per square foot and about 65 mg. coupler per square foot.
  • the emulsion passes the coater at the same rate it is passing by the corona discharge apparatus.
  • the coated sample is chill set, dried and processed exactly as described in Col. 5, line 40 through Col. 6, line 44 of Van Campen U.S. Patent 2,956,879.
  • the coating is then exposed to green radiation, i.e., radiation of about 500-600 nm.
  • the dye image is free from mottle.
  • Example 2 The procedure of Example 1 is duplicated except that the emulsion is spectrally sensitized with 162 mg. per mole of silver of the dye anhydro-9-ethyl-5,5'-diphenyl- 3,3-di(3-sulfobutyl)-oxacarbocyanine hydroxide, monosodium salt. The sample obtained is tested exactly as described in Example 1. The magenta dye image is free from mottle.
  • Example 3 The procedure of Example 1 is duplicated except that the emulsion is spectrally sensitized with 157 mg. per mole of silver of the dye anhydro-5,5-dichloro-9-ethy1- 3,3'-di(3-sulfopropyl)-oxacarbocyanine hydroxide, monosodium salt. The sample obtained is tested exactly as described in Example 1. The magenta dye image is free from mottle.
  • Example 4 The procedure of Example 1 is duplicated except that the emulsion is spectrally sensitized With 156 mg. per mole of silver of the dye anhydr-5,5,6,6-tetrachloro-1,1-diethyl 3,3 di(3 sulfobutyl)benzimidazolocarbocyanine hydroxide. The sample obtained is tested exactly as described in Example 1. The magenta dye image is free from mottle.
  • Example 5 The procedure of Example 1 is duplicated except that the emulsion is spectrally sensitized with 137 mg. per mole of silver of the dye anhydro-5,5,6,6-tetrachloro-1,1',3- triethyl 3' (3 sulfobutyl) benzimidazolocarbocyanine hydroxide. The sample obtained is tested exactly as described in Example 1. The magenta dye image is free from mottle.
  • Example 6 The procedure of Example 1 is duplicated except that the emulsion is spectrally sensitized with 114 mg. per mole of silver of the dye anhydro-5,6-dichloro-1,3'-diethyl-3-(3- sulfopropyl) benzimidazolooxacarbocyanine hydroxide. The sample obtained is tested exactly as described in Example 1. The magenta dye image is free from mottle.
  • Example 7 The procedure of Example 1 is duplicated except that the emulsion is spectrally sensitized with 149 mg. per mole of silver of the dye 5-(3-ethyl-2-benzothiazolinylidene)- 3-,8-sulfoethylrhodanine. The sample obtained is tested exactly as described in Example 1. The magenta dye image is free from mottle.
  • EXAMPLES 814 The procedures of Examples 1-7 are repeated except that the dispersion of pyrazolone coupler is replaced with about 50 mg. per square foot of a cyan forming coupler, e.g., coupler number 1 of Fierke et al. US. Patent 2,801,- 171 (Col. 2) in a conventional coupler solvent such as tri-ocresyl phosphate.
  • the emulsion is coated at about 65 mg. silver per square foot, 50 mg. cyan coupler per square foot and 110 mg. gelatin per square foot.
  • the results obtained in Examples 8-14 are essentially the same as those of Examples 1-7; i.e., the cyan dye images are free from mottle.
  • EXAMPLES l5-21 The procedure of Examples 1-7 is repeated except that the pyrazolone coupler dispersion is replaced with a yellow image dye-forming coupler, e.g., coupler No. l of McCrossen et al., US. Pat. 2,875,057, issued Feb. 24, 1959, dispersed in dibutyl phthalate, and the emulsion is coated at about 70 mg. square foot silver, mg. per square foot gelatin and 50 mg. per square foot coupler.
  • the yellow dye images obtained are free from mottle. Similar results are obtained when the polyethylene coated support is replaced with polypropylene coated paper, the polypropylene being electron bombarded to provide a contact angle of less than about 54 as described by Alsup and Venor in British Pat.
  • Examples 22-28 illustate the severe mottle which occurs when basic dyes, various acid-substituted cyanine and merocyanine dyes are used instead of the sulfo-substituted spectral sensitizing methine dyes utilized in the process of this invention.
