US3928686A - Heat-sensitive recording materials - Google Patents

Heat-sensitive recording materials Download PDF

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Publication number
US3928686A
US3928686A US335670A US33567073A US3928686A US 3928686 A US3928686 A US 3928686A US 335670 A US335670 A US 335670A US 33567073 A US33567073 A US 33567073A US 3928686 A US3928686 A US 3928686A
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US
United States
Prior art keywords
silver
compound
recording
heat
silver compound
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Expired - Lifetime
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US335670A
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English (en)
Inventor
Albert Lucien Poot
Frans Clement Heugebaert
Wilhelmus Janssens
Antoon Leon Vandenberghe
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Agfa Gevaert NV
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Agfa Gevaert NV
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Publication date
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Publication of USB335670I5 publication Critical patent/USB335670I5/en
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Publication of US3928686A publication Critical patent/US3928686A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/10—Aza-phenanthrenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the recording system of the present invention is based on the use of an organic compound that is capable of reducing a noble metal salt as a fatty acid silver salt by the action of heat.
  • Heat-sensitive copy-sheets capable of undergoing a colour change by the thermally initiated reduction of a silver compound with an organic reducing compound are known from the United Kingdom Patent Specification No. 866,076.
  • Image-forming reactants disclosed in said specification are silver behenate and 2,3-dihydroxybenzoic acid.
  • a heat-sensitive copy-sheet containing said compounds is suited for the thermographic copying of originals containing infrared-absorbing image markings.
  • the infrared-absorbing image portions of the original are selectively heated and by heat transfer cause the development in the adjacent heat-sensitive sheet of a silver image corresponding with the image markings of the original.
  • a photo-thermographic process is described in the United Kingdom Patent Specification No. 1,110,046.
  • a photosensitive and heat-developable recording material is applied, which contains:
  • a catalytic amount of photolytically reducible silver halide being formed from the silver salt and being in catalytic proximity of the silver salt.
  • Said process comprises the exposure to a light-image of said recording material and the heating of the exposed material in order to cause reduction of the silver salt and image-formation at the light-exposed areas.
  • an organic reducing compound contained in a photosensitive copy sheet is first rendered inactive and non-transferable by heat through an informationwise exposure in the presence of a compound that helps in the deactivation of the reducing compound.
  • the reducing compound left in the unexposed or less exposed portions is transferred by heat to a receptor sheet on which it causes color formation.
  • This latter system has the advantage that the final copy is not heat-sensitive and cannot obtain a background coloration anymore, as the reactivity or transferability of the reducing compound has been destroyed information-wise by the photo-exposure.
  • the present invention provides a process for recording information in which an organic reducing compound under the influence of heat is allowed to effect an information-wise reduction of a reaction partner in order to form an information-wise detectable change.
  • R represents a C -C alkyl group, for example methyl, ethyl, propyl or butyl, preferably methyl, and
  • Z represents the necessary atoms to close an adjacent aromatic nucleus, e.g., a benzene nucleus or an adjacent aromatic ring system including a substituted aromatic nucleus or aromatic ring system.
  • Suitable substituents are, e.g., an alkyl group including a substituted alkyl group for example methyl, a halogen atom (F, Cl, Br or I), an alkoxy group, e.g., methoxy, a substituted alkoxy group, e.g., a hydroxy-substituted ethoxy group, an amino group, a substituted amino group, e.g., a monoalkylamino or dialkylamino group or cyano.
  • the adjacent aromatic ring system closed by the atoms represented by Z is preferably one of the following unsubstituted or substituted nuclei represented by their structural formula:
  • R represents hydrogen or an alkyl group
  • R represents hydrogen or an alkyl group
  • the residue was dissolved in methylene chloamino compound, in which the primary amino group is 5 id d h d i subsequent order: present on an aromatic nucleus, with an aliphatic ke- 3 times with 5N aqueous hydrochloric acid tone containing at least one methyl group linked di- 3 times with aqueous 30 Sodium hydroxide Sohb rectly to the carbonyl group of the ketone in a pretion ferred molar ratio of at least 1:2 in the presence of a 3 times with t suitable catalyst, such as toluenesulfonic acid, benzene- W3 sulfonic acid, sulfuric acid, iodine or bromine.
  • suitable catalyst such as toluenesulfonic acid, benzene- W3 sulfonic acid, sulfuric acid, iodine or bromine.
