US3817752A - Free radical photographic system containing a pyrylium dye former - Google Patents

Free radical photographic system containing a pyrylium dye former Download PDF

Info

Publication number
US3817752A
US3817752A US00288780A US28878072A US3817752A US 3817752 A US3817752 A US 3817752A US 00288780 A US00288780 A US 00288780A US 28878072 A US28878072 A US 28878072A US 3817752 A US3817752 A US 3817752A
Authority
US
United States
Prior art keywords
group
vinylcarbazole
image
compound
exposure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00288780A
Other languages
English (en)
Inventor
U Laridon
Den Houte J Van
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Application granted granted Critical
Publication of US3817752A publication Critical patent/US3817752A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances

Definitions

  • R represents an aliphatic group, an aryl group, or represents together with R' the necessary atoms to close a homocyclic ring
  • R represents hydrogen, a C -C alkyl group, a phenyl group, or a phenoxy group
  • R represents a C -C alkyl group
  • n 1 or 2.
  • the invention relates to photographic recording and reproduction of information and to materials suited therefor.
  • a typical photosystem which has been investigated in detail comprises leuco crystal violet, carbon tetrabromide, triphenylstibine and polystyrene as a binder.
  • a photosensitive composition which is capable of producing directly a visible image as a result of an image-wise modulated exposure to actinic electromagnetic radiation and of producing a visible image by the steps of (1) image-wise exposing the recording material to activating electromagnetic radiation of a dose sufiicient to bring about a latent or barely visible image and of (2) subsequently overall exposing the recording material to light of the wavelength range for which it has been made more sensitive in the image-wise exposure, said composition comprising in admixture:
  • R represents an organic group, e.g. a saturated or unsaturated aliphatic group, e.g. an alkyl group including a substituted alkyl group, or an aryl group including a substituted aryl group, or together with IR represents the necessary atoms to close a homocyclic ring, e.g. a cyclohexylen-Z-one
  • R' represents hydrogen, a lower alkyl group, e.g. methyl, or a substituted lower alkyl group, e.g. benzyl, a phenyl group including a substituted phenyl group or phenyloxy,
  • Z represents the necessary atoms to close a homocyclic nucleus including a substituted homocyclic nucleus e.g. a benzene or a naphthalene nucleus including a substituted benzene or naphthalene nucleus,
  • R represents a lower alkyl (C -C group
  • n 1 or 2.
  • Table 1 contains an illustrative list of compounds according to the general formula 1) with their melting point and the colour formed by exposure in the presence of OBr in polystyrene as binding agent.
  • the compounds of general formula (I) can be prepared e.g. according to:
  • a suitable compound according to the general formula (II) has the following structure:
  • a high photosensitivity combined with a very low fog formation is obtained by the use of the compounds according to general formula I and more particularly by those having a methoxy group in the ortho-position to the hydroxyl group.
  • each of A, B, X and Y is a halogen atom of the group of chlorine, bromine or iodine, or
  • one of said symbols A, B, X or Y represents an alkyl group, including a substituted alkyl group e.g. a halogen substituted alkyl group, a hydroxyalkyl group or an aralkyl group e.g. benzyl, an aryl group, a substituted aryl group or an aroyl group, and the other symbols chlorine, bromine or iodine, or wherein at least two of said symbols A, B, X or Y represent an aromatic acyl group, e.g. benzoyl, and the other symbols chlorine, bromine or iodine.
  • Suitable representatives falling within the scope of that general formula are organic halides such as carbon tetrabromide, bromoform, iodoform, hexachloroethane, hexabromoethane, pentabromoethane, 1,1,2,2 tetrabromoethane, a,a,a-tribromoacetophenone and tribromoethanol.
  • organic halides such as carbon tetrabromide, bromoform, iodoform, hexachloroethane, hexabromoethane, pentabromoethane, 1,1,2,2 tetrabromoethane, a,a,a-tribromoacetophenone and tribromoethanol.
  • A represents a single bond or a divalent hydrocarbon group e.g. -CH
  • R represents hydrogen or a lower alkyl group, e.g.
  • R represents hydrogen or a lower alkyl group, e.g. methyl or ethyl
  • each of Q and Q represents hydrogen or together represent the necessary atoms to close an adjacent carbocyclic ring or ring system including such ring or ring system in substituted form, preferably an aromatic ring (e.g. a benzene ring) including a substituted aromatic ring e.g. a halogen substituted (chlorine, bromine or iodine substituted) benzene ring,
  • aromatic ring e.g. a benzene ring
