US3615432A - Energy-sensitive systems - Google Patents

Energy-sensitive systems Download PDF

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US3615432A
US3615432A US766307A US3615432DA US3615432A US 3615432 A US3615432 A US 3615432A US 766307 A US766307 A US 766307A US 3615432D A US3615432D A US 3615432DA US 3615432 A US3615432 A US 3615432A
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image
compound
formula
nucleus
forming
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Philip W Jenkins
Donald W Heseltine
John D Mee
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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
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/09—Sensitisors or activators, e.g. dyestuffs
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • 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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • 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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >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
    • 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
    • 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
    • C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser 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
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
    • G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings

Definitions

  • This invention relates to a novel class of organic compounds and to novel photographic elements, compositions and processes using these compounds.
  • Dyes are also used to sensitize silver halide emulsions which produce direct positive images.
  • Emulsions of this type may contain an electron acceptor and silver halide grains that have been fogged with a combination of a reducing agent and a compound of a metal more electropositive than silver.
  • One of theadvantages of such direct positive emulsions is that the highlight areas of the images obtained with these materials are substantially free from fog.
  • known materials of this type have not exhibited the high speed required for many applications of photography. Also, such known materials have not shown the desired selective sensitivity, especially to radiation in the green to red region of the spectrum.
  • bleachable dyes can be used as photosensitive materials. Generally, these dyes are bleached in proportion to the exposure and direct positive images are attainable. Color direct positives are produced by an appropriate mixture of photobleachable cyan, magenta and yellow dyes. The loss of color usually proceeds at a relatively slow rate and even the use of sensitizers does not speed up the process enough tomake it commercially attractive. I
  • Dyes are also useful in thermographic systems. Recording elements frequently are impregnated with dyes which change color when subjected to localized heating.
  • the heat necessary to cause the dye to react can be provided either by direct contact, such as hot stylus, or by exposure of a differentially radia-.- tion-absorptive graphic original to intense radiant energy while in contact with a dye-containing heat-sensitive element;
  • the heat pattern established at the irradiated original causes a.- corresponding visible pattern to appear in the heat-sensitive layer, without deterioration of the original.
  • a convenientf source of radiation for thermographic reproduction is a tungsten filament lamp.
  • thermographic materials which have been previously described are only slightly sensitive to visible light, and, consequently, prolonged exposures are necessary in order to produce acceptable copies. It is obvious that such materials have only limited use, and, in certain instances, cannot be used at ts. as mmsrsia bas s.
  • Still another use of dyes in sensitive photographic elements is in layers for the reduction of halation or filtration of certain undesirable rays from the exposing radiation, either upon direct exposure or for reexposure in a photographic reversalprocess.
  • Antihalation layers can be coated as backing layers on either side of a transparent support carrying the light-sensitive composition.
  • Light-filtering layers can be coated over the light-sensitive layers or between such layers in multilayer elements.
  • the dyes used for such layers must have the desired spectral absorption characteristics. They should be easily incorporated in a water-permeable hydrophilic colloidal layer and yet firmly held in the layer so that they do not diffuse from it either during the manufacture of the element or on storing it.
  • Another object of this invention is to provide novel imageforming compositions and elements containing these compounds.
  • Another object is to provide novel photographic elements containing negative silver halide emulsions sensitized with these compounds.
  • Another object is to provide novel direct positive silver halide emulsions containing these compounds and a color former.
  • An object of this invention is also to provide heat-sensitive elements containing these novel compounds.
  • Another object is to provide novel photobleachable elements.
  • Another object is to provide novel nonsilver direct positive dye-bleach photographic elements capable of producing full color photographic prints.
  • an object is to provide photographic elements having novel antihalation layers.
  • R can be any of the following:
  • an aryl radical including a substituted aryl radical such as a phenyl radical, a naphthyl radical, a tolyl radical, etc.;
  • a hydrogen atom e. an acyl radical having the formula wherein R is hydrogen or analk yl group piferslsi 'iiivfii'ib 8 carbon atoms;
  • an anilinovinyl radical such as a radical having the formula R3 wherein R is hyd or g. a styryl radical including substituted styryl radicals, e.
  • R is hydrogen, alkyl, aryl, amino including dialkylamino such as dimethylamino;
  • R can be either of the following: v
  • a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes, e.g., those set forth in Mees and James (cited above); the methine linkage can be substituted or unsubstituted; or
  • an allylidene radical including a substituted allyidene radical such as a cyanoallylidene radical, an alkylcarboxyallylidene radical or an alkylsulfonylallyliclene radical;
  • R can be either:
  • an alkyl radical preferably having 1 to 8 carbon atoms such as methyl, propyl, ethyl, butyl, etc., including a substituted alkyl radical such as sulfoalkyl, e.g., (CH S an aralkyl, e.g., benzyl or pyridinato-oxalkyl salt, e.g., (Cl-l -O-Y wherein Y is a substituted or unsubstituted pyridinium salt;
  • R is an alkyl radical preferably having 1 to 8 carbon atoms or aryl radical, e.g., methyl, ethyl, propyl, butyl, phenyl, naphthyl, etc.;
  • an aryl radical including a substituted aryl radical e.g., 40
  • Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus including a substituted heterocyclic nucleus which nucleus can contain at least one additional hetero atom such as oxygen, sulfur, selenium or- 45 nitrogen, e.g., a pyridine nucleus, an indole nucleus, a quin-- oline nucleus, etc.; and
  • X represents an acid anion, e.g., chloride, bromide, iodide, perchlorate, sulfamate, thiocyanate, p-toluenesulfonate, methyl sulfate, tetrafluoroborate, etc.
  • These compounds are very versatile and can function in several different manners when used in photographic elements. They can be used as sensitizers in both direct positive and negative silver halide emulsions; they are heat bleachable and thus useful in thermographic recording elements; they are photobleachable and can be used for producing direct positives merely by coating them on a substrate; they make excellent antihalation layers and filter layers since they can be removed without the use of special baths simply by subjecting them to light for a sufficient period of time; and, when a mixture of a cyan, a magenta and a yellow dye having the above formula are coated on a support and exposed to a colored transparency, a direct color positive is obtained as a result of photobleaching. They are also useful in preparing holographic elements.
  • the compounds of this invention are chemically altered when subjected to various forms of energy such as (l) electromagnetic radiation including ultraviolet, visible and infrared light, X-rays, electron beams, laser beams, etc., (2) heat derived from various sources such as infrared radiation, (3) energy produced by mechanical means such as that produced by the local application of pressure, (4) sound waves, etc. 7
  • energy such as (l) electromagnetic radiation including ultraviolet, visible and infrared light, X-rays, electron beams, laser beams, etc.
  • heat derived from various sources such as infrared radiation
  • energy produced by mechanical means such as that produced by the local application of pressure, (4) sound waves, etc. 7
  • the pursuant alteration is generally a fragmentation of the compound molecule. It is the resultant components of the fragmentation which may be used in the formation of images.
  • the particular route of the fragmentation reaction is 5 somewhat dependent upon the structure of the original compound. However, based upon observations, it is believed that the route followed when a dye of this invention (such as the one given below) is exposed to a form ofenergy (such as light) is the following:
  • fragments are useful as initiators for other reactions such as polymerization and cross-linking as described in our copending application Ser. No. 766,304 titled 1Photopolymerization and our copending application Ser. -No. 766,280 titled Crosslinkable Polymer Compositions lfiled concurrently herewith.