  • the methylene Chlonde Solutwn was n on y- Examples of suitable ketones are acetone, methyl drous sodfum sulphate and the splvent duvet ⁇ ethyl ketone, methyl iso ro l k t d th l b l
  • the residue was purified by boiling it three times with ketone. active carbon and a small amount of a petroleum frac-
  • the production of said organic reducing agents is tion boiling between 80-120C.
  • reaction mass was distilled under reduced pressure and the fraction with boiling point 105C at about 0.5 mm Hg was collected.
  • the organic reducing compound is used in a layer or sheet in conjunction with a reaction partner that on heating produces a visible colour change by reduction.
  • a reaction partner that on heating produces a visible colour change by reduction.
  • noble metal compounds that through an oxidation-reduction reaction are capable of separating free metal.
  • Preferred noble metal compounds are silver compounds, which under the conditions encountered in thermographic copying, i.e., preferably in a temperature range of 50 to 200C are poorly light-sensitive, e.g., the silver salts of aliphatic carboxylic acids with a thioether group such as described e.g. in the United Kingdom Patent Specification No. 1,111,492 filed Aug. 13, 1965 by Agfa AG, or silver salts of long chained aliphatic (at least C carboxylic acids such as silver behenate, silver palmitate, silver stearate and others.
  • Silver behenate and silver stearate are preferred salts.
  • the use of silver behenate or silver stearate in combination with free behenic acid and free stearic acid respectively increases the moisture-resistant properties of the recording composition.
  • R represents a saturated or unsaturated aliphatic group or an alkoxy group, preferably having from 1 to 6 carbon atoms, a cycloalkyl group or cycloalkoxy group, e.g., cyclopentyl or cyclohexyl.
  • auxiliary reducing agents sterically hindered phenols that on heating become reactive partners in the reduction reaction, e.g., 2,4,6-tri-tert.butylphenol and- /or 2,6-dicyclohexyl-p-cresol may be used.
  • the reducing agents described in the present invention may be advantageously used in conjunction with a substantially non-light-sensitive silver salt of an organic acid from which a catalytic amount of photolytically reducible silver halide has been formed as described in the United Kingdom Patent Specification No. 1,1 10,047. They may be likewise used in the recording materials containing a higher aliphatic acid silver salt and spectral sensitizing agent described in the German Patent application No. P 2140462.
  • the reactants are preferably applied to a thin flexible carrier or backing such as paper, e.g., glassine paper or baryta-coated paper, or transparent film, e.g., consisting of a cellulose ester or polyethylene terephthalate, in admixture with a film-forming polymeric or resinous binder.
  • a thin flexible carrier or backing such as paper, e.g., glassine paper or baryta-coated paper, or transparent film, e.g., consisting of a cellulose ester or polyethylene terephthalate, in admixture with a film-forming polymeric or resinous binder.
  • the binder can yield a self-supporting sheet or tape when it has a sufficient mechanical strength.
  • the reactants may be supported in a fibrous web in the absence of a binder.
  • Pigments e.g., zinc oxide or titanium dioxide, fillers, meltable substances, e.g., waxes, dyes and various other additives may be included for obtaining special effects aimed at.
  • the reducible compound such as the noble metal salt and the reducing agent are preferably intermixed prior to coating, but may be applied in separate but contiguous layers if desired from which the reducing agent can diffuse to the noble metal salt, e.g., during the heating of the recording material.
  • binder agent for the reducing compound and the compound thermally reducible therewith all kinds of natural, modified natural or synthetic resins can be used, e.g., proteins such as gelatin, cellulose derivatives, e.g., a cellulose ether such as ethylcellulose, cellulose esters, carboxymethylcellulose, alginic acid and derivatives, starch ethers, galactomannan, polyvinyl alcohol, poly-N-vinylpyrrolidone, polymers derived from a,B-ethylenically unsaturated compounds, e.g., vinylhomoand copolymers such as polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, partially saponified polyvinyl acetate, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters or polyethylene.
  • proteins such as gelatin, cellulose derivatives, e.g., a cellulose ether such as eth
  • Heat-sensitive copying materials of the present invention may be used in any process in which heat is information-wise applied to or generated in the copying material, e.g., by means of hot bodies for example a hot stylus or by means of heat producing radiation.
  • Heat-sensitive sheet-like copying materials of the present invention are particularly suited for the thermographic copying of originals containing infraredabsorbing image markings.