  • substituted aromatic ring e.g. a halogen substituted (chlorine, bromine or iodine substituted) benzene ring
  • each of Q and Q represents hydrogen or together represent the necessary atoms to close an adjacent carbocyclic nucleus or ring system including such a ring or ring system in substituted form, preferably an aromatic ring (e.g. a benzene ring) including a substituted aromatic ring e.g. a halogen substituted (chlorine, bromine or iodine'substituted) benzene ring, and
  • n 1 or 2.
  • the N-vinyl polymers and copolymers can be prepared by application of one of the various known polymerization procedures, e.g., by pearlor emulsion polymerization or by polymerization in solution, whereby the initiation of the polymerization can occur by free radicals, by ion formation, or by radiation eg, with actinic light.
  • the polymerization degree is not critical and can vary between wide limits.
  • the content of groups corresponding to the general formula given hereinbefore is not critical and, as shown furtheron in the table of copolymers containing N-vinylcarbazole units, can vary between wide limits, say, e.g.
  • copolymers having a content of vinyl carbazole units between 40 and 90%.
  • poly-N-vinyl indoles are described in the published German patent applications 1,906,831 and 1,917,747.
  • the poly-N-vinyldiphenylamine is described in the published German patent application 2,007,692.
  • Halogen-substituted poly-N-vinylcarbazoles are described in the published Japanese patent applications 7,592/68l9,751/67 and 7,591/68.
  • a preferred photosensitive recording material according to the present invention contains the color forming 9 compounds and poly-N-vinylcarbazole in a ratio b weight within the range of 80: 100 to 10:400.
  • N-vinylcarbazole polymers are preferably used in admixture with carbon tetrabromide or iodoform or in a mixture of both of said polyhalogen compounds.
  • Said polyhalogen compounds are preferably used with respect to poly-N-vinylcarbazole in a ratio by weight in the range of 160: 100 to 20:100.
  • one or more other binding agents for forming a selfsupporting or supported layer are used.
  • hydrophobic polymers are elected that shield as much as possible to ingredients from a direct contact with the atmosphere and more especiall from oxygen.
  • Particularly suitable binders for use in the present invention are hydrophobic polymers and copolymers e.g. containing styrene, vinyl acetate, acrylonitrile, acrylate, methacrylate, or butadiene units, hydrophobic cellulose derivatives, phenoxy resins or polycondensates of the polyester type, e.g. polycarbonates.
  • These polymers may be used in admixture for improvement of the mechanical strength or adhering power of the recording layer to its support when no self-supporting layer is produced.
  • anti-foggants may be added to the photosensitive composition.
  • Suitable anti-foggants include sterically hindered phenols, e.g. 2,6-ditert.butyl p-cresol and other reducing compounds or agents accepting atmospheric oxygen.
  • Preferred amounts of anti-fogging agent such as said cresol compound with respect to photosensitive carbon tetrabromide and/ or iodoform are within the weight ratio range of 1:100 to 2.5:100.
  • a dry photographic coating containing the above mentioned ingredients can be formed by dissolving the binding agent(s) in a suitable inert solvent, which acts as dispersing or dissolving medium for the other ingredients, and by removing the solvent from the coating composition by evaporation so that a solid photographic recording layer is left on a properly chosen support.
  • the supports may be of any kind encountered in silver halide photographic materials, e.g. paper and film supports, e.g. subbed and unsubbed polyethylene terephthalate ester supports.
  • the recording materials of the present invention containing the color-forming compounds of the general formulae especially in combination with polymers and copolymers containing N-vinylcarbazole units and that serve as binding agent show a remarkable high sensitivit to U.V. radiation. This high sensitivity is still increased when during the U.V. exposure the temperature of the recording layer composition is raised above 40 C. A very suitable operating temperature is in the range of 40-70 C.
  • the recording materials according to the present invention are suited to produce print-out images of different color according to the particular color forming compound applied.
  • a mixture of carbon tetrabromide and iodoform is used, which yields a superadditive sensitivity effect.
  • the stabilisation of the obtained prints may proceed by Washing out the residual free radical generator with a suitable solvent or solvent mixture, e.g. a hydrocarbon liquid such as petroleum ether optionally mixed with acetone, or by simply evaporating it by raising the temperature when the compound involved is sufliciently volatile.