  • EXAMPLE 22 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with 31 mg. per mole of silver of the dye 3,3-di(/3-hydroxethyl)thiadicarbocyanine bromide. Severe mottle is readily apparent in the magenta dye image.
  • EXAMPLE 23 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with 139 mg. per mole of silver of the dye 5-[(3-ethyl-2(3H)-naphth[2,1joxazolyidene)ethylidene]-3-n-heptyl-1-phenyl-2 thiohydantoin. Severe mottle is readily apparent in the magenta dye magenta dye image.
  • EXAMPLE 24 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with mg. per mole of silver of the dye 3,3',9-triethyl-5,5-diphenyloxacarbocyanine bromide. Severe mottle is readily apparent in the magneta dye image.
  • EXAMPLE 25 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with 145 mg. per mole of silver of the dye 9-ethyl-3,3-di( ⁇ 8-methoxyethyl)-5,5- diphenyloxacarbocyanine iodide. Severe mottle is readily apparent in the magenta dye image.
  • EXAMPLE 26 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with 131 mg. per mole of silver of the dye anhydro-3,3-di-(fl-carboxyethyl)-9-ethyl-5,5' diphenyloxacarbocyanine hydroxide. Severe mottle is readily apparent in the magenta dye image.
  • EXAMPLE 27 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with 135 mg. per mole 1 l of silver of the dye 3-ethyl-5-[(3-methyl-2-(3H)-thiazolinylidene -ethylidene] -2-thio-2,4-oxazolidinedione. Severe mottle is readily apparent in the magenta dye image.
  • EXAMPLE 28 The procedure of Example 1 is repeated except that the emulsion is spectrally sensitized with 135 mg. per mole of silver of the dye 3-carboxymethyl-5-[(3-methyl-2 (3H) thiazolinylidene isopropylidene] rhodanine. Severe mottle is readily apparent in the magenta dye image.
  • Example 29 illustrates the practice of this invention with overlying blue, green and red sensitive silver halide layers containing, respectively, yellow, magenta and cyan color former.
  • EXAMPLE 29 A polyethylene coated paper support is electron bombarded to provide a contact angle of less than 75 on the polyethylene surface. Substantially immediately after the electron bombardment, i.e., within seconds after the elec tron bombardment, blue, green and red sensitive silver halide emulsion layers containing, respectively, yellow, magenta, and cyan color formers are simultaneously coated, from a multiple coating hopper, onto the electron bombarded polyolefin surface, the blue sensitive layer containing yellow color former being closest to the electron bombarded polyethylene surface with the green sensitive layer containing magenta coupler over the blue sensitive layer and the red sensitive layer containing cyan color former overlying the green sensitive layer and being furthest from the polyethylene surface.
  • the blue sensitive layer does not contain a spectral sensitizing dye.
  • the yel low image formingcoupler is coupler No. l of McCrossen et al. U.S. Pat. 2,875,057, issued Feb. 24, 1959, dispersed in dibutyl phthalate and coated at a concentration of 115 mg. per square foot gelatin, 70 mg. per square foot silver and 50 mg. per square foot coupler.
  • the green sensitive silver halide emulsion layer is spectrally sensitized with 149 mg.
  • the green sensitive emulsion layer has dispersed therein pyrazole coupler No. 7 of Fierke et al. U.S. Pat. 2,801,171 (Col. 2), dissolved in coupler solvent, such as tri-o-cresyl phosphate.
  • coupler solvent such as tri-o-cresyl phosphate.
  • the green sensitive layer is coated at the rate of 165 mg. per square foot gelatin, 95 mg. per square foot silver and 65 mg. per square foot coupler.
  • the red sensitive layer is spectrally sensitized with a conventional sensitizer, such as anhydro-3,3'-di(,8 sulfoethyl)thiadicarbocyanine hydroxide at a concentration of about 130 mg. sensitizing dye per mole of silver.
  • the red sensitive layer contains a dispersion of coupler No. 1 of Fierke et al. U.S. Pat. 2,801,171 (Col. 2) in a coupler solvent, such as tri-o-cresyl phosphate.
  • the red sensitive emulsion layer is coated at the rate of 110 mg. per square foot gelatin, 65 mg. per square foot silver, 50 mg. per square foot cyan coupler.