  • the original color of the dye appears when it is treated with acid so that the pH of the material is below 7, but no further photobleaching results when the dye is exposed to energy.
  • Each of the fragments produced can be used in various processes, e.g., the aldehyde is an effective cross-linking agent as described in the aforementioned application, or as a dye mordant.
  • the free radicals and cations are useful as polymerization initiators as described in the aforementioned application.
  • the ether layer is decanted, the viscous residue dissolved in CH0 methanol (25 ml.) and 60 percent HCIO (1.0 ml.) in MeOH l5 (5 ml.) added. The mixture is chilled and the solid collected and washed with methanol. After recrystallization from a mixture of methanol and acetonitrile, the yield of purified dye is N 1.20 43 crcent m. .266 C.
  • the new class of cyanine dyes of the invention includes: those comprising first and second 5- to 6-membered nitrogen containing heterocyclic nuclei joined by a methine linkage; the first of these nuclei being a l-alkoxy-Z-arylindole nucleus joined at the 3-carbon atgmthereof to the linkage; and the second nucleus being a desensitizing nucleus joined at a carbon atom thereof to the linkage, to complete the cyanine dye.
  • the methine linkage preferably contains from 2 to 3 carbon atoms in the chain, i.e.. a dimethine linkage, or a trimethine linkage which may also contain at least one side chain group.
  • novel cyanine dyes of the invention include those defined by the following formulas:
  • Q represents the atoms necessary to complete an indole nucleus
  • E and J are aryl radicals, e.g., phenyl, naphthyl, tolyl, chlorophenyl, etc.;
  • R is an alkyl group, including substituted alkyl (preferably a lower alkyl containing from 1 to 4 carbon atoms), e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl, etc., and substituted alkyl groups (preferably a substituted lower alkyl containing from 1 to 4 carbon atoms);
  • substituted alkyl preferably a lower alkyl containing from 1 to 4 carbon atoms
  • Typical representative dyes particularly suited for this portion of the invention include compounds 21-24, 28-31 and 40-43 described above.
  • the cyanine dyes of the invention defined above are powerful electron acceptors for direct positive photographic silver halide emulsions. In addition, they are also useful desensitizers in emulsions used in the process described in Stewart and Reeves, US. Pat. No. 3,250,618, issued May 10, 1966.
  • desensitizing nucleus refers to those nuclei which, when converted to a symmetrical carbocyanine dye and added to gelatin silver chlorobromide emulsion containing 40 mole percent chloride and 60 mole percent bromide, at a concentration of from 0.01 to 0.2 gram of dye per mole of silver, cause (by electron trapping) at least about an percent loss in the blue speed of the emulsion when sensitometrically exposed and developed three minutes in Kodak developer D-l 9 at room temperature.
  • the desensitizing nuclei are those which, when converted to a symmetrical carbocyanine dye and tested as just described essentially completely desensitize the test emulsion to blue radiation (i.e., cause more than about to percent loss of speed to blue radiation).
  • novel and improved direct positive photographic silver halide emulsions are prepared by incorporating one or more of the cyanine dyes described above into a suitable fogged silver halide emulsion.
  • the emulsion can be fogged in any suitable manner, such as by light or with chemical fogging agents, e.g., stannous chloride, formaldehyde, thiourea dioxide, and the like.
  • the emulsion may be fogged by the addition thereto of a reducing agent, such as thiourea dioxide, and a compound of a metal more electropositive than silver, such as a gold salt, for example, potassium chloroaurate, as described in British Pat. No.
  • emulsions which may be used are solarizing silver halide emulsions. These emulsions are silver halide emulsions which have been effectively fogged either chemically or by radiation, to a point which corresponds approximately to the maximum density of the reversal curve as shown by Mees, The Theory of the Photographic Process, published by MacMillan Co., New York, New York, 1942, pages 261-297.
  • Conventional silver halide developing solutions can be used to develop a direct positive image in solarizing emulsions.
  • the concentration of added dye can vary widely, e.g., from about 50 to 2,000 mg. and preferably from about 400 to 800 mg. per mole of silver halide in the direct positive emulsions.
  • the compounds of this invention are also advantageously incorporated in direct positive emulsions of the type in which a silver halide grain has a water-insoluble silver salt center and an outer shell composed of a fogged water-insoluble silver salt that develops to silver without exposure.
  • the compounds of the invention are incorporated, preferably, in the outer shell ofsuch emulsions.
  • These emulsions can be prepared in various ways, such as those described in Berriman U.S. Pat. No. 3,367,778 issued Feb. 6, 1968.
  • These compounds are highly useful electron acceptors in high speed direct positive emulsions comprising fogged regular grain monodispersed silver halide grains and a compound which accepts electrons, as described and claimed in lllingsworth Belgian Pat. No. 695,366 ofSept. ll, 1967.
  • the silver halides employed in the preparation of the direct positive photographic emulsions useful herein include any of the photographic silver halides as exemplified by silver bromide, silver iodide, silver chloride, silver chlorobromide, silver bromoiodide, silver chlorobromide, and the like.
  • Silver halide grains having an average grain size less than about one micron, preferably less than about 0.5 micron, give particularly good results.
  • the silver halide grains can be regular and can by any suitable shape such as cubic or octahedral, as described and claimed in Illingsworth Belgian Pat. No. 695,366 of Sept. l l, l967. Such grains have a uniform diameter frequency distribution.
  • At least 95 percent, by weight, of the photographic silver halide grains can have a diameter which is within about 40 percent, preferably within about 30 percent of the mean grain diameter.
  • Mean grain diameter i.e., average grain size, can be determined using conventional methods, e.g., as shown in an article by Trivelli and Smith entitled Empirical Relations Between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series in The Photographic Journal, Vol. LXXIX, 1949, pages 330-338.
  • the compounds of the invention are advantageously incorporated in the washed, finished silver halide emulsion and should, of course, be uniformly distributed throughout the emulsion.
  • the methods of incorporating such compounds 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., along or in admixtures, have proven satisfactory as solvents for this purpose.
  • the type of silver halide emulsions that can be used with these compounds 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, agar-agar, gum arabic, alginic acid, etc., and hydrophilic synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, and the like.
  • the compounds of the invention can be used with emulsions prepared, as indicated above, with any of the light-sensitive silver halide salts including silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc.
  • Particularly useful are direct positive fogged emulsions in which the silver salt is a silver bromohalide comprising more than 50 mole percent bromide.
  • Certain compounds of this invention are also useful in emulsions which contain color formers.
  • novel emulsions of this invention may be coated on any suitable photographic support, such as glass, film base such as cellulose acetate, cellulose acetate butyrate, polyesters such as poly(ethylene terephthalate), polystyrene, paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which can be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
  • film base such as cellulose acetate, cellulose acetate butyrate
  • polyesters such as poly(ethylene terephthalate), polystyrene, paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which can be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
  • EXAMPLE 56 l,l-Dimethoxy-2,2-diphenyl-3,3indolocarbocyanine perchlorate is photographically tested for its usefulness as an electron acceptor and spectral sensitizer for fogged direct positive photographic silver halide emulsions by the following procedure.