  • the infrared-absorbing image portions of the original are selectively heated and by heat transfer cause the formation in the adjacent heat-sensitive sheet of a visible color-change resulting from the reaction of the organic reducing agent with a suitable reaction partner of an oxidation-reduction reaction, e.g., a noble metal salt.
  • the copying material is heated information-wise or image-wise by radiation absorbed in the copying material.
  • the copying material in heatconductive relationship with the oxidation-reduction partner(s) contains a certain amount of a substance or substances that are capable of converting absorbed electromagnetic radiation energy into heat. Suitable substances for that purpose are, e. g., heavy metal particles and finely divided carbon.
  • Heat-sensitive copying materials of the present invention containing said noble metal salts are suitable 'for making direct, high contrast, clear detail, black permanent copies of typewritten, printed and other graphic subject matter.
  • the copying materials are stable at room and normal storage temperatures, and may be stored in daylight without visible change either before or after heat-copying when no light-sensitive silver halide is present in their composition.
  • ethyl acet ate stearic acid "polymethyl" hethacrylate (the viscosity of a 5 76 solution in p l rqipm at. 2 is -9 .SPf-EE cellulose acetate butyrate (substitution degree of acetate and butyrate 0.5 and 2.4 respectively the viscosity of a 20 solution in zinc oxide (average grain size ais q slsilver stearate mm m Before coating the following ingredients were added to the ball-milled composition:
  • Example 1 was repeated with the compounds 6 and 7 of Table I and the same results as described in Example 1 were obtained with the thus modified recording materials.
  • a recording process comprising the step of applying a heat pattern corresponding to an image to a recording material containing a silver compound that is generally non-light sensitive at a temperature below about 200C and is adapted to undergo chemical reduction to release silver metal, while said silver compound is in reactive contact with an organic reducing compound corresponding to the following general formula:
  • R represents a C -C, alkyl group
  • Z represents the necessary atoms to close a benzene, naphthalene, anthracene, carbazole, indole, benzo furan, dibenzofuran, phenothiazine, tluorene, indene, xanthene, or quinolin-2-one nucleus,
  • said silver compound is reduced in the heated regions of said material to silver metal and forms a visible image of said pattern.
  • a recording process according to claim 2 wherein said heat pattern is formed by exposing said recording material to infrared while said layer is in heat-conductive contact with an original to be reproduced carrying infrared-absorbing image-markings.
  • a recording process according to claim 1 wherein said heat pattern is formed by exposing said material to imagewise modulated electromagnetic radiation, which is absorbed in said material and converted therein into heat.
  • R represents a C -C alkyl group
  • Z represents the necessary atoms to close a benzene, naphthalene, anthracene, carbazole, indole, benzo furan, dibenzofuran, phenothiazine, fluorene, indene, xanthene, or quinolin-2 -one nucleus
  • a sheet material according to claim 9, wherein the silver compound is a silver salt of an aliphatic carboxylic acid containing a thioether group.
  • a sheet material according to claim 9, wherein the silver compound is a silver salt of an aliphatic carboxylic acid containing at least 14 carbon atoms.
  • a sheet material according to claim 12, wherein the silver compound is silver behenate or silver stearate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Quinoline Compounds (AREA)
  • Indole Compounds (AREA)
US335670A 1972-02-28 1973-02-26 Heat-sensitive recording materials Expired - Lifetime US3928686A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB914172A GB1413288A (en) 1972-02-28 1972-02-28 Heat-sensitive recording materials

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USB335670I5 USB335670I5 (enrdf_load_stackoverflow) 1975-01-28
US3928686A true US3928686A (en) 1975-12-23

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BE (1) BE795696A (enrdf_load_stackoverflow)
DE (1) DE2308766A1 (enrdf_load_stackoverflow)