  • the element is given a color sensitometric exposure and processed as described in Van Campen U.S. Pat. 2,956,879, Col. 5, line 40 through Col. 6, line 44.
  • the yellow, magenta and cyan dye images obtained are free from mottle. No speed loss is observed when the speed of each of the emulsion layers is compared to an element having the same emulsion layers but coated on a baryta coated paper which is not electron bombarded. Similar results are obtained when the polyethylene coated support is replaced with polypropylene coated paper, the polypropylene being electron bombarded to provide a contact angle of less than about 54 as described by Alsup and Venor in British Pat.
  • Example 29 is repeated except that the blue sensitive silver halide emulsion layer is spectrally sensitized with about 140 mg. per mole of silver of the dye 5-(3-ethyl-2- benzothiazolinylidene)-3-fl-sulfoethylrhodanine.
  • the dye images obtained, including the yellow dye image are free from mottle.
  • this example is repeated but using the dye 3-carboxymethyl-5-(3-ethyl-2(3H)-benzothiazolylidene)rhodanine as the sole spectral sensitizing dye in the blue sensitive emulsion layer, the yellow dye image obtained exhibits objectionable mottle.
  • Example 29 is repeated except that the green sensitive emulsion layer is spectrally sensitized with about mg. per mole of silver of dye anhydro-3,3di(,8-carboxyethyl) 9-ethyl-5,5'-diphenyloxacarbocyanine hydroxide, severe mottle appears in the magenta dye image.
  • the green sensitive emulsion exhibits an undesirable speed loss of .09 when compared to the speed of the same emulsion containing the same spectral'sensitizer and coupler but using a baryta coated paper support which is not electron bombarded.
  • the sensitizing dyes can be incorporated in the washed, finished silver halide emulsion and should, of course, be uniformly distributed throughout the emulsion.
  • the methods of incorporating dyes and other addenda in emulsions are relatively simple and well known to those skilled in the art of emulsion making. For example, it is convenient to add them from solutions in appropriate solvents, in which case the solvent selected should be completely free from any deleterious effect on the ultimate light-sensitive materials. Methanol, isopropanol, pyridine, water, etc., alone or in admixtures, have proven satisfactory as solvents for this purpose.
  • the type of silver halide emulsions that can be sensitized in the process of this invention include any of those prepared with hydrophilic colloids that are known to be satisfactory for dispersing silver halides, for example, emulsions comprising natural materials such as gelatin, albumin, agaragar, gum arabic, alginic acid, etc. and hydrophilic synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers partially hydrolyzed cellulose acetate, and the like. Any suitable silver halide can be used, such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, etc.
  • the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized 'vinyl compounds.
  • dispersed polymerized 'vinyl compounds are disclosed, for example, in U.S. Patents 3,142,568; 3,193,386; 3,062,674 and 3,220,844 and include the water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
  • the sulfo-substituted methine dyes can be used in any suitable concentration in the practice of this invention. Good results are obtained, for example, with from about 50 to 200 mg. dye per mole of silver. However, optimum concentrations vary widely, depending on the particular dye and emulsion used.
  • Certain dyes of this invention are especially useful since they are free from any speed loss when coated on a polyolefin surface after it has been electron bombarded.
  • Such preferred dye species include N,N-disulfoalkyl substituted oxacarbocyanine dyes (i.e., the dyes contain two benzoxazole nuclei joined, at the respective Z-carbon atoms thereof, by a methine linkage, and the hetero nitrogen atom of each benzoxazole nucleus has a sulfoalkyl group attached thereto) and unsymmetrical benzimidazole oxacarbocyanine dyes wherein at least one of the nitrogen atoms in one of the heterocyclic rings of the cyanine dye (i.e., the nitrogen atom of either the benzoxazole ring, the benzimidazole ring, or both of those nitrogen atoms) contains a sulfoalkyl group.
  • Specific preferred dyes which result in emulsion
  • the method for preparing a light sensitive photographic element which provides dye images substantially free from mottle which comprises:
  • hydrophobic surface is selected from the group consisting of a poly-a-olefin, a polyester, a polyamide, a polyacetal, a polycarbonate, cellulose ester, cellulose ether and hardened gelatin.
