EP0587411B1 - Latent image receiving sheet and microcapsules for use therein - Google Patents

Latent image receiving sheet and microcapsules for use therein Download PDF

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Publication number
EP0587411B1
EP0587411B1 EP93307060A EP93307060A EP0587411B1 EP 0587411 B1 EP0587411 B1 EP 0587411B1 EP 93307060 A EP93307060 A EP 93307060A EP 93307060 A EP93307060 A EP 93307060A EP 0587411 B1 EP0587411 B1 EP 0587411B1
Authority
EP
European Patent Office
Prior art keywords
sheet
latent image
image receiving
receiving sheet
microcapsules
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
EP93307060A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0587411A2 (en
EP0587411A3 (en
Inventor
Robert E. Miller
Robert W. Brown
Lowell Schleicher
Lucy Feldman
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.)
Appvion Operations Inc
Original Assignee
Appleton Papers 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 Appleton Papers Inc filed Critical Appleton Papers Inc
Publication of EP0587411A2 publication Critical patent/EP0587411A2/en
Publication of EP0587411A3 publication Critical patent/EP0587411A3/en
Application granted granted Critical
Publication of EP0587411B1 publication Critical patent/EP0587411B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38271—Contact thermal transfer or sublimation processes using microcapsules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/055—Thermographic processes for producing printing formes, e.g. with a thermal print head
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/287—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using microcapsules or microspheres only