  • a suitable solvent or solvent mixture e.g. a hydrocarbon liquid such as petroleum ether optionally mixed with acetone
  • carbon tetrabromide or a mixture of carbon tetrabromide and iodoform is preferred.
  • a useful stabilisation tempera- 10 ture is in the range of to C. During the heat stabilisation an increase of the image density is obtained.
  • the information-wise exposure is carried out in such a way that first a latent image is produced, which subsequently is transformed into a visible dye image by means of a so-called optical developmen
  • the optical development proceeds by overall exposing the recording layer containing the latent or barely visible image with visible radiation that lies in the spectral absorption band of the products formed by the image-wise exposure and image-wise interaction of the photoexposed ingredients (1) and (2) of the mentioned photosensitive composition.
  • no light is applied to which the photosensitive polyhalogen compound is inherently sensitive since thereby the effect of the imagewise exposure is masked by an overall colouration.
  • a filter absorbing all the light corresponding with the wavelength range that is inherently absorbed by the ingredients of the non-previously exposed recording layer.
  • the optical development effect is marketdly speeded up and the image density increased by applying heat, e.g. supplied by contact with a hot body or through infrared radiation during the overall exposure to visible light.
  • heat e.g. supplied by contact with a hot body or through infrared radiation during the overall exposure to visible light.
  • optical development speed obtains a particularly high value by the use of poly-N-vinylcarbazole or the copolymers containing N-vinylcarbazole units in combination with the present colour forming compounds.
  • optical development speed is likewise increased by means of an organic compound corresponding to the following general formula:
  • each of R R and R represents an aryl group including a substituted aryl group, e.g. phenyl or a phenyl group substituted with a hydroxyl group or a halogen atom, e.g. chlorine or iodine.
  • the recording material is first overall exposed to electromagnetic radiation in order to produce non-differentially over the whole recording layer latent dyestuif centres that afterwards are optically developed information-wise by a sufficiently strong information-wise exposure in the absorption band of the dyestutf centres.
  • the information-wise exposure proceeds simultaneously with an overall heating, effected e.g., by an overall infra-red exposure.
  • the information-wise exposure applied in the present invention may be a contact exposure of the direct or reflex type and likewise an optical projection exposure as is used, e.g., in an optical enlarging apparatus.
  • the infor mation-wise exposure need not be simultaneous in all parts of the recording material.
  • the exposure may be progressive in one continuous step as, e.g., in sound track recording, or in successive intermittent steps provided that the required information-wise change is obtained.
  • the recording material may be scanned with an imagewise modulated radiant energy spot of high intensity e.g. a laser beam, or the material may be progressively exposed through a slit, e.g. to copying light of a tubular lamp that is given a translation movement along the original.
  • a recording material of the present invention being suited for the recording of information in the form of modulated ultraviolet radiation can be used in X-ray and electron-beam recording.
  • X-ray beams can be absorbed in substances absorbing high energy and by means of them create so-called secondary photos, e.g. of the ultraviolet radiation energy band, and photo-electrons that are absorbed by the photosensitive polyhalogen compound forming through its photoradicals a dyestutf salt with the colour forming compound.
  • Substances for high energy absorption that may be incorporated into the recording element contain the elements lead, mercury, bismuth, barium and/or tungsten.
  • Lead compounds that are photosensitive by themselves are preferred, e.g. lead monoxide, lead bromide and lead iodide.
  • Suitable light sources for use in a recording method of the present invention are ultra-violet radiation sources, xenon-gas lamps, incandescent bulbs and flash lamps. Sunlight is also suited in the overall exposure. For the optical development an infra-red lamp emitting also in the visible spectrum is preferably used.
  • Electron beam and laser beam recording proceed with the apparatus suited for that purpose and known to those skilled in the art.