GB (1) GB1413288A (enrdf_load_stackoverflow)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4243668A (en) * 1979-07-09 1981-01-06 E. I. Du Pont De Nemours And Company Octahydro-1H-benzo[4,5]furo[3,2-e]-isoquinoline analgesic and narcotic antagonistic compounds
US4260761A (en) * 1978-10-02 1981-04-07 E. I. Du Pont De Nemours And Company Intermediates for the preparation of octahydro-1H-benzo[4,5]furo[3,2,-e]-isoquinoline analgesic and narcotic antagonistic compounds
US4839332A (en) * 1987-01-16 1989-06-13 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US5409798A (en) * 1991-08-30 1995-04-25 Canon Kabushiki Kaisha Plate blank, process for producing printing plate from plate blank, and printing method and apparatus using plate
US5599648A (en) * 1990-08-03 1997-02-04 Canon Kabushiki Kaisha Surface reforming method, process for production of printing plate, printing plate and printing process
US5688810A (en) * 1994-12-22 1997-11-18 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US6462038B1 (en) 1999-08-27 2002-10-08 Ligand Pharmaceuticals, Inc. Androgen receptor modulator compounds and methods
EP1180722A3 (en) * 2000-08-15 2003-01-02 Eastman Kodak Company Photothermographic materials providing improved image stability and methods of use
US6534516B1 (en) 1996-06-27 2003-03-18 Ligand Pharmaceuticals Incorporated Androgen receptor modulator compounds and methods
US6566372B1 (en) 1999-08-27 2003-05-20 Ligand Pharmaceuticals Incorporated Bicyclic androgen and progesterone receptor modulator compounds and methods
US6593493B1 (en) 1999-09-14 2003-07-15 Ligand Pharmaceuticals, Inc. RXR modulators with improved pharmacologic profile
US6667313B1 (en) 1999-08-27 2003-12-23 Ligand Pharmaceuticals Inc. 8-substituted-6-triflouromethyl-9-pyrido [3,2-G] quinoline compounds as androgen receptor modulators
US6696459B1 (en) 1994-12-22 2004-02-24 Ligand Pharmaceuticals Inc. Steroid receptor modulator compounds and methods
US20060128740A1 (en) * 2001-02-23 2006-06-15 Lin Zhi Tricyclic androgen receptor modulator compounds and methods
US20070066650A1 (en) * 2003-08-22 2007-03-22 Lin Zhi 6-Cycloamino-2-quinolinone derivatives as androgen receptor modulator compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1590678A (en) 1976-08-18 1981-06-03 Canon Kk Image-forming member
JPS5334515A (en) * 1976-09-10 1978-03-31 Canon Inc Thermodevelopable photosensitive material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074809A (en) * 1959-10-26 1963-01-22 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3094417A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Heat sensitive copy sheet, process of making and using
US3446648A (en) * 1965-09-27 1969-05-27 Minnesota Mining & Mfg Reactive copying sheet and method of using
US3666477A (en) * 1970-06-03 1972-05-30 Eastman Kodak Co Element,composition and process
US3667959A (en) * 1970-05-01 1972-06-06 Eastman Kodak Co Photosensitive and thermosensitive element,compositions and process
US3679426A (en) * 1970-04-09 1972-07-25 Eastman Kodak Co Photosensitive and thermosensitive elements,compositions and processes
US3707377A (en) * 1971-02-02 1972-12-26 Minnesota Mining & Mfg Photothermic dry silver coatings stabilized with halogen-containing organic oxidizing agents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3074809A (en) * 1959-10-26 1963-01-22 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3094417A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Heat sensitive copy sheet, process of making and using
US3446648A (en) * 1965-09-27 1969-05-27 Minnesota Mining & Mfg Reactive copying sheet and method of using
US3679426A (en) * 1970-04-09 1972-07-25 Eastman Kodak Co Photosensitive and thermosensitive elements,compositions and processes
US3667959A (en) * 1970-05-01 1972-06-06 Eastman Kodak Co Photosensitive and thermosensitive element,compositions and process
US3666477A (en) * 1970-06-03 1972-05-30 Eastman Kodak Co Element,composition and process
US3707377A (en) * 1971-02-02 1972-12-26 Minnesota Mining & Mfg Photothermic dry silver coatings stabilized with halogen-containing organic oxidizing agents

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4260761A (en) * 1978-10-02 1981-04-07 E. I. Du Pont De Nemours And Company Intermediates for the preparation of octahydro-1H-benzo[4,5]furo[3,2,-e]-isoquinoline analgesic and narcotic antagonistic compounds
US4243668A (en) * 1979-07-09 1981-01-06 E. I. Du Pont De Nemours And Company Octahydro-1H-benzo[4,5]furo[3,2-e]-isoquinoline analgesic and narcotic antagonistic compounds
