US3445261A - Heat-sensitive record material - Google Patents

Heat-sensitive record material Download PDF

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Publication number
US3445261A
US3445261A US3445261DA US3445261A US 3445261 A US3445261 A US 3445261A US 3445261D A US3445261D A US 3445261DA US 3445261 A US3445261 A US 3445261A
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Prior art keywords
material
coating
water
record
heat
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Expired - Lifetime
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Shashikant G Talvalkar
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Appvion Inc
NCR Corp
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NCR Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337Additives; Binders
    • B41M5/3372Macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/423Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/44Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31801Of wax or waxy material
    • Y10T428/31804Next to cellulosic
    • Y10T428/31808Cellulosic is paper

Description

United States Patent US. Cl. 117-363 1 Claim ABSTRACT OF THE DISCLGSURE There is provided by this invention an improved heatsensitive record material wherein such material, comprises: (1) a base sheet such as paper; (2) a coating of finely dispersed acidic particles such as a di-phenol, finely dispersed colorless chromogenic particles such as a benzoindolinospiropyran derivative which give color when in liquid contact with an acidic material, and a film-forming polymeric material such as polyvinyl alcohol to act as a matrix for the two color-forming reactants; and 0ptionally; (3) a protective overcoat such as a film of polyvinyl alcohol which may also have soditun carboxy methyl cellulose present in it to give a proper viscosity to the coating slurry for ease in machine application; is made resistant to pick-off of the record sheet surface and freezesticking of the record sheet to the printing head when the record material is used in conjunction with a rapidly heated and cooled printing head, particularly one of the planographic class. The improvement consists of providing the heat-sensitive record material with a lubricating overcoat comprising a film of hydrophilic, polymeric material, such as polyvinyl alcohol (with or without added sodium carboxy methyl cellulose), having dispersed therein to the extent of about 2% fine particles of a lubricating or nontacky wax, melting about 140 C.; optionally a primer coat of the same composition; and finally as a further option an added dispersion of calcium stearate in the coating or layer which bears the colorforming coreactants.

This invention relates to heat-sensitive coated record material that will not pick-01f onto hot type surfaces.

Heat-sensitive record materials of the type shown in an application for Letters Patent of the United States, Ser. No. 366,524, filed by Henry H. Baum on May 11, 1964, owe their heat-sensitive characteristics to a thermoplastic film coating which contains in it heat-responsive chemically reactive color-producing material in dispersed solid particulate form. The flowing together of these materials under conditions of the coatings being subjected to a printing contact with hot type causes coloration of the film coating at the typed points.

As long as the applied type is hot as it is withdrawn from contact with the record material and does not pick up the melted material, all is Well, and there is no picko'if problem to spoil the print or dirty the type face. However, there have been developed planographic surface printing plates or surfaces that have heatable matrices flush with the lano-surface, which matrices are selectively operable by flash heating to print the selected symbol. These symbols, for example, may be made up of selected elements of a Solomons Seal type of matrix, which elements are, individually for an instant, rendered very hot (250 degrees centigrade) and suddenly cooled by heat conduction into a heat sink to make them ready for printing another selected symbol, the record material being advanced or moved across the printing plate between symbol-printing operations to form a contextual data message. The heating and sudden cooling of the type face may freeze the melted film to the printer plate, re-

3,445,261 Patented May 20, 1969 sulting in rupture of the film coating or its supporting substrate of paper or paper-like material and, in addition, fouling the printing head. A printer head of the planar matrix type is disclosed in United States Patent No. 3,161,457, which issued on the application of Hans Schroeder et al. on Dec. 15, 1964.

A preferred embodiment of a pair of heat-sensitive reactants selected from among those appearing in the Baum disclosure, and as used in a coating system for the purpose of providing the anti-pick record material of this invention, is the pair comprising, as the color reactants, (a) the chromogenic material ture and having a melting point of 156 degrees centigrade. This acidic material will be called Bis phenol A, as it is commonly sold under that designation.

These reactants may be dispersed as solid fine particles in a water solution of a suitable grade If polyvinyl alcohol and water-wettable calcium stearate, and the dispersion may be applied to and subsequently dried on a prepared paper sheet to produce a heat-sensitive coating which responds by blue coloration to hot type pressed thereagainst. This coated sheet has the infirmity, however, of sticking to or picking-off onto a planographic type surface having rapidly heating and cooling configurations adjacent to constantly cool areas (room temperature) across which the sheet is passed step by step. The damage to the record is more apparent with finer printing than with larger printing, as would be obvious, so the invention is mainly directed to a pressing problem with fineprinting species of planar printing heads. The printing head itself, by picking up the coating, is likewise subject to fouling and consequently is rendered incapable of giving a sharp print.

