WO1992007297A1 - Composition permettant la formation d'images par laser - Google Patents

Composition permettant la formation d'images par laser Download PDF

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Publication number
WO1992007297A1
WO1992007297A1 PCT/US1991/006587 US9106587W WO9207297A1 WO 1992007297 A1 WO1992007297 A1 WO 1992007297A1 US 9106587 W US9106587 W US 9106587W WO 9207297 A1 WO9207297 A1 WO 9207297A1
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WO
WIPO (PCT)
Prior art keywords
composition
component
polyacetylene
dye
polycarbocyanine
Prior art date
Application number
PCT/US1991/006587
Other languages
English (en)
Inventor
David F. Lewis
Original Assignee
Isp Investments Inc.
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 Isp Investments Inc. filed Critical Isp Investments Inc.
Publication of WO1992007297A1 publication Critical patent/WO1992007297A1/fr

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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
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • 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
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds

Definitions

  • a composition of the invention which is readily imageable with relatively low-output semi-conductor lasers or a similar light source comprises between about 1 and about 90 weight %, preferably between about 25 and 75 weight % of fine polyacetyleni ⁇ crystals having thermosensitivity at temperatures above 80 ⁇ C, preferably above 100°C. , and having the formula
  • thermochromic polyacetylene in a binder matrix and a polycarbocyanine dye, or a polycarbocyanine dye mixture, capable of absorbing energy within the 400-1500 nm wavelength range said dye present in an amount sufficient to absorb energy and transmit heat in excess of a critical temperature of the thermochromic polyacetylene, and said polycarbocyanine dye having the formula
  • n has a value greater than 1, e.g. from 2 to 10, preferably 2;
  • R is a polar hydrophilic moiety containing a radical of the group of amino, amido, hydroxy, ester, ether, phenol, carboxy, halo, sulfonyl, sulfoxy, sulfinyl, silyl, " siloxy, phosphoro, phosphate, keto, aldehyde, carbonate, urethane, urea radicals and a metal salt group;
  • R' is hydrogen, alkyl, aryl, aralkyl, alkaryl or is selected from the group defined for R;
  • p has a value of from 2 to 5;
  • R" is hydrogen, lower alkyl, phenoxy, methylate or any of the polycarbocyanine moieties of compounds disclosed in Volume 6, pages 616-622 of Kirk-Othmer's Encyclopedia of Chemical Technology, Second Edition, Interscience Publishers which absorb energy in the 600-1
  • thermosensitive polyacetylenic compounds those dispersed microcrystalline diacetylenes containing an amido, carboxy, hydroxy, ether, urea or urethane radical in a water soluble binder are preferred. Also preferred are water soluble polycarbocyanine dyes of the above formula or their mixtures.
  • the polycarbocyanine dyes of this invention have an advantage over many other energy absorbing dyes in that most of these compounds are water soluble and therefore require no extraneous solvent when added to aqueous dispersions of the crystalline polyacetylene.
  • polyacetylenic compounds include
  • the energy absorbing heat transmitting dye can also comprise a mixture of polycarbocyanines as well as their mixtures with other auxiliary energy absorbing dyes capable of operating in the 600-1500 nm wavelength range, which auxilary dyes may comprise up to 50% of the energy absorbing component of the present compositions.
  • Examples of other suitable energy absorbing dyes include metal complexes such as diimine iron complex, dithiol nickel complex, indigo, anthraquinone, azulenium, polycarbocyanine, squarylium, indolizinium, naphthalocyanine, naphthoquinone and its analogs, phthalocyanine, poly ethine, pyrylium, thiapyrylium, telluropyrylium, triaryl ammonium, triquinocycloalkane, or the specific dyes disclosed in the Journal of Imaging Science, Volume 32, number 2, March/April 1988, pages 51-56 (ORGANIC ACTIVE LAYER MATERIALS FOR OPTICAL RECORDING by James E.
  • metal complexes such as diimine iron complex, dithiol nickel complex, indigo, anthraquinone, azulenium, polycarbocyanine, squarylium, indolizinium, naphthalocyanine
  • polycarbocyanine dyes or their mixtures are preferred as the heat transmitting agents of this invention for the reason that, they possess narrow absorption bands with high extinction coefficients not shared with many of the other energy absorbing compounds mentioned above. Accordingly, significantly smaller amounts of these dyes are needed to provide the desired absorption.