  • a regular grain monodispersed silver bromoiodide gelatin emulsion (2.5 mole percent of the halide being iodide) and having an average grain size of about 0.2 micron is prepared by adding an aqueous solution of potassium bromide and potassium iodide, and an aqueous solution of silver nitrate, simultaneously to a rapidly agitated aqueous gelatin solution at a temperature of 70 C., over a period of about 35 minutes.
  • the emulsion is chill-set, shredded and washed by leaching with cold water in the conventional manner.
  • the emulsion is reduction-gold fogged by first adding 0.2 mg. of thiourea dioxide per mole of silver and heating for 60 minutes at 65 C. and then adding 4.0 mg.
  • N-melhyl-p-aminophenol sulfate 2.0 g. Sodium sulfite (anhydrous) 90.0 g. Hydroquinone 8.0 g. Sodium carbonate (monohydrule) 52.5 g. Potassium bromide 5.0 g. Water to make L0 liter then fixed, washed and dried. The results are listed in table lV hereinafter. Referring thereto, it will be seen that the dye of this example has a maximum density in the unexposed areas of 1.38 and a minimum density in exposed areas of 0.02, a maximum sensitivity at 650 nm.
  • EXAMPLE 57 Compound 22 is tested for reversal and sensitizing properties by the procedure described in above example 56. The results are recorded in table 1V hereinafter. Referring to the table, densities of 1.70 and 0.03 for the unexposed and exposed areas, respectively, a maximum sensitivity at 660 nm. and a relative speed of 3,800 are shown for this dye. Accordingly, the above prepared dye is an excellent electron acceptor and spectral sensitizer for fogged direct positive emulsions.
  • EXAMPLE 58 Compound 28 is tested for reversal and sensitizing properties by the procedure described in above example 56. The results are recorded in table IV hereinafter. Referring thereto, it will be noted that the densities are 1.46 and 0.06 for the unexposed and exposed areas, respectively, with a maximum sensitivity at 575 nm., and a relative speed of 3,020. These results indicate that this dye is an outstanding electron acceptor and spectral sensitizer for fogged direct positive emulsions.
  • EXAMPLE 59 To one mole of a silver chloride gelatin emulsion containing an equivalent of 100 grams of silver nitrate is added 0.029 gram of compound 21. The emulsion is coated on a nonglossy paper support, and is flashed with white light to give a density of 1.2 when developed in the following developer, diluted l part to 2 parts of water:
  • N-methyl-p-aminophenol sulfate 3.1 g. Sodium sulfite, des. 45 g. Hydroquinone 12 g. Sodium carbonate, des. 67.5 g. Potassium bromide 1.9 g. Water to 1 liter
  • the light fogged material thus obtained can be exposed to an image with light modulated by a Wratten No. 15 filter to give a direct positive image. Similar results are obtained when compounds 22, 28, 30,40 and 41 are substituted for the aforementioned compound of this example.
  • EXAMPLE 60 One mole of a silver chloride gelatin emulsion is heated to 40 C. and the pH is adjusted to 7.8. Fourteen ml. of (40 percent) formalin solution is then added and the emulsion is held at 40 C. for 10 minutes. At the end of the holding period, the pH is adjusted to 6.0 and 0.21 g. of compound 28 is incorporated therein. The emulsion is then coated on a support, and the element so obtained provides good direct positive images. Similar results are obtained when compounds 21, 22, 30, 40 and 41 are used in place ofthe dye of this example.
  • the photographic silver halide emulsion and other layers present in the photographic elements made according to the invention can be hardened with any suitable hardener, including aldehyde hardeners such as formaldehyde, and mucochloric acid, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy starch or oxy plant gums, and the like.
  • the emulsion layers can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including, for example, lubricating materials, stabilizers, speed increasing materials, absorbing dyes, plasticizers, and the like. These photographic emulsions can also contain in some cases additional spectral sensitizing dyes.
  • these emulsions can contain color forming couplers or can be developed in solutions containing couplers or other color generating materials.
  • useful color formers are the monomeric and polymeric color formers or couplers, e.g., S-pyrazolone, phenolic and open chain couplers having a reactive methylene group.
  • the color forming couplers can be incorporated into the direct positive photographic silver halide emulsion using any suitable technique, e.g., techniques of the type shown in .lelley et al. U.S. Pat. No. 2,322,027, issued June 15, 1943, Fierke et al. U.S. Pat. No. 2,801,171, issued July 30, 1957, Fisher U.S. Pat.
  • Silver halide emulsions containing the compounds of this invention can be dispersed in any of the binders disclosed and referred to in Beavers U.S. Pat. No. 3,039,873 issued June 19, 1962, col. 13, or polymerized vinyl compounds such as those disclosed in U.S. Pat. Nos. 3,142,568; 3,193,386; 3,062,674; and 3,220,844, and including the water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
  • cyanine dyes derived from l-alkoxypyridines and l-alkoxyquinolines are useful spectral sensitizers for negative-type photographic silver halide emulsions. They provide emulsions that are characterized by both good speed and desired sensitivity to radiation in the green to red region of the spectrum with maximum sensitivity occurring in most cases in the region of about 520-620 nm.
  • the images produced with these novel emulsions of the invention are clear and sharp, and of excellent contrast.
  • This new class of cyanine dyes includes those comprising a first and a second 5 to 6 membered nitrogen-containing heterocyclic nucleus joined by a methine linkage; the first of these nuclei being either a l-alkoxypyridyl nucleus or a l-alkoxyquinolyl nucleus, each of these nuclei being joined at the 2-carbon atom thereof to the linkage.
  • the second nucleus is a heterocyclic nucleus of the type commonly contained in cyanine dyes and is joined at a carbon atom to the above-mom tioned methine linkage, to complete the cyanine dye.
  • the methine linkage preferably contains one or three carbon atoms in the methine chain.
  • novel cyanine dyes of the invention include those defined by the following formula:
  • Q is either a pyridine nucleus or a quinoline nucleus
  • R is an alkyl group, including substituted alkyl (preferably a lower alkyl containing from one to four carbon atoms), e.g.,
  • decyl, benz yl, dodecyl, etc. an aryl group, efgi, phenyl, naphthyl, tolyl, chlorophenyl, etc.; or an acyl group, e.g., acetyl.
  • R L, R 0,, X, g and n have previously been defined.
  • Typical representative dye salts best suited for this. portion of the invention include compounds 1-20, 25 and. 27 of table I.
  • heterocyclic nucleus of the type commonly contained in cyanine dyes includes any of the following nuclei: the, thiazole series (e,g., thiazole, 4-methylthiazole, 5;- methylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4,5- dimethylthiazole, 4,5-diphenylthia2ole, 4-(2-thienyl)thiazole, etc. those of the benzothiazole series (e.g., benzothiazole, 4-
  • chlorobenzothiazole 5-chlorobenzothiazole. 6- chlorobenzothiazole, 7-chlorobenzothiazole, 4-methyl'-, benzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, o-iodobenzothiazole, 4- ethoxybenzothiazole, 5-ethoxybenzothiazole, a.