Definitions

  • This invention relates to record material in the form of a latent image receiving sheet.
  • U.S. Patent No. 4,529,681 discloses a light- and heat-sensitive record material relying on use of permeable capsules relying on heat to effect coloring component permeation through the thermoplastic capsule wall.
  • US-A-4873168 discloses heat treatment of an imaging sheet carrying a coating of microcapsules containing a radiation curable composition and an associated image-forming agent. Imaging is accomplished not by heating but by subjecting the microcapsules to a uniform rupturing force after they have been image-wise exposed to actinic radiation.
  • US-A-4682194 discloses a heat-sensitive recording material incorporating microcapsules having a glass transition point of from 60 to 200°C.
  • a latent image receiving sheet comprising a substrate carrying microcapsules containing a core material, characterized in that:
  • the invention also extends to the use of the latent image receiving sheet in a thermal imaging process, and to the latent imaging process itself.
  • the latent image receiving sheet can take the form of a variety of useful products including:
  • the latent image receiving sheet of the invention comprises a substrate bearing microcapsules having walls selected from non-meltable or thermoset resin.
  • the walls of the microcapsules are selected to have an elongation not more than 1%.
  • the non-meltable walls of the microcapsules rupture upon application thereto of a point source energy input comprising a ⁇ T of at least 115°C per one millisecond.
  • the latent image receiving sheet has adhered microcapsules having walls of thermosetting or non-meltable resin with critically an elongation of not more than 1%.
  • the thermosetting resin is selected from methylated methylol melamine, or selected from combinations of melamine and formaldehyde, or methylol melamine polymerized at a temperature of at least 65°C, preferably about 75°C.
  • the microcapsule walls are non-meltable.
  • the microcapsules can contain any core material conventionally used in microencapsulation. These can include various combinations of a solvent, a hydrophobic or hydrophillic material, liquid preferably hydrophobic liquid, gas, developer or chromogen, inks, dyes, toners, or pigments.
  • the novel sheet with microcapsules of the invention has a variety of new uses. Upon exposure of the sheet with microcapsules to a point source energy input comprising a ⁇ T ("change in temperature") of at least 115°C per one millisecond, the microcapsules rupture.
  • a point source energy input comprising a ⁇ T ("change in temperature") of at least 115°C per one millisecond
  • microcapsule and sheet material characteristics are described in terms of a point source energy input such as a thermal print head, it is readily apparent and understood that such record material or image receiving sheet can be imaged with a larger input device such as a rapidly heating block or multiplicity of thermal print heads assembled as a larger unit.
  • Point sources for purposes of the invention can take the form of a thermal print head, laser, focussed hot jets, heated stylus and the like.
  • the ability to effect a change in temperature of at least 115°C per one millisecond at the receiving sheet's surface is needed to effect the unusual shattering of the non-meltable capsules of the invention. Shattering is believed attributable to induced or produced thermal stresses though the invention disclosed herein should not be construed as limited to this one underlying theory, as other mechanisms may also be operating.
  • a latent image is recorded on the sheet by virtue of rupture of the microcapsules, which one can think of in terms of an assembly of sealed bottles, some of which, however, are selectively shattered so that they have open tops, thus becoming open containers.
  • An appropriate developer material can be applied across the surface of the sheet by conventional applicator means such as sponging, spraying, cotton swab or other applicator to develop the image.
  • a hydrophobic material is placed in the capsule, a hydrophobic ink or dye applied across the surface of the sheet will, preferentially, adhere to the hydrophobic material resulting in an image.
  • the capsules of the latent image receiving sheet unlike the prior art, do not melt or become porous, but rather fracture from the rapid change in temperature or energy input.
  • microcapsules are constructed such as to encapsulate a hydrophobic material, then after recording a latent image on the receiving sheet with a thermal print head, a hydrophobic ink can be applied across the surface of the sheet, and it will preferentially occupy the capsules with shattered tops exposing hydrophobic material when the freely applied hydrophobic ink is squeegeed or wiped away from the surface of the sheet.
  • hydrophillic materials can be encapsulated for use with hydrophillic inks. The result is a low-cost gravure type of print plate or transfer sheet.
  • ink or dye can be encapsulated in the capsules to also create a similar transfer sheet.
  • the substrate is typically selected of more rigid stock or even synthetic material for better durability.
  • the latent image receiving sheet can be used as optical recording medium, such as for recording of digitized information by laser or thermal print head.
  • the latent image receiving sheet also finds use for transfer of information in latent form. Being created by a thermal print head, transmission of cryptic messages is made possible.
  • the latent image can be subsequently developed as herein earlier described.
  • the capsules of the receiving sheet unlike the prior art, do not melt or become porous upon energy input, but rather fracture from the rapid change in temperature or energy input such as an energy pulse. Exposure of the receiving sheet to an energy input, such as with a thermal print head, or other source capable of generating the appropriate ⁇ T shatters the microcapsules and encodes the latent image.