  • compositions are prepared under atmospheric conditions by forming a dispersion, emulsion or suspension, preferably an aqueous dispersion, of from about 0.02 urn to about 5 urn diameter crystals, preferably from 0.1 urn to 1.0 um diameter crystals, of the polyacetylene in a binder to provide a dispersion containing from about 1 to about 50%, preferably from about 4 to about 20% of solid polyacetylenic microcrystals.
  • binder materials are natural and synthetic plastics, resins, waxes, colloids, gels and the like including gelatins, desirably photographic-grade gelatin, various polysaccharides including dextran, dextrin, hydrophilic cellulose ethers and esters, acetylated starches, natural and synthetic waxes including paraffin, beeswax, polyvinyl-lactams, polymers of acrylic and methacrylic esters and amides, hydrolyzed interpolymers of vinyl acetate and unsaturated -addition polymerizable compounds such as aleic anhydride, acrylic and methylacrylic esters and styrene, vinyl acetate polymers and copolymers and their derivatives including completely and partially hydrolyzed products thereof, polyvinyl acetate, polyvinyl alcohol, polyethylene oxide polymers, polyvinylpyrrolidone polyvinyl acetals including polyvinyl acetaldehyde acetal, polyvinviny
  • binders that can be applied from an aqueous medium, as a dispersion, emulsion or solution and particularly preferable are water soluble binder materials.
  • water soluble binder materials As is well known in the art in the preparation of smooth uniform continuous coatings of binder materials, or mixtures of binder materials, there may be employed therewith small amounts of conventional coating aids as viscosity controlling agents, surface active agents, leveling agents dispersing agents and the like.
  • the polycarbocyanine and dye or dye mixture is added to the aqueous dispersion in an amount sufficient to provide a peak optical density of between about 0.1 and about 3, preferably between about 0.2 and about 2, after which the resulting composition is coated and dried on a substrate.
  • Coatings of the present compositions are applied to a substrate by any of the known techniques, preferably in the form of an aqueous dispersion; although one or more monomolecular layers of the polyacetylene compound can be applied to the substrate as formed by the Langmuir-Blodgette, spin or spray coating methods.
  • Suitable substrates include polyethylene terephthalate, nylon, polystyrene, cellulose acetate, cellulose nitrate, cellophane, polyvinyl chloride, polyvinylidene chloride, teflon, polychlorotrifluoro- ethylene, polyethylene, polypropylene, paper, ceramic, glass, metal, wood and the like.
  • the coating composition is applied to the substrate in a thickness of from about 0.02 um to about 100 um, preferably from about 0.1 um to about 5 um or sufficient to produce an optical contrast of at least 1.0 in the image.
  • Application of the composition on the substrate is accomplished by any of the numerous and known techniques.
  • the dye can be dissolved in a suitable inert solvent such as a ketone, alcohol, benzene and the like for addition to the dispersion.
  • the weight ratio of polyacetylene to dye in the resulting coating mixture can vary from about 1000:1 to about 1:10.
  • the dried, coated composition is then exposed to laser, or other light emanation which impinges on the coating surface in precise areas of a design consistent with the desired image to create a latent image on the coating composition.
  • a suitable light source e.g. a GaAlAs laser, a xenon arc lamp, a mercury arc lamp, a tungsten-quartz halogen lamp, a YtAl garnet laser, and the like, it is necessary to match the optical absorbance of the polycarbocyanine dye or dye mixture to the wavelength of the light source.
  • a laser has an output wavelength of up to 1500 nm, preferably within a range of from about 650 to about 900 nm and a power sufficient to generate heat greater than 80 ⁇ C, preferably greater than 100°C, in the coating, which presumably deactivates the polyacetylene compound by causing it to undergo a change from its original crystalline solid state to an amorphous solid state after the exposure.
  • polyacetylene compounds are generally incapable of absorbing energy much above 400 nm wavelength, they are not directly imageable by the semi-conductor laser or other light source emitting energy above about 400 nm wavelength; hence the dye component is included to absorb energy and to generate heat which is instantly transferred to the thermosensitive polyacetylenic compound.
  • the latent imaged composition is then given an overall exposure to short wavelength radiation generated from a source such as UV light, electron beam, gamma-ray.