  • tetrahydrobenzothiazole nucleus 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.
  • those of the naphthothiazole series e.g., a-naphthothiazole (i.e., [2,l]-. naphthothiazole), fi-naphthothiazole, (i.e., l ,2]-
  • naphthothiazole 7-methoxy-wnaphthothiazole, 8-methoxy-anaphthothiazole, etc.
  • those of the thianaphtheno-7, 6, 4, 5,- thiazole series e.g., 4-methoxythianaphtheno-7', 6, 4, 5 thiazole, etc.
  • those of the oxazole series e.g., 4-methyloxazole, S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-eth,yloxazole, 4,5-dimethyloxazole, S-phenyloxazole, etc.
  • those of the benzoxazole series e.g., benzoxazole, 5- chlorobenzoxazole, S-phenylbenzoxazole, S-methylbenzoxazole, G-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6- dimethylbenz
  • those of the naphthoxazole series e.g., a-naphthoxazole, B-naphthoxazole, etc.
  • those of the selenazole series e.g., 4-methylselenazole, 4-phenylselenazole, etc.
  • those of the benzoselenazole series e.g., benzoselenazole, 5 chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-h-ydroxybenzoselenazole, a tetrahydrobenzoselenazole nucleus, etc.
  • those of the naphthoselenazole series e.g., a naphthoselenazole, B-naphthoselenazole. etc.
  • those of the thiazoline series e.g., thiazoline, 4-methylthiazoline, etc.
  • those of the 2-quinoline series e.g., quinoline, 3-methylquin,- oline, S-methylquinoline, 7-methylquinoline, 8-methylquinoline, o-chloroquinoline, S-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.
  • those of the 4-quinoline series e.g., quinoline, 6- methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.
  • Sensitization by means of these new dyes is particularly useful with the ordinarily employed negative speed, gelatinoil sa halide emi gt em ls ons-E y E iasvantageously incorporated in the emulsion and should be uniformly distributed throughout the emulsion.
  • the methods of incorporating dyes in the emulsion are simple and well known to those skilled in the art of emulsion making. It is convenient to add the dyes from solutions in appropriate solvents. The solvent should be compatible with the emulsion and substantially free from any deleterious effecton the light-sensitive materials.
  • the concentration of thedyes in the negative-type, developing-out emulsions can vary widely, i.e., from about 5 to about mgs. per liter of flowable emulsion.
  • the concentration of the dye will vary according to the type of light-sensitive material in the emulsion and according tovjthe effects desired.
  • the suitable and most economical concentration for any given emulsion willbe apparent to those skilled in the art upon making theordinary tests and observations customarily used in the art ofemulsion making.
  • gelatino-silver halide developing out emulsion sensitized with one of these dyes the following procedure is satisfactory: A quantity of the dye is dissolved" in methyl alcoholor other suitable solvent and a volume of this solution (which may be diluted with water) containing from 5 to I00 mgs. of dye is slowly added to about l,000 cc. of a gelatino-silver halide emulsion, with stirring. Stirring is continued until the dye is uniformly distributed throughout the emulsion, With most of the dyes, l0 to 20 mgs.
  • Photographic silver halide emulsions which can advantageously be sensitized by means of the new dyes of the invention comprise the customarily employed silver chloride, silver chlorobromide, gelatino-silver bromide, silver chlorobromoiodide and gelatino-silver bromoiodide negativespeed developing-out emulsions
  • Photographic silver halide emulsions such as those listed above, containingthe sensitizing dyes can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), selenium compounds, tellurium compounds, various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see US, Pat.
  • Dispersing agents for color couplers such as those set forth in U.S. Pat. Nos. 2,322,027 and 2,304,940, can also be employed in the above described emulsions.
  • EXAMPLE 61 in order to demonstrate the sensitization which these dyes impart, a negative-speed developing-out gelatino-silver bromoiodide emulsion containing 0.77 mole percent iodide of the type described by Trivelli and Smith, Phot. Journal, 79, 330 (1939) is prepared.
  • Various dyes are dissolved in suitable solvents and the solutions added to separate portions of the emulsion at concentrations set forth in the following table.
  • the emulsions After digestion at 52 C. for minutes, the emulsions are coated at a thickness of 432 mg. of silver per square foot on a cellulose acetate film support. A sample of each coating is exposed on an Eastman IB sensitometer to a wedge spectrograph, processed for 3 minutes in Kodak Developer D-l9, fixed in hypo, washed and dried.
  • the maximum sensitivity is set forth in the following table.
  • the dyes of the invention are useful in the production of direct positive photographic images by bleaching of such dyes. It has been found that the dyes of the invention are bleached in proportion to the exposure energy they receive. The bleaching results from the fragmentation of the dye molecule, fragmentation being caused, at least in part, by the cleavage of the N-O linkage. Thus, when the dyes are coated on or imbibed into a suitable support and exposed in an imagewise manner, direct positive reproductions are obtained.
  • the advantages of this process are numerous, e.g., no chemical development is necessary nor is there any need for any other material in the coating composition other than the dye itself. Since the dyes of the invention are of different colors, images having various colors can be made. For coating purposes, it is often convenient to disperse the dye in a film-forming binder.
  • Useful binders include those which are commonly used in preparing photographic elements.
  • R, R R R R L, 0,, Q,, X, G, n, g and m are each defined above.
  • Typical compounds exemplary of the above include compounds 1-13, 18, 26, 52 through 59.
  • bleachable dyes are of various colors, as explained previously, they can be used in the production of direct positive color prints.
  • a white substrate is coated with a layer of a yellow dye, a layer of a magenta dye and a layer of a cyan dye and the resultant element is exposed to while light through a color transparency, a direct positive color print is obtained.
  • the three dyes need not be present as separate layers but may be in a uniform admixture.
  • the color image is obtained by virtue of the fact that these dyes are bleached when exposed to a light source of substantially the same wavelength which they absorb. Since yellow absorbs blue, where light in the blue region strikes the yellow layer, the yellow layer bleaches and becomes colorless.
  • EXAMPLE 63 A solution of 46.1 mg. of compound 12 (magenta), 43,7 mg. of compound 10 (cyan) and 39.8 mg. of compound 4 (yellow) in 50 g. of 20 percent poly-(Z-vinylpyridine) binder is prepared by rotary mixing. After two hours mixing 1,46 g. of triethanolamine is added and the solution is mixed for an additional 2 hours. The solution is then coated on a white pigmented cellulose acetate base at a thickness of 0.002 in. After drying, the elements are exposed through a color positive transparency with a high intensity flash lamp. Instant color positives are obtained.
  • the dyes of the invention can be used to prepare thermographic copy elements.
  • the compounds of this invention fragment when subjected to various forms of energy. Accordingly, when these compounds are exposed to heat, fragmentation occurs. The compounds lose their original color and generally are bleached. Because of this feature, they can be used in thermographic copy sheets as the heat-sensitive material. Dyes of formula E are preferred.
  • the compounds forming the heat-sensitive areas of a copy sheet can be coated on or imbibed into any suitable support (especially supports having low thermal conductivity).
  • any suitable support especially supports having low thermal conductivity.