It has been found that, by confining the heat-sensitive film coating between an under layer of sheet-supported film material of polyvinyl alcohol, sodium carboxymethyl cellulose (CMC), and Acra Wax C, and an overlayer or top coating of the same material, and by providing the so-sandwiched color-producing film coating with calcium sterate particles, the sticking, or picking-oil", of the material onto the planar printing element is prevented, and the sharp print property is preserved.

Acra Wax C is a reaction product of hydrogenated castor oil and ethanola-mine, is insoluble in boiling water, and has a melting point of to 143 degrees centigrade, a flash point of 285 degrees centigrade (open cup), and a specific gravity of 0.97 at 25 degrees centigrade. It may be purchased as a fine powder under the quoted brand name from Glyco Chemicals, Inc., 417 Fifth Avenue, New York, N.Y., United States of America. Although Acra Wax C has been specified as preferred, any similar anti-blocking wax or nontacky wax in powdered form and insoluble in water may be used and will be specified in the claims as nontacky Wax.

The calcium stearate used is of fine powder particle size and has water-Wettable characteristics to permit of its dispersion in a water solution of polyvinyl alcohol. A suitable material is the Disperso grade of Witco Chemical Company, Inc., 122 East Forty-Second Street, New York, N.Y., United States of America, but the controlling factor in its selection, from whatever source it is obtained, is that of its dispersibility in water, so the preferred embodiment will be specified as water-dispersible calcium stearate powder.

The polyvinyl alcohol preferred for the substrate coating (or primer) is a medium-viscosity grade of 99% hydrolysis, and this grade also is used for the overcoating. while one of 98% hydrolysis is used for the middle layer, containing the calcium stearate and the dispersed mixture of color reactants. Water solutions of the specified polyvinyl alcohols gel at room temperature (20 to 25 degrees centigrade). Polyvinyl alcohols of this type can be purchased as Elvanol brand from E. I. DuPont de Ncmours and Company, Inc., of Wilmington, Del., United States of America, their grade 71-30 being of 99% hydrolysis and their grade 71-24 being of 98% hydrolysis. The medium-viscosity range of these materials lies between 23 and 32 centipoises in a 4% water solution at 20 degrees centigrade as determined by the Hoeppler falling-ball method.

The primer and the top coating composition contain sodium carboxy methyl cellulose, with enough sodium carboxymethyl groups to make it water-soluble. This kind of material and the process of making it are set out in the pamphlet Hercules Cellulose Gum Properties and Uses, printed and copyrighted in 1960 by Hercules Powder Company, Wilmington, Del., United States of America. It lends a coating viscosity property to the coating composition as a whole, but, as it is not an essential in the coloror mark-forming property of the record material, equivalents acting with the same physical properties may be substituted therefor.

Other waxes, other metal stearates, and heat-meltable gels of other water-soluble polymers having characteristics similar to those of the preferred materials may be substituted because these materials are used for their physical characteristics of antitackiness, temperature melting, film-forming characteristics, and general aptitude for forming a compatible reaction environment for the color reactants.

EXAMPLE I In this, the preferred, embodiment, the substrate is bond paper of 13 pounds weight per ream of 500 sheets 17 by 22 inches having a medium calendered surface.

The primer coating for it when dried is one pound per specified ream, and the wet composition is as follows:

Percent solids Polyvinyl alcohol (99% +hydrolyzed) 73 Sodium carboxymethyl cellulose (water-soluble) 25 Acra Wax C 2 Water, to make a suitable coating dispersion.

The color-reactant-containing middle coating of 3.25 pounds per specified ream is as follows:

Percent solids 6-Cl, 8-OCH BIPS 15 Polyvinyl alcohol (98% hydrolyzed) 15 Bis phenol A 65 Calcium stearate water-wettable The BIPS type of compound may color slightly prematurely on aging, and this may be prevented by adding to the composition of the coating several percent of the compound 2,4-bis-acetoamido ethane. As a practical matter in making a water solution-dispersion of the solids, a nominal amount of defoaming and dispersing agents may be used.

The top coating is 1.75 pounds per specified ream (dry) of the same composition used for the primer coating.

The essential feature of the invention is the use of powdered nontacky wax in the primer coating and the top coating, and a small percentage of a metal stearate in the middle coating, which contains the color-reactant com ponents, the latter not being restricted to the patricular MP8 or to the acid phenolic material noted in the preferred example but being applicable, for example, where the reactant systems may be selected from among the many disclosed in the Baum United States patent application to which reference has been made. Another pair of color reactants useful and representing another type of chromogenic material is crystal violet lactone and Bis phenol A.