  • Recording materials of the present invention are very versatile in that by the use of a proper sensitizing agent they can be applied for continuous tone or halftone reproduction. They can offer very contrasty images so that they are very suited for the reproduction of line and screen type originals and find a successful use in a great variety of graphic art applications. Due to the very high resolving power of the recording materials (the dyestuffs are formed in molecularly divided form) the recording materials of the present invention are particularly suited for microfilm reproduction and high precision image rendering as e.g. in the production of optical mieromask masters used in the manufacturing of microelectronic circuitry.
  • the reflex-exposure properties of the present recording materials make them very useful in the document reproduction sector since in a reflex-contact exposure they otfer print-out images of a sufiiciently intense spectral density.
  • a recording layer as described herein is used in conjunction with a magnetic recording layer and is more particularly applied to the rear side of a flexible tape support carrying the magnetic recording layer.
  • a sound track is formed in the magnetic recording layer and a visual text image corresponding with the sound track is photographed on the recording layer of the present invention.
  • Such a recording material thus allows the storing of optical and acoustic signals and makes it possible to reproduce both informations simultaneously.
  • EXAMPLE 1 A mixture of 500 mg. of carbon tetrabromide, 20 mg. of a colour forming compound indicated by number in Table 1 and 2 mg. of 2,6-di-tert.butyl-p-cresol was dissolved in 8 ml. of a poly-N-vinylcarbazole solution in methylene chloride.
  • the solution was coated at a thickness of 0.12 mm. onto a non-subbed polyethylene terephthalate support and dried in the dark at room temperature.
  • the obtained images were stabilized by means of a 3 min. heat treatment at C.
  • Optical development processing The same recording materials as used in the print-out processing were exposed through a transparent line original operating with the same U.V. lamp and exposure distance and applying for the image-wise exposure an exposure time as indicated in the Table.
  • the optical development was effected by overall exposing the image-Wise exposed recording material with a 250 w. infrared lamp of Bie and Berntsen, Copenhagen, Denmark, emitting also in the visible spectrum and placed at a distance of 15 cm.
  • the overall exposure time for reaching a maximum density (d equal to 1 is listed in the Table.
  • a cut-off filter was used absorbing all the light having a wavelength smaller than 580 nm.
  • the solution was coated at a thickness of 0.12 mm. onto a non-subbed polyethylene terephthalate support and dried in the dark at room temperature.
  • the recording layer was exposed for 2 min. through a step wedge of constant 0.15 by means of an 80 w. high pressure mercury vapour lamp type HPL of Philips placed at a distance of 10 cm.
  • the obtained images were stabilized by means of a 3 min. heat treatment at 150 C.
  • the present example illustrates the image density intensification obtained by applying a heat treatment subsequent to the image-wise exposure.
  • the solution was coated at a thickness of 0.12 mm. onto a baryta coated paper support and dried in the dark at 50 C.
  • the obtained recording material was exposed for 2 min. through a step wedge with constant 0.15 by means of an -80 w. high pressure mercury vapour lamp placed at a distance of 10 cm.
  • the image density obtained in the several reproduced steps was measured before heating the exposed recording layer for 2 sec. at 150 C. and after such heat treatment. The results are listed in the following Table. The densities were measured with white light in a Macbeth-densitometer.
  • EXAMPLE 4 The following coating solution was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.12 mm.:
  • Eponol a phenoxy resin prepared from epichlorohydrin and 2,2-bis (4- hydroxyphenyl)-propane of Shell-Netherlands
  • EXAMPLE 5 The following coating solution was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.10 mm.:
  • the recording layer was exposed for 1 min. through a continuous tone transparency (negative) 'by means of an w. U.V. lamp (type HPL) held at a distance of 10 cm.
  • EXAMPLE 6 The following coating solution was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.10 mm.:
  • the recording layer was exposed for 1 min. through a continuous tone transparency (negative) by means of an 80 w. U.V. lamp (type HPL) held at a distance of 10 cm.
  • EXAMPLE 7 The following coating solution was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.12 mm.:
  • the same recording layer applied to a baryta coated paper yielded an image of the same quality.
  • EXAMPLE 8 The following coating solution was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.12 mm.: a
  • the recording layer was exposed for 10 see. through a continuous tone transparency (negative) by means of an 80 w. U.V. lamp (type HPL) held at a distance of 10 cm.
  • a latent image was obtained that was optically developed by overall exposing the recording layer for 3 min. with a 250 w. infrared lamp (Bie and Berntsen) through a cut-01f filter absorbing all the light of a wavelength below 540 nm.