  • ordinary paper can be used as a support for the heatsensitive composition and the paper can be transparent, translucent or opaque. It is frequently desirable to use a support which transmits the exposing radiation, especially where the original does not transmit such radiation (i.e., at least one of these should transmit such radiation).
  • a paper or other fibrous material can be employed which has a charring temperature above about C.
  • the heat-sensitive dye is usually coated on a translucent or opaque support. After a period of drying, the heat-sensitive, copying sheet can then be placed in contact with an original containing line copy, such as typewritten characters, and exposed to infrared radiation.
  • an original containing line copy such as typewritten characters
  • infrared radiation The portions of the original which are highly absorptive of the infrared radiation convert the radiation to heat which is conducted to the copying material producing a rapid color change in those portions of the copying sheet which are in heat-conductive relationship with the original.
  • the portions of the copying sheet which are not in heat-conductive relationship with the original transmit or reflect the infrared radiation so that no color change occurs.
  • the heat-sensitive compounds of the invention can be dispersed in a binding material and the entire composition coated on the surface of the support.
  • Suitable binding agents include ethyl cellulose, polyvinyl alcohol, gelatin, collodion, polyvinyl acetal, cellulose esters, hydrolyzed cellulose esters, etc.
  • colloidal binding agent When a colloidal binding agent is employed, the amount thereof used can be varied in order to vary the contrast of the resulting copy.
  • Various esthetic effects may be produced by adding inert pigments or colorants to the colloidal dispersions, although there is generally no advantage to be gained by the use of such materials. in some instances, an apparent increase in contrast can be obtained by using a coloring pigment in the colloidal binding material.
  • the source of infrared radiation can be arranged so that the rear surface of the original receives the infrared radiation, although in such cases it may be convenient to have an insulating surface applied to the rear surface of the original in order to localize and intensify the heat received by the original.
  • the heat-sensitive layer of the copying material can be placed in contact with the printed characters of the original and the assembly then exposed either from the rear side of the original or the rear side of the copying sheet.
  • thermographic element can be accomplished by reflex (as explained above) or by bireflex techniques. According to the latter method, a support for such an exposure should be readily permeable to radiant energy, such as infrared radiation. Also, the support is advantageously relatively thin so that the heat generated in the printed characters of the original can be transmitted to the heat-sensitive layer thereby causing a color change to take place in a pattern corresponding to the printed characters. If desired, the support can be ordinary paper which has been transparentized temporarily, so that exposure can be made as described. The transparentizing substance can then be removed after exposure to provide an opaque reflecting support. Such transparentizing treatment is well known to those skilled in the art.
  • the application of the heat-sensitive layer to the support need not be done in a uniform manner, but that the heat-sensitive layer can be applied nonuniformly in a regular pattern, such as lines or dots.
  • Such coatings can be used for special purposes, such as in the graphic arts field.
  • the source of radiation is selected so that it is strongly absorbed by the characters or printed materials being reproduced.
  • the characters absorb the radiant energy and transform it into heat which is transmitted to the heat-sensitive coating.
  • Incandescent bodies can conveniently be employed as the source of radiant energy, since such incandescent material is generally rich in the radiant energy absorbed by many of the printing materials currently being used. Where the radiant energy is not transmitted by the support bearing the heat-sensitive material, the material being copied should transmit such radiant energy so that exposure can be made through the rear surface of the material bearing the printed characters.
  • EXAMPLE 64 A paper support is coated with a layer ofa composition containing gelatin and compound 12. A graphic original having printed material thereon is placed in contact with the uncoated surface of the paper. Upon exposure ofthe assembly to infrared radiation supplied by an infrared lamp, a facsimile copy of the printed characters of the original is obtained.
  • EXAMPLE 65 A composition containing compound 32 in gelatin is coated on an aluminum base. The element is written on with a hot stylus on the noncoated side. A good image is recorded in the heated areas.
  • the dyes described herein have been found to be useful in light-screening layers, including antihalation and filter layers, in photographic light-sensitive elements employing one or more sensitive silver halide layers. They can be incorporated readily in colloidal binders used for forming such layers or they can be coated without the aid of a vehicle. They are especially useful in gelatin layers adjacent to the silver halide layers and also in dry processes.
  • the dyes can be readily bleached without the need for removing the layers containing them, Bleaching of the dyes occurs when the layer containing them is subjected to some form of energy, e.g., light or heat. The energy causes the compound to fragment and become colorless, as explained previously.
  • These dye compounds can be mordanted in layers coated in contact with light-sensitive silver halide emulsion layers since the mordanted dyes have very good stability at the pH of most sensitive silver halide emulsions and have little or no undesirable effect on the silver halide.
  • the dyes can be used as light-screening dyes in layers coated directly on top of sensitive silver halide emulsion layers or between two sensitive silver halide emulsion layers or between the support and a sensitive silver halide emulsion layer or on the back of the support as an antihalation layer.
  • the elements in which these materials are used as screening layers can contain either the conventional developing-out silver halide emulsions or lightdevelopable silver halide emulsions such as those described in Ser. No. 481,918, filed Aug. 23, 1965, now U.S. Pat. No. 3,418,122 and Ser. No. 625,590, filed Mar. 24, 1967, now U.S. Pat. No. 3,447,927.
  • the light-screening layers of this invention are prepared by coating on the photographic element or on its support, by methods well known in the art, a solution of the dye, a hydrophilic colloid binder and a coating aid such as saponin. in addition to these materials, it is advantageous to add a mordant to this solution to render the dye nonwandering. For most purposes it is desirable to add agents to harden the colloidal binder material so that the light-screening layer will remain intact in the photographic element during and following the processing operation.
  • the pH of the coating solution is adjusted when necessary to a level that is compatible with the light-sensitive emulsion layer by the usual methods.
  • the proportions of the dye, colloidal binder, mordant, hardener, and coating aid used in making the light-screening layers can be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The methods used to determine the optimum composition are well known in the art and need not be described here.
  • the light-sensitive layer or layers and the light-screening layer or layers of the photographic element can be coated on any suitable support material used in photography such as cellulose nitrate, cellulose acetate, synthetic resins, paper, metal, ss t
  • Hydrophilic colloidal materials used as binders for lightscreening dyes of the invention include gelatin, collodion, gum arabic, cellulose ester derivatives such as alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, carboxymethyl hydroxyethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Pat. No. 2,949,442 issued Aug. 16, 1960, polyvinyl alcohol, and others well known in the art.
  • the above-mentioned amphoteric copolymers are made by polymerizing a monomer having the formula:
  • CII2 CR .QQQ wherein R represents an atom of hydrogen or a methyl group, and a salt ofa compound having the general formula:
  • R has the above-mentioned meaning, such as an allylamine salt.
  • These monomers can further be polymerized. with a third unsaturated monomer in an amount ofO to 20 per-. cent of the total monomer used, such as an ethylene monomer; that is copolymerizable with the two principal monomers.
  • the third monomer can contain neither a basic group nor an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc.
  • polymeric gelatin substitutes examples include copolymers of allylamine and methacrylic acid; copolymers of allylamide, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; copolymers of allylamine, acrylic acid and styrene; the copolymer of allylamide, methacrylic acid and acrylonitrile; etc.
  • the dye is generally added to the water-permeable colloidal binder in water solution.