The practitioner of this invention may use the solid powdered nontacky-when-melted wax in any record material coating meant to be melted to cause the bringing together of the color reactants and otherwise having a composition tending to be picked-off by hot type members as they are cooled.

EXAMPLE II This is the same as Example I except that the primer coating is omitted. The heat-sensitive record material of this example performs satisfactorily, but it is not as completely free of film-coating rupture when in contact with the printing head as the material of Example I which has been designated the preferred embodiment.

I claim:

1. In a record material including a base sheet having a coating of heat-meltable hydrophilic film-forming material having dispersed in the coating powdered chromogenic material of substantially colorless state and particles of heat-meltable acid phenol compound which when in liquid contact with the chromogenic material reacts therewith to form color, the improvement of also including an overcoating of polymeric film-forming material of hydrophilic characteristics having dispersed therein to the extent of about 2 percent particles of a wax nonblocking when melted, said polymeric film-forming material consisting of about three parts of polyvinyl alcohol and about one part of water-soluble sodium carboxy methyl cellulose.

References Cited UNITED STATES PATENTS 2,348,128 5/1944 Groak 11736.4 2,777,781 1/ 1957 Kordig et al 117-3 6.4 2,943,952 7/ 1960 Clark 1l736.4 3,062,676 11/ 1962 Newman et al 117-36.4 3,076,721 2/ 1963 Coles et al. 1l736.9 3,108,896 10/1963 Owen 117 36.9 3,111,423 11/1963 Ostlie 117-36.9 3,244,550 5/1966 Farnham et al. 11736.8 3,347,696 10/1967 Newman 11736.4

FOREIGN PATENTS 953,150 3/1964 Great Britain.

MURRAY KATZ, Primary Examiner.

US. Cl. X.R.

US3445261A 1965-10-23 1965-10-23 Heat-sensitive record material Expired - Lifetime US3445261A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
US3792481A (en) * 1971-07-13 1974-02-12 Canon Kk Method of recording by heat sensitive multicolor indication
US3970769A (en) * 1973-10-12 1976-07-20 Fuji Photo Film Co., Ltd. Recording sheet and method for the production thereof
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4065595A (en) * 1974-11-05 1977-12-27 Weber Marking Systems, Inc. Thermographic stencil sheet and method of making an imaged stencil sheet
US4097288A (en) * 1977-02-25 1978-06-27 Lawton William R Heat sensitive recording composition containing a complexed phenolics and a spiropyran or leuco lactone
US4255491A (en) * 1978-07-18 1981-03-10 Fuji Photo Film Co., Ltd. Heat-sensitive recording paper
US4283458A (en) * 1978-08-18 1981-08-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording paper containing a novel electron accepting compound
US4288531A (en) * 1978-12-20 1981-09-08 Eastman Kodak Company Imaging elements
US4333984A (en) * 1979-12-18 1982-06-08 Fuji Photo Film Co., Ltd. Heat-sensitive recording sheets
FR2501398A1 (en) * 1981-03-05 1982-09-10 Ricoh Kk Sheet labeling has thermosensitive recording
EP0076490A1 (en) * 1981-10-05 1983-04-13 Kuraray Co., Ltd. Paper coating agent
FR2521070A1 (en) * 1982-02-05 1983-08-12 Ricoh Kk thermosensitive recording sheet
US4567019A (en) * 1977-05-11 1986-01-28 Graphic Controls Corporation Color reversing compositions
US5614463A (en) * 1983-07-25 1997-03-25 Dai Nippon Insatsu Kabushiki Kaisha Heat transferable sheet
US20020155372A1 (en) * 2000-06-01 2002-10-24 Sipix Imaging, Inc. Imaging media containing heat developable photosensitive microcapsules
US20050156013A1 (en) * 2004-01-21 2005-07-21 Bhatti Mohinder S. Method of making high performance heat sinks
US20100266322A1 (en) * 2009-04-17 2010-10-21 Timothy Croskey Apparatus and method for destroying confidential medical information on labels for medicines

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2931083C2 (en) * 1978-08-01 1982-02-25 Ricoh Co., Ltd., Tokyo, Jp
JPS57144793A (en) * 1981-03-05 1982-09-07 Ricoh Co Ltd Heatsensitive recording material