  • a source such as UV light, electron beam, gamma-ray.
  • X-ray, beta-ray, neutron, alpha-particle and the like to convert the unexposed portion of the coating composition to a color or color intensity which is readily distinguishable from the portion exposed to the light source which remains colorless.
  • Lasers or other light sources transmitting energy in the 400-1500 nm output range provide the highest image resolution, which is an important consideration in recording data transmissions.
  • high speed can be achieved as well.
  • a latent image is encoded on the polyacetylene compound which, when developed to a visual image, has excellent resolution and high color contrast.
  • the speed of recording and image density varies directly with the output power of the laser and the thickness of the polymer coating.
  • thin coatings of from about 0.02 to 100 micrometers, preferably from about 0.1 to 5 micrometer are recommended, whereupon the optical density change, developed by short wavelength exposure within the imaged area, is from about 1.0 to greater than 5.0 density units and preferably from about 1.5 to about 4.5 density units.
  • thermochromic change dramatically altering the absorption of blue light (e.g. a blue to yellow thermochromic change) since this change will provide the highest contrast for duplication to other recording photosensitive recording media, particularly those containing photopolymers, sensitive to blue and ultraviolet light as are commonly employed in commercial photolithographic printing plates and etch resists used in the preparation of printed board circuits.
  • polyacetylenes which are converted to other contrasting hues or hue intensities in the red, magenta, green, brown, blue and other color spectra all provide good image definition.
  • the types of laser which are suitably employed with the present composition include compact semi-conductor, solid state, gas, metal-vapor, and dye lasers.
  • semi-conductor diode lasers or solid state lasers are preferred and semi-conductor diode lasers are most preferred.
  • the techniques of short wavelength exposure to develop the latent image are well known, thus further amplification is not required.
  • a second solution, Solution B was prepared by dissolving 15 g. of a deionized photographic gelatin and 0.6 g. of ALKANOL XC ⁇ 1 ) in 250 g. of water.
  • Solution B was heated to 75°C. and introduced into a high shear blender. While mixing at high speed, Solution A, at 50°C. , was added to Solution B over a period of about 30 seconds and mixing was continued for an additional 2 minutes. The mixture was cooled to 40°C. and then poured into stainless steel containers and chill set at about 4°C. The resulting gelled dispersion was then placed in a vacuum oven at about 20°C. and evacuated to about 5 torr pressure for sufficient time to undergo a 60 g. weight loss at which time n-butanol was removed. The gelled dispersion was then reconstituted by melting at 40°C. and adding 60 g. of water to replace the liquid lost in drying.
  • Sample A was prepared by coating the reconstituted dispersion of Example 1 on 3 mil polyester film base to provide a layer having a dry thickness of about 1.5 um.
  • Sample B was prepared by dissolving 0.1 g. of IR-125 ⁇ 2 ) dye in 100 g. of the reconstituted dispersion of Example 1 and coating this mixture on 3 mil polyester film base to provide a dry coating having a thickness of about 1.5 um.
  • Sample A was exposed to the emission from a GaAlAs semi-conductor diode laser with a wavelength of about 830 nm.
  • the laser emission was focused onto the surface of the Sample and scanned across the surface at the rate of about 300 cm/sec.
  • the power output of the laser was varied in order to expose different portions of the Sample to various energies in the range of from about 10 mJ/cm 2 to about 1 J/cm 2 .
  • Example 3 When the laser exposure process of Example 3 was repeated on a portion of Sample B, again no marks could be discerned from the laser transmitted light. However, when the Sample was subsequently exposed to short wavelength UV radiation the image of the original laser exposure could be seen as colorless areas against a blue background with a visual contrast exceeding 1.5 du. The markings were evident at exposures equal to or greater than about 50 mJ/cm 2 . These markings were extremely well defined and of very high resolution and edge acuity, indicating that the Sample and imaging process were suitable for high resolution imaging or digital data recording.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