  • it can be advantageous to form an alkali metal salt of the dye by dissolving the dye in a dilute aqueous alkali metal carbonate solution.
  • a coating aid such as saponin is added to the dye colloidal suspension before coating it as a layer on the photographic element.
  • the dye is advantageously mordanted with a suitable basic mordant added to the colloidal suspension before coating.
  • Mordants that can be used include the mordants described by Minsk in U.S. Pat. No. 2,882,156, issued Apr. 14, 1959, prepared by condensing a polyvinyl-oxo-compound such as a polyacrolein, a poly-'y-methylacrolein, a polyvinyl alkyl ketone such as polyvinyl methyl ketone, polyvinyl ethyl ketone, polyvinyl propyl ketone, polyvinyl butyl ketone, etc., or certain copolymers containing acrolein, methacrolein, or the above mentioned vinyl alkyl ketone components, for example, 1 to 1 molar ratio copolymers of these components with styrene or alkyl methacrylates wherein the alkyl group contains from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl methacrylates in the porportions from about
  • C-aminopyridines or alkyl group substituted C- aminopyridines such as 2-aminopyridine, 4-aminopyridine, the aminopicolines such as 2-amino-3-methylpyridine, 2- amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino- 6-methylpyridine and corresponding 4-aminomethyl derivatives which react in this reaction in exactly the same way, 2- amino-6-ethylpyridine, 2-amino-6-butylpyridine, 2-amino-6- amylpyridine, etc.; the various aminotoluidines such as, for example, 2-amino-3-ethyl-4-methylpyridine, etc.; the dialkylaminoalkyl esters of dialkylaminoalkylamides, e.g., such as those described by Carroll et al.
  • U.S. Pat. No. 2,675,316 isd W1 .3. fiia i by EFEEFFQE qq ttqu containing carboxyl groups with a basic dialkylamino compound, for example, N-dialkylamine ethyl esters of polymers or copolymers containing carboxyl groups; the addition type polymers containing periodically occurring quaternary groups of Sprague et al. U.S. Pat. No. 2,548,564, issued Apr.
  • Hardening materials that can be used to advantage in the described light-screening layer include such hardening agents as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Pat. No.
  • Photographic elements utilizing these novel light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material.
  • the silver halide emulsions may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.
  • the dyes of this invention are valuable for preparing lightfiltering layers for light-sensitive photographic elements containing silver halide emulsion layers.
  • the light-filtering layers containing these dyes are used to advantage, either over the light-sensitive silver halide emulsion layers, or between the light-sensitive silver halide emulsion layer and the support, between two different light-sensitive layers, or as an antihalation backing layer.
  • EXAMPLE 66 A solution containing compound 12 dissolved in a mixture of dimethylformamide and methyl alcohol is added to an aqueous gelatin solution. The mixture is agitated thoroughly to ensure complete and uniform mixing. The resultant solution is coated on a film support so that each square foot of support contains 300 mg. of gelatin and 240 mg. of dye. Superimposed on the thus formed filter layer is a conventional photographic silver halide emulsion layer. After drying, the element is exposed and developed by usual techniques. A sharp image is obtained with no discoloration due to residual dye in background areas. In this example, the dye was bleached by light energy absorbed during the exposure step. When this example is repeated without compound 12, a blurred and fuzzy image is obtained because of the lack of filter protection.
  • Example 6 6 i repeated except the dye employed is compound 3 and the silver halide emulsion used and photographic process employed is that used in stabilized print out systems such as described in example 18 of Ser. No. 625,590 filed Mar. 24, 1967, now U.S. Pat. 3,447,927, Bacon et al. Again, a good reproduction is obtained.
  • the bleaching in this example is caused by both light and heat energy.
  • the dyes of this invention are useful in the preparation of holographic elements.
  • the development of improved holograms has been carried out on a continuous basis since their introduction in 1948 by Prof. D. Gabor.
  • a typical system for laser holograms is described in Scientific American, Feb. I968, Vol. 2l8, No. 2, p. 43.
  • Holograms have in the past been recorded with silver halide emulsions.
  • the dyes described herein can be used in holographic elements to record holograms.
  • Holograms produced in this manner have the advantage of affording higher resolution than the silver halide-based systems since the active particles are of molecular size (i.e., I 35 A. for dye molecules vs. 500 A.
  • Another advantage is that no processing is required since the dyes are photobleachable (as explained previously) and the image is recorded directly. Therefore, dimensional stability is not a problem.
  • the replacement of silver halide with the dyes of this invention is also economically advantageous.
  • the holographic elements of this invention are prepared by mixing any of the dyes of this invention with a polymeric binder such as polymethacrylate, gelatin, poly(vinylalcohol), etc.
  • a polymeric binder such as polymethacrylate, gelatin, poly(vinylalcohol), etc.
  • the composition is coated on a support such as glass, Estar, cellulose acetate, Teflon, etc.
  • the thickness of the coating may be varied from a few microns upward.
  • EXAMPLE 68 A holographic element is prepared by mixing a solution of 0.00793 g. of compound 18 in methanol (14 g.) with 36 grams of 28 percent poly(2-vinylpyridine) in methanol for about 17 hours. The resulting solution is hand coated at room temperature on 5X7 inch glass spectroscopic plates using a knife setting of 0.030 in. The coating is covered and allowed to dry slowly at room temperature.
  • EXAMPLE 69 A holographic element is prepared in the same manner as example 68 except compound 1 l is used instead of compound 18.
  • EXAMPLE 70 The elements of examples 68 and 69 are used in the production of laser holograms.
  • the system employed is similar to that described in the Scientific American article (op. cit.).
  • a laser beam is divided by a beam splitter and directed by a combination of mirrors and lenses such that the reference beam impinges directly on the test coating while the other illuminates a ground glass object.
  • the object used is a 1 cm. square spot of illuminated ground glass placed close to the holographic element so that the reference beam and object beam illuminate an area approximately 1% inches square on the coating.
  • the exposure times range from l5 seconds with a 900 mw. laser.
  • Each of the coatings produce good recordings of holographic fringes.
  • An image-forming composition comprising an energysensitive compound having a formula selected from the group consisting of:
  • Q and 0 each represent the nonmetallic atoms necessary I to complete a 5- to 6-membered heterocyclic nucleus;
  • R is selected from the group consisting of:
  • R is selected from the group consisting of:
  • a an aryl radical, b. a hydrogen atom, and L is a methine linkage;
  • X is an acid anion;
  • g is a positive integer from I to 2;
  • n is a positive integer from 1 to 4; and
  • R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical.
  • 0, represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus, a quinoline nucleus and an indole nucleus.
  • An image-forming composition comprising an energysensitive compound having the formula:
  • Q and 0 each represent the nonmetallic atoms necessary to complete a 5- to 6-membered heterocyclic nucleus
  • R is selected from the group consisting of:
  • R is selected from the group consisting of:
  • L is a methine linkage
  • X is an acid anion
  • n is a positive integer from l to 4.
  • R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical
  • D and E are each selected from the group consisting of a hydrogen atom, an alkyl radical and an aryl radical.
  • Q represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus, a quinoline nucleus and an indole nucleus.