  • the capsules of the latent image receiving sheet unlike the prior art, do not melt upon energy input, but rather appear to rupture from rapid change in temperature or energy input. Significantly this gives rise to a novel material which is heat resistant.
  • the latent image receiving sheet of the invention can be placed in a hot oven (150°C) for substantial time periods such as one minute and the capsules do not become permeable. Conventional thermal paper by contrast images in an oven almost instantaneously.
  • the insulating characteristics of the wall material and the absence of heat dissipation via phase change appears to lead to a high concentration of energy at the contact area between the point source and the capsule.
  • the elongation value for the wall material of the microcapsules can be taken from tables for various resins. The published values correlated well with the observed phenomena and provide a convenient means to select appropriate resins. Resins having elongation values of not more than 1% selected to be used as wall material result in microcapsules with nonmeltable polymeric shells or wall material displaying the unusual characteristics of shattering attributable to induced thermal stresses.
  • Table 1 summarizes elongation values for a variety of resin materials.
  • Resin Elongation (%) acetal 60-75 acrylic 20-50 cellulose 5-100 fluorcarb 80-400 ionomers 100-600 polyamides 25-300 polycarbonates 60-100 polyethylenes 5-900 polypropylenes 3-700 polystyrenes 1-140 vinyls 2-400 epoxies 1-70 phenolics 1-2 phenol formaldehyde 0.4-2 melamine formaldehyde 0.6-1.0 polyester 40-300 polyester alkyd 0.5-2 silicone 100 urea formaldehyde 0.5 urethane 300-1000 nylon 300
  • the elongation of the polymeric shells or wall is determined for purposes of the invention, from the elongation (%) value of the bulk resins when polymerized and using standards tests such as ASTM test method D638.
  • the wall of the capsules of the invention appears to rupture. Failure of the capsule wall appears attributed to a high temperature gradient and nonsteady state of heat transfer. Such conditions create localized thermal stresses. The magnitude of the stress depends on the properties of the material. A brittle wall can sustain less strain and thus ruptures.
  • Elongation properties appear to correlate well with wall brittleness and facilitate selection of resin.
  • the capsules of the invention surprisingly fracture upon application of a point source energy input comprising a change in temperature ( ⁇ T) of at least 115°C per one millisecond.
  • ⁇ T is T-To in the above formula.
  • S which is stress ranges for melamine formaldehyde polymers from 5x10 3 psi to 13x10 3 psi and for phenol formaldehyde polymers ranges from about 5x10 3 psi to about 9x10 3 psi.
  • S is taken as (5x10 3 ) psi.
  • the modulus of elasticity ranges from about (11x10 5 ) to (14x10 5 ) psi.
  • E is taken as 11x10 5 .
  • the coefficient of linear thermal expansion is (4x10 -5 )°C.
  • the calculated threshold ⁇ T is about 115°C.
  • Example 1 demonstrates that the temperature at the record system surface when using a conventional fax such as a Canon Fax 230 is greater than 170°C. This is the temperature that the surface of the paper or media sees. The temperature of the thermal print head is higher, but the temperature observed at the surface of the media is alone relevant as regards the thermal stresses to which the capsules on the surface of the paper are subjected.
  • capsules are nonmeltable or thermoset in character, there is no latent heat capacity and substantially no phase change.
  • the latent image receiving sheet when subjected to a thermal print head resulted in ruptured capsules observed with a scanning electon microscope.
  • the capsule core material can include inks, dyes, toners, chromogens, solvents, gases, liquids, and pigments.
  • the capsule core material is relatively independently selected.
  • the core can be any material which is substantially water insoluble. Extensive lists of other core materials are listed in U.S. Patent 4,001,140.
  • the core material can be any material dispersible in water and wrappable by the wall material. This can include air.
  • an imaging material such as chromogen, dye, toner, or pigment and the like can be prepositioned in the microcapsules as the core material.
  • the core can be selected to be colorless electron donating compounds, dye precursor or chromogens which form color by reacting with a developer material.
  • Such compounds include substantially colorless compounds having a lactone, a lactam, a sulfone, a spiropyran, an ester or an amido structure in their partial skeleton such as triarylmethane compounds, bisphenylmethane compounds, xanthene compounds, fluorans, thiazine compounds, spiropyran compounds and the like.
  • Eligible electron donating dye precursors which are chromogenic compounds, such as the phthalide, leucauramine and fluoran compounds, for use in the color-forming system are well known.
  • the chromogens include Crystal Violet Lactone (3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide.
  • U.S. Patent No. Re. 23,024 phenyl-, indol-, pyrrol-, and carbazol-substituted phthalides (for example, in U.S. Patent Nos.
  • Patent 4,510,513 also known as 3-dibutylamino-6-methyl-7-anilino-fluoran; 3-dibutylamino-7-(2-chloroanilino) fluoran; 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-3-5'6-tris(di-methylamino)spiro[9H-fluorene-9'1(3'H)-isobenzofuran]-3'-one; 7-(1-ethyl-2-methylindol-3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one(U.S.
  • Patent No. 4,246,318 3-diethylamino-7-(2-chloroanilino)fluoran (U.S. Patent No. 3,920,510); 3-(N-methylcyclohexylamino)-6-methyl-7-anilino-fluoran (U.S. Patent No.
  • Solvents such as the following can optionally be included in the microcapsules:
  • the solvent if included, can be selected to facilitate dissolving the dye mixture, if included.
  • the latent image of the receiving sheet can be made visible by various conventional acidic developer materials preferably as dispersions or solutions applied to the latent image receiving sheet following application of the latent image. Other variations can include prepositioning the acidic developer material in substantially contiguous relationship to the chromogen material. Developer can be positioned in the capsules and chromogen applied following rupture, or alternatively, chromogen can be positioned in the capsules.