US4839332A (en) * 1987-01-16 1989-06-13 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US5599648A (en) * 1990-08-03 1997-02-04 Canon Kabushiki Kaisha Surface reforming method, process for production of printing plate, printing plate and printing process
US5409798A (en) * 1991-08-30 1995-04-25 Canon Kabushiki Kaisha Plate blank, process for producing printing plate from plate blank, and printing method and apparatus using plate
US20040186132A1 (en) * 1994-12-22 2004-09-23 Jones Todd K. Steroid receptor modulator compounds and methods
US5688808A (en) * 1994-12-22 1997-11-18 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US5693647A (en) * 1994-12-22 1997-12-02 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US5693646A (en) * 1994-12-22 1997-12-02 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US5696130A (en) * 1994-12-22 1997-12-09 Ligand Pharmaceuticals Incorporated Tricyclic steroid receptor modulator compounds and methods
US5696127A (en) * 1994-12-22 1997-12-09 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US5696133A (en) * 1994-12-22 1997-12-09 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US5994544A (en) * 1994-12-22 1999-11-30 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US6093821A (en) * 1994-12-22 2000-07-25 Ligand Pharmaceuticals Incorporated Process for preparing steroid receptor modulator compounds
US6121450A (en) * 1994-12-22 2000-09-19 Ligand Pharmaceuticals Incorporated Intermediates for preparation of steroid receptor modulator compounds
US6448405B1 (en) 1994-12-22 2002-09-10 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US5688810A (en) * 1994-12-22 1997-11-18 Ligand Pharmaceuticals Incorporated Steroid receptor modulator compounds and methods
US6696459B1 (en) 1994-12-22 2004-02-24 Ligand Pharmaceuticals Inc. Steroid receptor modulator compounds and methods
US6534516B1 (en) 1996-06-27 2003-03-18 Ligand Pharmaceuticals Incorporated Androgen receptor modulator compounds and methods
US20030130505A1 (en) * 1999-08-27 2003-07-10 Lin Zhi Bicyclic androgen and progesterone receptor modulator compounds and methods
US20070167445A1 (en) * 1999-08-27 2007-07-19 Higuchi Robert I Androgen receptor modulator compounds and methods
US6667313B1 (en) 1999-08-27 2003-12-23 Ligand Pharmaceuticals Inc. 8-substituted-6-triflouromethyl-9-pyrido [3,2-G] quinoline compounds as androgen receptor modulators
US6462038B1 (en) 1999-08-27 2002-10-08 Ligand Pharmaceuticals, Inc. Androgen receptor modulator compounds and methods
US6964973B2 (en) 1999-08-27 2005-11-15 Ligand Pharmaceuticals Incorporated Bicyclic androgen and progesterone receptor modulator compounds and methods
US6566372B1 (en) 1999-08-27 2003-05-20 Ligand Pharmaceuticals Incorporated Bicyclic androgen and progesterone receptor modulator compounds and methods
US7696246B2 (en) 1999-08-27 2010-04-13 Ligand Pharmaceuticals Incorporated Bicyclic androgen and progesterone receptor modulator compounds and methods
US6593493B1 (en) 1999-09-14 2003-07-15 Ligand Pharmaceuticals, Inc. RXR modulators with improved pharmacologic profile
EP1180722A3 (en) * 2000-08-15 2003-01-02 Eastman Kodak Company Photothermographic materials providing improved image stability and methods of use
US20060128740A1 (en) * 2001-02-23 2006-06-15 Lin Zhi Tricyclic androgen receptor modulator compounds and methods
US20070293528A9 (en) * 2001-02-23 2007-12-20 Lin Zhi Tricyclic androgen receptor modulator compounds and methods
US7727980B2 (en) 2001-02-23 2010-06-01 Ligand Pharmaceuticals Incorporated Tricyclic androgen receptor modulator compounds and methods
US20100210678A1 (en) * 2001-02-23 2010-08-19 Lin Zhi Tricyclic androgen receptor modulator compounds and methods
US20080227810A9 (en) * 2003-08-22 2008-09-18 Lin Zhi 6-Cycloamino-2-quinolinone derivatives as androgen receptor modulator compounds
US20070066650A1 (en) * 2003-08-22 2007-03-22 Lin Zhi 6-Cycloamino-2-quinolinone derivatives as androgen receptor modulator compounds
US7816372B2 (en) 2003-08-22 2010-10-19 Ligand Pharmaceuticals Incorporated 6-cycloamino-2-quinolinone derivatives as androgen receptor modulator compounds

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USB335670I5 (enrdf_load_stackoverflow) 1975-01-28
DE2308766A1 (de) 1973-09-06
GB1413288A (en) 1975-11-12
BE795696A (nl) 1973-08-21

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