On décrit une composition comprenant des composés d'acétylène cristallins fins qui possèdent une pluralité de liaisons d'acétylène conjuguées (par exemple, un polyacétylène) ayant une thermosensibilité à une température supérieure à 80 °C, ainsi qu'un colorant de polycarbocyanine ou un mélange de colorants de polycarbocyanine pouvant absorber de l'énergie dans la plage de longueurs d'onde de 400 à 1500 nm; ladite composition, quand elle est exposée à des émissions de lumière jusqu'à 1500 nm peut être encodée avec une image latente, qui peut ensuite être développée en une image visuelle par exposition à une source de rayonnement d'une longueur d'onde courte, tels que ceux transmis par la lumière ultraviolette, un faisceau d'électrons, des rayonnements gamma, des rayons X, des rayonnements bêta, des neutrons, des particules alpha et similaires. On décrit en outre la méthode permettant de former des images dans la composition susmentionnée, ainsi qu'un film d'enregistrement constitué de ladite composition.
PCT/US1991/006587 1990-10-23 1991-09-13 Composition permettant la formation d'images par laser WO1992007297A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60153790A 1990-10-23 1990-10-23
US601,537 1990-10-23

Publications (1)

Publication Number Publication Date
WO1992007297A1 true WO1992007297A1 (fr) 1992-04-30

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009081385A2 (fr) * 2008-01-25 2009-07-02 The Procter & Gamble Company Matériau thermoplastique contenant des substances polychromes
US20120021362A1 (en) * 2009-04-02 2012-01-26 Anthony Jarvis Laser Imaging
US9017425B2 (en) 2008-09-10 2015-04-28 Datalase Ltd. Textile colouration
US9580618B2 (en) 2012-12-19 2017-02-28 Innovia Films Limited Film
US9916777B2 (en) 2012-12-19 2018-03-13 Innovia Films Limited Label

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536473A (en) * 1983-10-11 1985-08-20 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4782006A (en) * 1985-12-16 1988-11-01 Canon Kabushiki Kaisha Optical recording employing diacetylene compound and dye to form and visualize a latent image
US4784934A (en) * 1986-12-15 1988-11-15 Gaf Corporation Sensitivity of processless recording media

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536473A (en) * 1983-10-11 1985-08-20 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4782006A (en) * 1985-12-16 1988-11-01 Canon Kabushiki Kaisha Optical recording employing diacetylene compound and dye to form and visualize a latent image
US4784934A (en) * 1986-12-15 1988-11-15 Gaf Corporation Sensitivity of processless recording media

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2470791C2 (ru) * 2008-01-25 2012-12-27 Дзе Проктер Энд Гэмбл Компани Термопластичный материал, содержащий полихромные вещества
US8211620B2 (en) 2008-01-25 2012-07-03 The Procter & Gamble Company Thermoplastic material comprising polychromic substances
WO2009081385A3 (fr) * 2008-01-25 2009-08-20 Procter & Gamble Matériau thermoplastique contenant des substances polychromes
CN101925469A (zh) * 2008-01-25 2010-12-22 宝洁公司 包含多色物质的热塑性材料
WO2009081385A2 (fr) * 2008-01-25 2009-07-02 The Procter & Gamble Company Matériau thermoplastique contenant des substances polychromes
CN101925469B (zh) * 2008-01-25 2013-05-29 宝洁公司 包含多色物质的热塑性材料及其加工方法
EP2082890A1 (fr) * 2008-01-25 2009-07-29 The Procter and Gamble Company Matériau thermoplastique comprenant des substances polychromes
US7897320B2 (en) 2008-01-25 2011-03-01 The Procter & Gamble Company Thermoplastic material comprising polychromic substances
US9017425B2 (en) 2008-09-10 2015-04-28 Datalase Ltd. Textile colouration
CN102804062A (zh) * 2009-04-02 2012-11-28 数据激光有限公司 激光成像
US20120021362A1 (en) * 2009-04-02 2012-01-26 Anthony Jarvis Laser Imaging
US8663902B2 (en) * 2009-04-02 2014-03-04 Datalase Ltd Laser imaging
CN102804062B (zh) * 2009-04-02 2015-06-10 数据激光有限公司 激光成像
US9580618B2 (en) 2012-12-19 2017-02-28 Innovia Films Limited Film
US9916777B2 (en) 2012-12-19 2018-03-13 Innovia Films Limited Label
US10125275B2 (en) 2012-12-19 2018-11-13 Innovia Films Limited Film

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