  • a dense fog free magneta image was obtained. It was stabilized by heating the recording material for 3 min. at 150 C.
  • a same recording layer as described above but not containing said sensitizing agent yielded by an image-wise exposure of 30 sec. and an overall exposure of min. only a very faint magenta image.
  • EXAMPLE 9 The following coating composition was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.12 mm.:
  • Carbon tetrabromide mg.. 120 Compound 20 of Table 1 mg 600 1,1,2-trichloroethane ml 12
  • the applied coating was dried for 1 h. at 60 C. and thereupon exposed for 2 min. through a step wedge of constant 0.15 by means of an 80 w. high pressure mercury vapour lamp (type HPL) placed at a distance of cm. A yellow wedge image was obtained, which was stabilized by heating the exposed coating for 30 sec. at 150 C.
  • EXAMPLE 10 The following coating composition was applied to an unsubbed polyethylene terephthalate support at a thickness of 0.12 mm.:
  • each of A, B, X and Y is chlorine, bromine and iodine, or one of A, B, X or Y represents an alkyl group, an aryl group or an aroyl group and the others represent chlorine, bromine or iodine, or at least two of A, B, X or Y represent an aromatic acyl group and the others represent chlorine, bromine or iodine, and p (2) at least one color forming compound corresponding to one of the following general formulae:
  • R represents an alkyl group, a phenyl group, a
  • R represents hydrogen, a C -C alkyl group, a
  • said visible image being formed by the step of: imagewise exposing the recording material to activating electromagnetic radiation of a dose being sufiicient to bring about a directly visible image, or by the steps of: imagewise exposing the recording material to activating electromagnetic radiation of a dose sufficient to create therein an at most barely visible image which has a spectral sensitivity in a wawelength range outside the inherent sensitivity range of the organic polyhalogen compound, and overall exposing the imagewise exposed recording material to light within the wavelength range to which the initially exposed portions were made more sensitive than the initially non-exposed portions, to thereby increase the visibility of said image, or by the steps of: overall exposing the recording materal to electromagnetic radiation of a dose su
  • a photosensitive recording material for producing directly a visible image upon imagewise exposure to activating electromagnetic radiation, said material containing an intimate mixture consisting essentially of:
  • each of A, B, X and Y is chlorine, bromine and iodine, or one of A, B, X'or Y represents an alkyl group, an aryl group, or an aroyl group and the others represent chlorine, bromine or iodine, or at least two of A, B, X or Y represent an aromatic acyl group and the others represent chlorine, bromine or iodine, and (2) at least one color forming compound corresponding to one of the following general formulae (1) or (H):
  • R represents an alkyl group, a phenyl group, a
  • R represents hydrogen, a C -C alkyl group, a
  • Z represents the necessary atoms to close a phenyl or naphthyl nucleus
  • Z represents the necessary atoms to close a henzene or naphthalene nucleus
  • R represents a C -C alkyl group
  • n 1 or 2.
  • Z represents sulphur or a single bond
  • A represents a single bond or a. divalent hydrocarbon group
  • each of R and R represents hydrogen or a lower alkyl radical
  • each of Q and Q represents hydrogen or together represent the necessary atoms to close an adjacent carbocyclic nucleus
  • each of Q and Q represents hydrogen or together rep resent the necessary atoms to close an adjacent carbocyclic nucleus
  • n 1 or 2.
  • polymeric compound is poly-N-vinylcarbazole or a copolymer containing N-vinylcarbazole units.
  • R represents hydroxyl, chlorine or iodine.
  • a photosensitive recording material wherein said ultraviolet-sensitive compound is carbon tetrabromide or iodoform.
  • a photosensitive recording material according to claim 2 which contains a mixture of carbon tetrabromide and iodoform.
  • a photosensitive recording material according to claim 2 which in addition to said mixture contains a polymeric compound containing recurring units of the following general structure:
  • a photosensitive recording material according to claim 2 which in addition to said mixture contains an organic compound having the following general formula:
  • R represents hydroxyl, chlorine or iodine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US00288780A 1971-09-14 1972-09-13 Free radical photographic system containing a pyrylium dye former Expired - Lifetime US3817752A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB4280271A GB1398265A (en) 1971-09-14 1971-09-14 Print-out and optically developable organic polyhalogen photographic material