  • Z represents non-metallic atoms to complete a heterocyclic nucleus of the type used in cyanine dyes
  • R represents a member selected from the group consisting of an alkyl group and an aryl group
  • Q represents the non-metallic atoms required to complete a 5 to 6 membered sulfo-substituted heterocyclic nucleus of the type used in merocyanine dyes, at least one of Q, Z and R containing a sulfo group
  • L and L each represents a methine group
  • a represents an integer of from 1 to 2
  • m represents an integer of from 1 to 3.
  • Q of said formula represents the atoms required to complete a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, three of said atoms being carbon, 1 of said atoms being nitrogen and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, a nitrogen atom included within the meaning of said Q containing a substituent selected from the group consisting of a sulfoalkyl group and a sulfoaryl group.
  • hydrophobic surface is selected from the group consisting of a poly-a-olefin, a polyester, a polyamide, a polyacetal, a polycarbonate, cellulose ester, cellulose ether and hardened gelatin.
  • hydrophobic surface is selected from the group consisting of a poly-a-olefin, a polyester, a polyamide, a polyacetal, a polycarbonate, cellulose ester, cellulose ether and hardened gelatin.
  • the method for preparing a light sensitive photographic element which comprises:

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713828A (en) * 1969-09-05 1973-01-30 Fuji Photo Film Co Ltd Multi-layer color photographic silver halide light-sensitive materials
US3930860A (en) * 1972-12-29 1976-01-06 Fuji Photo Film Co., Ltd. Spectrally sensitized color photographic materials suitable for high temperature rapid development
US5380644A (en) * 1993-08-10 1995-01-10 Minnesota Mining And Manufacturing Company Additive for the reduction of mottle in photothermographic and thermographic elements
US5532121A (en) * 1995-03-24 1996-07-02 Minnesota Mining And Manufacturing Company Mottle reducing agent for photothermographic and thermographic elements
EP0749038A1 (en) 1995-06-16 1996-12-18 Minnesota Mining And Manufacturing Company Light-sensitive photographic materials comprising tabular silver halide grains and azodicarbonamide derivatives
EP0843209A1 (en) 1996-11-13 1998-05-20 Imation Corp. Silver halide emulsion manufacturing method
US6689547B2 (en) 2001-12-05 2004-02-10 Eastman Kodak Company Thermally developable imaging materials with improved image uniformity
US6730461B2 (en) 2001-10-26 2004-05-04 Eastman Kodak Company Thermally developable imaging materials with reduced mottle providing improved image uniformity

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4969363B2 (ja) 2006-08-07 2012-07-04 東レ株式会社 プリプレグおよび炭素繊維強化複合材料
CN104508022B (zh) 2012-07-25 2016-03-16 东丽株式会社 预浸料坯及碳纤维增强复合材料

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713828A (en) * 1969-09-05 1973-01-30 Fuji Photo Film Co Ltd Multi-layer color photographic silver halide light-sensitive materials
US3930860A (en) * 1972-12-29 1976-01-06 Fuji Photo Film Co., Ltd. Spectrally sensitized color photographic materials suitable for high temperature rapid development
US5380644A (en) * 1993-08-10 1995-01-10 Minnesota Mining And Manufacturing Company Additive for the reduction of mottle in photothermographic and thermographic elements
US5532121A (en) * 1995-03-24 1996-07-02 Minnesota Mining And Manufacturing Company Mottle reducing agent for photothermographic and thermographic elements
EP0749038A1 (en) 1995-06-16 1996-12-18 Minnesota Mining And Manufacturing Company Light-sensitive photographic materials comprising tabular silver halide grains and azodicarbonamide derivatives
EP0843209A1 (en) 1996-11-13 1998-05-20 Imation Corp. Silver halide emulsion manufacturing method
US6730461B2 (en) 2001-10-26 2004-05-04 Eastman Kodak Company Thermally developable imaging materials with reduced mottle providing improved image uniformity
US20040146813A1 (en) * 2001-10-26 2004-07-29 Hunt Bryan V. Thermally developable imaging materials with reduced mottle providing improved image uniformity
US6689547B2 (en) 2001-12-05 2004-02-10 Eastman Kodak Company Thermally developable imaging materials with improved image uniformity

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