  • eligible acidic developer material examples include: clays, treated clays (U.S. Patent Nos. 3,622,364 and 3,753,761); aromatic carboxylic acids such as salicylic acid; derivatives of aromatic carboxylic acids and metal salts thereof (U.S. Patent No, 4,022,936); phenolic developers (U.S. Patent Nos. 3,244,550 and 4,573,063); acidic polymeric material such as phenol-formaldehyde polymers, etc. (U.S. Patent Nos. 3,455,721 and 3,672,935); and metal-modified phenolic resins (U.S. Patent Nos. 3,732,120; 3,737,410; 4,165,102; 4,165,103; 4,166,644 and 4,188,456).
  • U.S. Patent No. 4,100,103 describes a method for capsule formation involving reaction between melamine and formaldehyde; British Patent No. 2,062,750 describing a process for producing microcapsules having walls produced by polymerization of melamine and formaldehyde in the presence of a styrenesulfonic acid.
  • British Patent No. 2,062,750 describing a process for producing microcapsules having walls produced by polymerization of melamine and formaldehyde in the presence of a styrenesulfonic acid.
  • the process of U.S. Patent No 4,552,811 is preferred. Reference can be made to these patents for further details.
  • the latent image receiving sheet includes a substrate or support material which is in sheet form.
  • sheets can be referred to as support members and are understood to also mean webs, rolls, ribbons, tapes, belts, films, cards and the like. Sheets denote articles having two large surface dimensions and a comparatively small thickness dimension.
  • the substrate or support material can be opaque, transparent or translucent and could, itself, be colored or not.
  • the material can be fibrous including, for example, paper and filamentous synthetic materials. It can be a film including, for example, cellophane and synthetic polymeric sheets cast, extruded or otherwise formed.
  • Binder material can be included to assist adherence of the capsules to the substrate and can include materials such as polyvinyl alcohol, hydroxy ethylcellulose, methylcellulose, methyl-hydroxypropylcellulose, starch, modified starches, gelatin and the like. Latex such as polyacrylate, styrene-butadiene, rubber latex, polyvinylacetate and polystyrene can also be advantageously used.
  • Coatings of color former dispersion were prepared on a thin translucent paper substrate. Segments of the coatings were taped to a sheet of bond paper and used as the copy sheet in a Canon Fax-230. Melting was readily evident as clear (amorphous) characters on a relatively opaque background. Using this technique, the temperature at the surface of the media or sample was determined to be at least above 170°C with a Canon Fax-230. Color Former Melting Temp. + Melt in Fax? diButyl N102 ⁇ 170°C Yes PSD-150 ⁇ 200°C No Green 118 ⁇ 230°C No + As determined using the grinds on Kofler Hot Bar
  • TMPTA Trimethylolpropane triacrylate
  • Photo Initiator 2 g Ethyl-4-Dimethylamino benzoate
  • Photo Initiator 24 g 2,2-Dimethoxy-2-phenyl acetophenone Photo Initiator
  • This mixture is applied to paper or other desired substrate using, for example, a fixed gap applicator set at 2.54 x 10 -5 m (0.001 inch).
  • the resultant dried coating can be used to make a latent copy in a thermal printer such as a commercial facsimile machine.
  • the latent image copy can be developed by contacting with or applying on an appropriate developer for the N102 color former.
  • a typical example would be a 20% solution of Durez #27691 (p-phenylphenol formaldehyde resin) in xylene.
  • the resin can also be applied in aqueous dispersion or emulsion form and then heated to promote the development of the black copy.
  • the resultant copy may be "fixed” or deactivated to thermal and/or pressure response by exposing to U.V. to polymerize the components. Approximately 5 second exposure to 15 Watt GE Bulbs (F15T8-BLB) is sufficient to "fix” the copy. After fixing, the sheet is resistant to scuff or abrasive induced markings.
  • the coating can suffer handling damage. This damage can be reduced by applying an overcoat that does not interfere with the thermal imaging nor with the subsequent fixing exposure.
  • a typical overcoat would be the application of a 10% aqueous solution of Airvol* 540 using a #3 wire wound rod.
  • the photoinitiators can be omitted in the capsules of the latent image receiving sheet. Chromogen can be optionally included or excluded as desired. *Airvol is a trade mark of Air Products and Chemicals, Inc. and is a polyvinyl alcohol.
  • Example 2 With heating, dissolve the resin in the TMPTA, then add the photoinitiator and dissolve.
  • This IP was encapsulated as in Example 2 and resultant capsule dispersion coated and top coated.
  • the coated media was run through a commercial facsimile to produce an image.
  • This image was developed by application of a commercial toner such as Minolta MT Toner II.
  • the black toner particles selectively adhere to the image-wise broken capsules.
  • Toner in the background was removed by gentle brushing, etc.
  • the toner is fused by heating in an oven or on a heated drum or the like.
  • Multicolor images can be obtained using repetition of the process.
  • TMPTA trimethylolpropanetriacrylate
  • This IP was encapsulated as in Example 1 and resultant capsule dispersion applied to suitable substrate using a #12 wire wound rod.
  • the coating was dried and top coated with a 10% aqueous solution of Airvol 540 using a #3 wire wound rod.
  • the coated media was run through a commercial facsimile to produce a master image.
  • the master image was heated in contact with a developer sheet, a copy was obtained due to sublimation of the spiran from the image-wise broken capsules.
  • the imaged master could be used multiple times to make additional copies. Imaged copies are obtained on a commercially available carbonless CF sheet such as comprised of a p-phenylphenol formaldehyde type resin.