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2348128A (en) * 1941-06-30 1944-05-02 Groak Josef Transfer copying materials
US2777781A (en) * 1955-03-04 1957-01-15 Ditto Inc Transfer sheet having waxy top protective coating
US2943952A (en) * 1956-12-14 1960-07-05 Burroughs Corp Method of making duplicating transfer sheet and resultant article
US3062676A (en) * 1959-09-09 1962-11-06 Columbia Ribbon & Carbon Smudge-resistant pressure-sensitive transfer element for placing smudgeresistant marks
US3076721A (en) * 1959-10-19 1963-02-05 Minnesota Mining & Mfg Heat-sensitive copy-paper and method of making
US3108896A (en) * 1959-10-26 1963-10-29 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3111423A (en) * 1960-05-16 1963-11-19 Minnesota Mining & Mfg Heat-sensitive copy-sheet
GB953150A (en) * 1961-10-05 1964-03-25 Ncr Co A temperature-colourable record copy sheet
US3244550A (en) * 1961-08-31 1966-04-05 Burroughs Corp Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking
US3347696A (en) * 1961-12-27 1967-10-17 Columbia Ribbon & Carbon Thermographic method of imaging a copy sheet

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2348128A (en) * 1941-06-30 1944-05-02 Groak Josef Transfer copying materials
US2777781A (en) * 1955-03-04 1957-01-15 Ditto Inc Transfer sheet having waxy top protective coating
US2943952A (en) * 1956-12-14 1960-07-05 Burroughs Corp Method of making duplicating transfer sheet and resultant article
US3062676A (en) * 1959-09-09 1962-11-06 Columbia Ribbon & Carbon Smudge-resistant pressure-sensitive transfer element for placing smudgeresistant marks
US3076721A (en) * 1959-10-19 1963-02-05 Minnesota Mining & Mfg Heat-sensitive copy-paper and method of making
US3108896A (en) * 1959-10-26 1963-10-29 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3111423A (en) * 1960-05-16 1963-11-19 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3244550A (en) * 1961-08-31 1966-04-05 Burroughs Corp Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking
GB953150A (en) * 1961-10-05 1964-03-25 Ncr Co A temperature-colourable record copy sheet
US3347696A (en) * 1961-12-27 1967-10-17 Columbia Ribbon & Carbon Thermographic method of imaging a copy sheet

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619239A (en) * 1968-12-10 1971-11-09 Fuji Photo Film Co Ltd Pressure sensitive copying paper
US3792481A (en) * 1971-07-13 1974-02-12 Canon Kk Method of recording by heat sensitive multicolor indication
US3970769A (en) * 1973-10-12 1976-07-20 Fuji Photo Film Co., Ltd. Recording sheet and method for the production thereof
US4065595A (en) * 1974-11-05 1977-12-27 Weber Marking Systems, Inc. Thermographic stencil sheet and method of making an imaged stencil sheet
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4097288A (en) * 1977-02-25 1978-06-27 Lawton William R Heat sensitive recording composition containing a complexed phenolics and a spiropyran or leuco lactone
US4567019A (en) * 1977-05-11 1986-01-28 Graphic Controls Corporation Color reversing compositions
US4255491A (en) * 1978-07-18 1981-03-10 Fuji Photo Film Co., Ltd. Heat-sensitive recording paper
US4283458A (en) * 1978-08-18 1981-08-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording paper containing a novel electron accepting compound
US4288531A (en) * 1978-12-20 1981-09-08 Eastman Kodak Company Imaging elements
US4333984A (en) * 1979-12-18 1982-06-08 Fuji Photo Film Co., Ltd. Heat-sensitive recording sheets
FR2501398A1 (en) * 1981-03-05 1982-09-10 Ricoh Kk Sheet labeling has thermosensitive recording
EP0076490A1 (en) * 1981-10-05 1983-04-13 Kuraray Co., Ltd. Paper coating agent
FR2521070A1 (en) * 1982-02-05 1983-08-12 Ricoh Kk thermosensitive recording sheet
US5614463A (en) * 1983-07-25 1997-03-25 Dai Nippon Insatsu Kabushiki Kaisha Heat transferable sheet
US20020155372A1 (en) * 2000-06-01 2002-10-24 Sipix Imaging, Inc. Imaging media containing heat developable photosensitive microcapsules
US6740465B2 (en) 2000-06-01 2004-05-25 Sipix Imaging, Inc. Imaging media containing heat developable photosensitive microcapsules
US20050156013A1 (en) * 2004-01-21 2005-07-21 Bhatti Mohinder S. Method of making high performance heat sinks
US7537151B2 (en) * 2004-01-21 2009-05-26 Delphi Technologies, Inc. Method of making high performance heat sinks
US20100266322A1 (en) * 2009-04-17 2010-10-21 Timothy Croskey Apparatus and method for destroying confidential medical information on labels for medicines

Also Published As

Publication number Publication date Type
DE1571857B2 (en) 1971-12-16 application
GB1099880A (en) 1968-01-17 application
DE1571857A1 (en) 1971-01-21 application

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Owner name: APPLETON PAPERS INC.

Free format text: MERGER;ASSIGNORS:TUVACHE, INC.;GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS);REEL/FRAME:004108/0262

Effective date: 19811215