  • An image-forming composition comprising an energysensitive compound having the formula:
  • Q represents the atoms necessary to complete a 5- to 6- membered heterocyclic nucleus
  • R is selected'from the group consisting of a. an alkyl radical and b. an acyl radical; R is selected from the group consisting of:
  • L is a methine linkage
  • X is an acid anion
  • G is selected from the group consisting of an anilinovinyl radical and an aryl radical
  • n is a positive integer from l -3;
  • g is a positive integer from I -2.
  • Q represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus, a quinoline nucleus and an indole nucleus.
  • An image-forming composition comprising an energysensitive compound having the formula:
  • R is selected from the group consisting of:
  • R and J are each selected from the group consisting of:
  • R is selected from the group consisting of an alkyl radical.
  • L is a methine linkage
  • X is an acid anion
  • n is a positive integer from 1 to 3;
  • g is a positive integer from i to 2.
  • 0 represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus, a quinoline nucleus and an indole nucleus.
  • An image-forming element comprising a support and at least one layer of an energy-sensitive composition comprising a compound having a formula selected from the group consisting of:
  • R is selected from the group consisting of:
  • R is selected from the group consisting of:
  • R is selected from the group consisting of:
  • X is an acid anion
  • Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus, a quinoline nucleus and an indole nucleus.
  • R is a methine linkage terminated by a 5- to 6-membered heterocyclic nucleus.
  • An image-forming element comprising a support and at least one layer of an energy-sensitive com-position comprising a compound having a formula selected from the group consisting of:
  • R is an alkyleneoxy radical having l to 8 carbon atoms in the alkylene chain
  • g is a positive integer from 1 to 2;
  • X is an acid anion
  • L is a methine linkage
  • R is selected from the group consisting of an alkyl radical and an acyl radical
  • D, E. J, R and R are each selected from the group consisting of an aryl radical, a hydrogen atom and an alkyl radical;
  • R5 is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical;
  • G is selected from the group consisting of an anilinovinyl radical and an aryl radical
  • R and R are each a cyano radical.
  • composition comprises a compound having the formula:
  • R, R R Q1, Q2, L. X, g and n are as previously defined.
  • R, R R 0:, Q;,, L, D, E, X and n are as previously defined.
  • composition comprises a compound having the wherein R, R 0,, L, G, X, r n a nd g are as previously defined.
  • composition comprises a compound having the formula:
  • R, R R 0 and X are as previously defined.
  • R R Q Q X and R are as previously defined.
  • R, R Q 0,, L, g, and m are as previously defined.
  • a light-sensitive element comprising a support containing a photobleachable dye having a formula selected from the group consisting of wherein:
  • R is selected from the group consisting of an alkyl radical and an acyl radical; L is a methine linkage; G is selected from the group consisting of an anilino-vinyl radical and a phenyl radical; m is a positive integer from 1 to 3; X is an acid anion; Q, and Q each represent the atoms necessary to complete a 5- to 6 -membered heterocyclic nucleus; R is selected from the group consisting of an aryl radical, a
  • n is a positive integer from 1 to 4
  • R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical
  • g is a positive integer from 1 to 2. 25.
  • a light-sensitive element comprising a support having coated thereon a composition comprising gelatin and 3'-ethyll-methoxy-4 ,5 '-benzo-2-pyridothiacarbocyanine perchlorate.
  • a photographic element for producing positive color images from color originals comprising a support having coated thereon an energy-sensitive composition comprising:
  • said dyes having the for- Q represents the atoms necessary to complete a to 6- membered heterocyclic nucleus
  • R is selected from the group consisting of:
  • R is selected from the group consisting of:
  • L is a methine linkage
  • X is an acid anion
  • g is a positive integer from 1 to 2;
  • n is a positive integer from l to 4.
  • Q represents the nonmetallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring;
  • R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical.
  • a light-sensitive element for producing positive color images from color originals comprising a support having coated thereon a composition comprising a. 3-ethyll -methoxy-4',5 "benzo-Z-pyridothiacarbocyanine perchlorate;
  • a process for forming an image which comprises exposing an energy-sensitive element in an imagewise manner to electromagnetic energy, said element comprising a support having coated thereon a layer of a composition comprising a compound having a formula selected from the group consisting of:
  • R is selected form the group consisting of a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, an alkyl radical, an anilino vinyl radical, a hydrogen atom, an aryl radical, an aldehyde group, a styryl radical;
  • R is selected from the group consisting of:
  • R is selected from the group consisting of an alkyl radical and an acyl radical
  • X is an acid anion
  • Z represents the atoms necessary to complete a 5- to 6- membered heterocyclic nucleus.
  • Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus, a quinoline nucleus and an indole nucleus.
  • R is a methine linkage terminated by a 5 to fi-membered heterocyclic nucleus.
  • a process for forming an image which comprises exposing an energy-sensitive element in an imagewise manner to electromagnetic energy, said element comprising a support having coated thereon a layer of a composition comprising a compound having a formula selected from the group consisting of:
  • R is selected from the group consisting of an alkyl radical ..
  • R is selected from the group consisting of: Q; dl l a. an aryl radical,
  • L is a methine linkage; wherein R, R 0:, L, G, X, m and g are as previously defined. g is a positive integer from 1 to 2; and
  • R is selected from the group consisting of:
  • g is a positive integer from I to 2;
  • R4 R4 m is a positive integer from 1 to 3;
  • R and R are each a cyano radical. 46.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Indole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770451A (en) * 1968-10-09 1973-11-06 Eastman Kodak Co Silver halide emulsions sensitized with dyes containing heterocyclic nitrogen atoms substituted with an -or group
US4197080A (en) * 1979-02-14 1980-04-08 Eastman Kodak Company Radiation-cleavable nondiffusible compounds and photographic elements and processes employing them
US4410618A (en) * 1982-06-11 1983-10-18 Eastman Kodak Company Blocked photographic reagents