Landscapes

  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermal Sciences (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Printing Methods (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Toys (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
EP93307060A 1992-09-10 1993-09-07 Latent image receiving sheet and microcapsules for use therein Expired - Lifetime EP0587411B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US94308992A 1992-09-10 1992-09-10
US943089 1992-09-10

Publications (3)

Publication Number Publication Date
EP0587411A2 EP0587411A2 (en) 1994-03-16
EP0587411A3 EP0587411A3 (en) 1996-04-10
EP0587411B1 true EP0587411B1 (en) 1997-11-12

Family

ID=25479086

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93307060A Expired - Lifetime EP0587411B1 (en) 1992-09-10 1993-09-07 Latent image receiving sheet and microcapsules for use therein

Country Status (7)

Country Link
EP (1) EP0587411B1 (es)
JP (1) JPH06210156A (es)
AT (1) ATE160113T1 (es)
CA (1) CA2092232C (es)
DE (1) DE69315150T2 (es)
ES (1) ES2108831T3 (es)
FI (1) FI109190B (es)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001023081A1 (fr) * 1999-09-29 2001-04-05 Matsumoto Yushi-Seiyaku Co., Ltd. Procede de fabrication de microcapsules thermoexpansibles
DE102011000311A1 (de) 2011-01-05 2012-07-05 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Einlegekörper zum Einlegen in eine Lagervorrichtung
AU2012379930A1 (en) * 2012-05-18 2014-12-04 Claudio Selva Method and apparatus for providing a support for the transfer of an univocal design, and support thereby obtained

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5991438A (ja) * 1982-11-17 1984-05-26 Fuji Photo Film Co Ltd 感光感熱記録材料
JPS60242094A (ja) * 1984-05-17 1985-12-02 Fuji Photo Film Co Ltd 感熱記録材料
US4873168A (en) * 1988-03-07 1989-10-10 The Mead Corporation Imaging system utilizing heat treatment

Also Published As

Publication number Publication date
FI109190B (fi) 2002-06-14
ES2108831T3 (es) 1998-01-01
ATE160113T1 (de) 1997-11-15
CA2092232A1 (en) 1994-03-11
EP0587411A2 (en) 1994-03-16
CA2092232C (en) 2003-12-09
DE69315150D1 (de) 1997-12-18
FI933936A0 (fi) 1993-09-08
FI933936A (fi) 1994-03-11
EP0587411A3 (en) 1996-04-10
DE69315150T2 (de) 1998-03-05
JPH06210156A (ja) 1994-08-02

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