Publications (1)

Publication Number Publication Date
US3817752A true US3817752A (en) 1974-06-18

Family

ID=10426032

Family Applications (1)

Application Number Title Priority Date Filing Date
US00288780A Expired - Lifetime US3817752A (en) 1971-09-14 1972-09-13 Free radical photographic system containing a pyrylium dye former

Country Status (7)

Country Link
US (1) US3817752A (OSRAM)
JP (1) JPS4838727A (OSRAM)
BE (1) BE787339A (OSRAM)
CA (1) CA990569A (OSRAM)
DE (1) DE2244783A1 (OSRAM)
FR (1) FR2152997B3 (OSRAM)
GB (1) GB1398265A (OSRAM)

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066459A (en) * 1976-01-26 1978-01-03 Horizons Incorporated, A Division Of Horizons Research Incorporated Free radical photosensitive compositions with improved sensitivity and shelf life stability
US4263395A (en) * 1976-11-18 1981-04-21 Agfa-Gevaert N.V. High intensity photon-image recording
US4273787A (en) * 1973-08-20 1981-06-16 Sandoz, Inc. 1-Alkyl,1-phenyl-butenes
US4279930A (en) * 1978-10-10 1981-07-21 The Upjohn Company Process for treating inflammation
US4439418A (en) * 1981-07-29 1984-03-27 Henkel Kgaa Topical preparations for the treatment of seborrhea and process for inhibiting sebum production
US4474869A (en) * 1981-05-29 1984-10-02 Hughes Aircraft Company Polyvinylpyridine radiation resists
US5162218A (en) * 1988-11-18 1992-11-10 The Regents Of The University Of California Conjugated polypeptides and methods for their preparation
US5208353A (en) * 1989-06-14 1993-05-04 Smithkline Beecham Corp. Intermediates for preparing epoxy esters
US5616443A (en) 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5643356A (en) 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5686503A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and applications therefor
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5739175A (en) 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550A (en) 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5811199A (en) 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5837429A (en) 1995-06-05 1998-11-17 Kimberly-Clark Worldwide Pre-dyes, pre-dye compositions, and methods of developing a color
US5849411A (en) 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5885337A (en) 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6486227B2 (en) 2000-06-19 2002-11-26 Kimberly-Clark Worldwide, Inc. Zinc-complex photoinitiators and applications therefor
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US7147983B1 (en) * 1996-10-07 2006-12-12 Shipley Company, L.L.C. Dyed photoresists and methods and articles of manufacture comprising same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1422157A (en) * 1972-02-29 1976-01-21 Agfa Gevaert Electron beam recording material
JPS515634A (ja) * 1974-07-04 1976-01-17 Tokyo Gas Co Ltd Chitsusosankabutsuteihatsuseinenshohoho
JPS5273032A (en) * 1975-12-13 1977-06-18 Toyo Boseki Method of amplifying image
KR20120120267A (ko) * 2010-01-29 2012-11-01 닛뽄 가야쿠 가부시키가이샤 페놀 화합물, 에폭시 수지, 에폭시 수지 조성물, 프리프레그 및 그들의 경화물

Cited By (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4273787A (en) * 1973-08-20 1981-06-16 Sandoz, Inc. 1-Alkyl,1-phenyl-butenes
US4066459A (en) * 1976-01-26 1978-01-03 Horizons Incorporated, A Division Of Horizons Research Incorporated Free radical photosensitive compositions with improved sensitivity and shelf life stability
US4263395A (en) * 1976-11-18 1981-04-21 Agfa-Gevaert N.V. High intensity photon-image recording
US4279930A (en) * 1978-10-10 1981-07-21 The Upjohn Company Process for treating inflammation
US4474869A (en) * 1981-05-29 1984-10-02 Hughes Aircraft Company Polyvinylpyridine radiation resists
US4439418A (en) * 1981-07-29 1984-03-27 Henkel Kgaa Topical preparations for the treatment of seborrhea and process for inhibiting sebum production
US5162218A (en) * 1988-11-18 1992-11-10 The Regents Of The University Of California Conjugated polypeptides and methods for their preparation