EP0210660A2 (en) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Image forming process
US5773170A (en) * 1995-04-20 1998-06-30 Minnesota Mining And Manufacturing Co. UV-absorbing media bleachable by IR-radiation
US6207359B1 (en) 2000-02-22 2001-03-27 Eastman Kodak Company Method for reducing the dye stain in photographic elements
US6376163B1 (en) 2000-02-22 2002-04-23 Eastman Kodak Company Photobleachable composition, photographic element containing the composition and photobleachable method
US20050032009A1 (en) * 2003-08-04 2005-02-10 Eastman Kodak Company Thermal base precursors
US20110088924A1 (en) * 2009-10-16 2011-04-21 Michael Nashner Sub-surface marking of product housings
US20130075126A1 (en) * 2011-09-27 2013-03-28 Michael S. Nashner Laser Bleached Marking of Dyed Anodization
US9173336B2 (en) 2009-05-19 2015-10-27 Apple Inc. Techniques for marking product housings
US9185835B2 (en) 2008-06-08 2015-11-10 Apple Inc. Techniques for marking product housings
US9280183B2 (en) 2011-04-01 2016-03-08 Apple Inc. Advanced techniques for bonding metal to plastic
US9314871B2 (en) 2013-06-18 2016-04-19 Apple Inc. Method for laser engraved reflective surface structures
US9434197B2 (en) 2013-06-18 2016-09-06 Apple Inc. Laser engraved reflective surface structures
US9849650B2 (en) 2009-08-25 2017-12-26 Apple Inc. Techniques for marking a substrate using a physical vapor deposition material
US9962788B2 (en) 2009-10-16 2018-05-08 Apple Inc. Sub-surface marking of product housings
US10071583B2 (en) 2009-10-16 2018-09-11 Apple Inc. Marking of product housings
US10071584B2 (en) 2012-07-09 2018-09-11 Apple Inc. Process for creating sub-surface marking on plastic parts
US10220602B2 (en) 2011-03-29 2019-03-05 Apple Inc. Marking of fabric carrying case for a portable electronic device
US12324114B2 (en) 2021-09-24 2025-06-03 Apple Inc. Laser-marked electronic device housings

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5138994U (en(2012)) * 1974-09-14 1976-03-23
JPS525012A (en) * 1975-06-28 1977-01-14 Kubota Ltd Pipe joint
JPS5253093U (en(2012)) * 1975-10-13 1977-04-15
JPH0184698U (en(2012)) * 1987-11-27 1989-06-06
DE3833987A1 (de) * 1988-10-06 1990-04-12 Hans A Urban Verfahren zum herstellen einer dauerwellenfluessigkeit sowie zum wellen von haaren unter verwendung dieser dauerwellenfluessigkeit
DE8812988U1 (de) * 1988-10-15 1988-12-22 Ahsmann, Dieter, 4520 Melle Schrank
DE69027717T2 (de) * 1989-08-11 1996-11-28 Fuji Photo Film Co Ltd Licht- und wärmeempfindliches Aufzeichnungsmaterial
JP2520763B2 (ja) * 1990-04-20 1996-07-31 富士写真フイルム株式会社 水溶性メチン化合物および該化合物を含むハロゲン化銀写真乳剤
DE202012104055U1 (de) 2012-10-22 2012-11-13 Fluoron Gmbh Spritze zur Injektion eines chirurgischen Gases

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770451A (en) * 1968-10-09 1973-11-06 Eastman Kodak Co Silver halide emulsions sensitized with dyes containing heterocyclic nitrogen atoms substituted with an -or group
US4197080A (en) * 1979-02-14 1980-04-08 Eastman Kodak Company Radiation-cleavable nondiffusible compounds and photographic elements and processes employing them
US4410618A (en) * 1982-06-11 1983-10-18 Eastman Kodak Company Blocked photographic reagents
EP0210660A2 (en) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Image forming process
US5773170A (en) * 1995-04-20 1998-06-30 Minnesota Mining And Manufacturing Co. UV-absorbing media bleachable by IR-radiation
US6207359B1 (en) 2000-02-22 2001-03-27 Eastman Kodak Company Method for reducing the dye stain in photographic elements
US6376163B1 (en) 2000-02-22 2002-04-23 Eastman Kodak Company Photobleachable composition, photographic element containing the composition and photobleachable method
US6436624B2 (en) 2000-02-22 2002-08-20 Eastman Kodak Company Method for reducing the dye stain in photographic elements
US20050032009A1 (en) * 2003-08-04 2005-02-10 Eastman Kodak Company Thermal base precursors
WO2005043238A1 (en) * 2003-08-04 2005-05-12 Eastman Kodak Company Thermal base precursors
US9185835B2 (en) 2008-06-08 2015-11-10 Apple Inc. Techniques for marking product housings
US9173336B2 (en) 2009-05-19 2015-10-27 Apple Inc. Techniques for marking product housings
US10773494B2 (en) 2009-08-25 2020-09-15 Apple Inc. Techniques for marking a substrate using a physical vapor deposition material
US9849650B2 (en) 2009-08-25 2017-12-26 Apple Inc. Techniques for marking a substrate using a physical vapor deposition material
US20110088924A1 (en) * 2009-10-16 2011-04-21 Michael Nashner Sub-surface marking of product housings
US9845546B2 (en) 2009-10-16 2017-12-19 Apple Inc. Sub-surface marking of product housings
US9962788B2 (en) 2009-10-16 2018-05-08 Apple Inc. Sub-surface marking of product housings
US10071583B2 (en) 2009-10-16 2018-09-11 Apple Inc. Marking of product housings
US10220602B2 (en) 2011-03-29 2019-03-05 Apple Inc. Marking of fabric carrying case for a portable electronic device
US9280183B2 (en) 2011-04-01 2016-03-08 Apple Inc. Advanced techniques for bonding metal to plastic
US20130075126A1 (en) * 2011-09-27 2013-03-28 Michael S. Nashner Laser Bleached Marking of Dyed Anodization
US10071584B2 (en) 2012-07-09 2018-09-11 Apple Inc. Process for creating sub-surface marking on plastic parts
US11597226B2 (en) 2012-07-09 2023-03-07 Apple Inc. Process for creating sub-surface marking on plastic parts
US9434197B2 (en) 2013-06-18 2016-09-06 Apple Inc. Laser engraved reflective surface structures
US9314871B2 (en) 2013-06-18 2016-04-19 Apple Inc. Method for laser engraved reflective surface structures
US12324114B2 (en) 2021-09-24 2025-06-03 Apple Inc. Laser-marked electronic device housings

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CH517317A (fr) 1971-12-31
FR2020245A1 (en(2012)) 1970-07-10
FR2020247A1 (en(2012)) 1970-07-10
JPS505584B1 (en(2012)) 1975-03-05
BR6913047D0 (pt) 1973-01-25
DE1950779A1 (de) 1970-05-14
FR2020244A1 (en(2012)) 1970-07-10
DE1950726A1 (de) 1970-05-14
BE740042A (en(2012)) 1970-03-16
GB1281565A (en) 1972-07-12
BE738225A (fr) 1970-03-02
CH530027A (fr) 1972-10-31
GB1276129A (en) 1972-06-01
FR2020246A1 (en(2012)) 1970-07-10
BE738228A (en(2012)) 1970-03-02
DE1950766A1 (de) 1970-04-16
FR2022244A1 (en(2012)) 1970-07-31
BE740044A (en(2012)) 1970-03-16
BR6913050D0 (pt) 1973-06-07
GB1281567A (en) 1972-07-12
DE1950766B2 (de) 1971-03-18
DE1950735A1 (de) 1970-04-23
GB1281566A (en) 1972-07-12
CH506096A (fr) 1971-04-15
JPS4910691B1 (en(2012)) 1974-03-12
BR6913046D0 (pt) 1973-01-25
BR6913051D0 (pt) 1973-05-10
BE738230A (en(2012)) 1970-03-02
BE738226A (en(2012)) 1970-03-02
JPS4931127B1 (en(2012)) 1974-08-19
DE1950746A1 (de) 1970-04-09
BE738229A (en(2012)) 1970-03-02
BE738227A (fr) 1970-03-02
DE1950757A1 (de) 1970-05-14
BE740041A (fr) 1970-03-16
BE740043A (en(2012)) 1970-03-16
JPS4930131B1 (en(2012)) 1974-08-10
DE1950726C3 (de) 1982-02-04
DE1950726B2 (de) 1981-05-07
BR6913048D0 (pt) 1973-01-25
FR2020243A1 (en(2012)) 1970-07-10
BR6913049D0 (pt) 1973-01-25

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