US5208353A (en) * 1989-06-14 1993-05-04 Smithkline Beecham Corp. Intermediates for preparing epoxy esters
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US5733693A (en) 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5643356A (en) 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5645964A (en) 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5865471A (en) 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5683843A (en) 1993-08-05 1997-11-04 Kimberly-Clark Corporation Solid colored composition mutable by ultraviolet radiation
US5858586A (en) 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US5616443A (en) 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5700850A (en) 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US6127073A (en) 1993-08-05 2000-10-03 Kimberly-Clark Worldwide, Inc. Method for concealing information and document for securely communicating concealed information
US5721287A (en) 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5643701A (en) 1993-08-05 1997-07-01 Kimberly-Clark Corporation Electrophotgraphic process utilizing mutable colored composition
US6120949A (en) 1993-08-05 2000-09-19 Kimberly-Clark Worldwide, Inc. Photoerasable paint and method for using photoerasable paint
US6066439A (en) 1993-08-05 2000-05-23 Kimberly-Clark Worldwide, Inc. Instrument for photoerasable marking
US5773182A (en) 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US6060223A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Plastic article for colored printing and method for printing on a colored plastic article
US6060200A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms and methods
US6054256A (en) 1993-08-05 2000-04-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for indicating ultraviolet light exposure
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US5908495A (en) 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US6342305B1 (en) 1993-09-10 2002-01-29 Kimberly-Clark Corporation Colorants and colorant modifiers
US5685754A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US5709955A (en) 1994-06-30 1998-01-20 Kimberly-Clark Corporation Adhesive composition curable upon exposure to radiation and applications therefor
US6090236A (en) 1994-06-30 2000-07-18 Kimberly-Clark Worldwide, Inc. Photocuring, articles made by photocuring, and compositions for use in photocuring
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6071979A (en) 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US5686503A (en) * 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and applications therefor
US6008268A (en) 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6235095B1 (en) 1994-12-20 2001-05-22 Ronald Sinclair Nohr Ink for inkjet printers
US5837429A (en) 1995-06-05 1998-11-17 Kimberly-Clark Worldwide Pre-dyes, pre-dye compositions, and methods of developing a color
US5798015A (en) 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5786132A (en) 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5811199A (en) 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US6063551A (en) 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US5747550A (en) 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5739175A (en) 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5681380A (en) 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5849411A (en) 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6168655B1 (en) 1995-11-28 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5885337A (en) 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US6168654B1 (en) 1996-03-29 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US7147983B1 (en) * 1996-10-07 2006-12-12 Shipley Company, L.L.C. Dyed photoresists and methods and articles of manufacture comprising same
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6486227B2 (en) 2000-06-19 2002-11-26 Kimberly-Clark Worldwide, Inc. Zinc-complex photoinitiators and applications therefor

Also Published As

Publication number Publication date
DE2244783A1 (de) 1973-03-22
FR2152997B3 (OSRAM) 1974-10-31
FR2152997A1 (OSRAM) 1973-04-27
GB1398265A (en) 1975-06-18
CA990569A (en) 1976-06-08
JPS4838727A (OSRAM) 1973-06-07
BE787339A (nl) 1973-02-09

Similar Documents

Publication Publication Date Title
US3817752A (en) Free radical photographic system containing a pyrylium dye former
US3810763A (en) Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and zno or pb(ii) oxide and the use thereof
US3617288A (en) Propenone sensitizers for the photolysis of organic halogen compounds
US3980480A (en) Photographic recording and reproduction of information photochromic composition containing polyhalogenated hydrocarbon, spiropyran compound and heterocyclic mercapto compound and the use thereof
US4008085A (en) Photosensitive material containing an organic polyhalogen compound and a dye precursor and the use thereof
US3775130A (en) Photosensitive material comprising benzopyrylium dye sensitizer
US3305361A (en) Information recording
US3667954A (en) Tribromomethyl sulfonyl pyridazine or phthalazine photoactivators
US3844797A (en) Photosensitive recording material
US3846131A (en) Recording material containing a polyhalogenated hydrocarbon photoactivator and a dye forming combination of an indolizine derivative and an aldehyde and the use thereof
US3820995A (en) Photochromic material containing a spiropyran compound a polyhalogenated hydrocarbon photoactivator and an acetanilide sensitizer and the use thereof in photoimaging
US3887378A (en) Image recording and receiving materials
US3708297A (en) Stabilizing with iodide an imagewise exposed photosensitive composition containing a halogenated photoactivator and an organic amine color former
US3773512A (en) Photothermic material containing a light-insensitive silver salt and an indane-1,3-dione reducing agent
US3736139A (en) Heat and light stabilization of photosensitive elements containing poly-halogenated hydrocarbons,n-vinylcarbazoles and difurfurylidene pentaerythritols
US3753395A (en) Photo-thermographic recording process with 5-pyrazolane
US3936307A (en) Light and heat sensitive composition for producing a colored transfer complex image
US3510300A (en) Process for making latent dye salt image visible
US2666701A (en) Optical sensitization of photomechanical resists
US3887808A (en) Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole
US3773508A (en) Imagewise exposing and heating a photosensitive composition containing a spiropyran compound and an organic peroxide
US3519425A (en) Vesicular compositions and photographic elements containing 2-azido-1,4-quinones
EP0120601B1 (en) Oxidative imaging
US3164467A (en) Ultraviolet sensitive print-out compositions and process for image-wise exposure and fixing of same
US4184874A (en) Photosensitive composition containing chelate compound