US3674535A - Heat-sensitive record material - Google Patents

Heat-sensitive record material Download PDF

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Publication number
US3674535A
US3674535A US3674535DA US3674535A US 3674535 A US3674535 A US 3674535A US 3674535D A US3674535D A US 3674535DA US 3674535 A US3674535 A US 3674535A
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Prior art keywords
material
record
heat
record material
bisphenol
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Expired - Lifetime
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James H Blose
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
    • B41M5/30Thermography ; 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
    • B41M5/3375Non-macromolecular 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
    • B41M5/30Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333Colour developing components therefor, e.g. acidic compounds
    • B41M5/3338Inorganic 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

Abstract

A HEAT SENSITIVE RECORD MATERIAL WHICH COMPRISES (1) A BASE SHEET SUCH AS PAPER, AND (2) A COATING OF A COLORLESS CHROMOGENIC MATERIAL AND A BISPHENOL DISTRIBUTED IN A POLYVINYL ALCOHOL IN COMBINATION WITH A FILLER SUCH AS CLAY, A LUBRICANT SUCH AS ZINC STEARATE AND A NONTACKY WAX. CONVENTIONAL WETTING AGENTS AND DEFOAMERS ALSO ARE PRESENT IN THE RECORD MATERIAL. THIS MATERIAL IS RESISTANT TO PICK-OFF OF THE RECORD SHEET SURFACE AND FREEZESTICKING OF THE RECORD SHEET TO THE PRINTING HEAD WHEN THE RECORD MEATERIAL IS USED IN CONJUNCTION WITH A RAPIDLY HEATED AND COOLED PRINTING HEAD.

Description

Patented July 4, 1972 3,674,535 HEAT-SENSITIVE RECORD MATERIAL James H. Blose, Dayton, and Shashikant G. Talvalkar, Xenia, Ohio, assignors to The National Cash Register Company, Dayton, Ohio No Drawing. Filed July 15, 1970, Ser. No. 55,233 Int. Cl. B41m /18 U.S. Cl. 117-363 2 Claims ABSTRACT OF THE DISCLOSURE A heat sensitive record material which comprises (1) a base sheet such as paper, and (2) a coating of a colorless chromogenic material and a bisphenol distributed in a polyvinyl alcohol in combination with a filler such as clay, a lubricant such as zinc stearate and a nontacky wax. Conventional wetting agents and defoamers also are present in the record material. This material is 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.

This invention relates to heat-sensitive coated record material that does not pick-off onto hot type surfaces.

Heat-sensitive record materials of the type shown in an application for Letters Patent of the United States, Ser. No. 808,379, filed by Henry H. Baum on Mar. 14, 1969, now U .8. Pat. No. 3,539,375, 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, there is no pick-off 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 planosurface, which matrices are selectively operable by flash heating to print the selected symbol. These symbols, for example, can be made up of selected elements of a Solomons Seal type martix, which elements are, individually for an instant, rendered very hot (250 degrees centi grade) 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 or a single thermal head moved across the medium to form a contextual data message. The heating and sudden cooling of the type face can freeze the melted film to the printer plate, resulting in rupture of the film coating or its supporting substrate of paper or paper-like material and, in addition, fouling the printing head.

It has been discovered that the heat-sensitive reactants of the Baum disclosure can be employed in the anti-pick record material of this invention. Generally, the color reactants are comprised of the pair 3,3-bis(4-dimethylaminophenyl G-dimethylaminophenyl phthalide, hereinafter referred to as crystal violet lactone or CVL, and a bis phenol such as 4,4'-isopropylidenediphenol.

These reactants can be dispersed as solid fine particles in a water solution of a suitable grade of polyvinyl alcohol. The dispersion can 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 in another embodiment, the thermal head is moved across the medium and is cooled between the printing of two symbols. The damage to the record is more apparent with finer printing than with larger printing, as would be obvious. 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 combining the thermal sensitive dye and bisphenol with a filler, lubricant and wax, the sticking, or picking-off, of the materials onto the planar printing element is prevented, and the sharp print property is preserved. The resulting thermal medium is extremely stable to wide ambient conditions, i.e., at temperatures ranging from 0 to 140 F. and relative humidities ranging from 0 to percent.

As noted above, crystal violet lactone is the colorless chromogenic material. The phenols that can be employed in this invention have a low vapor pressure. Normally, the phenols liquefy or vaporize to a sufficient extent at the usual thermographic temperatures of 150 to 200 C. Examples of the phenols that can be employed in this invention are disclosed in the above-mentioned Baum disclosure.

The colorless chromogenic material and bisphenol are distributed in a polyvinyl alcohol film, which acts as a binder to hold the chemicals together on the support means. The polyvinyl alcohol preferred is a medium-viscosity grade of 99 percent hydrolysis. Various binders are Elvan-ols from Dupont, Vinols from Air Reduction and other non-reacting water soluble binders.

The fillers that can be employed in the invention are at least partially reactive with the colorless chromogenic material. Specific examples are Klondyke clay and other filler materials such as titanium dioxide, zinc oxide, clays, silicates and carbonates which are insoluble in water.

Lubricants also are employed in this invention. Generally, the lubricants increase light fade resistance as well as lubricate. Specific examples are zinc stearate's as well as other water insoluble stearates of calcium, iron, cobalt, nickel, aluminum, manganese, lead and the like.

The release agent is of high enough melting point so that it will not melt and react with the coating under normal storage conditions. A wide variety of waxes can be employed in this invention, preferably Acra Wax C is employed.

Acra Wax C is a reaction product of hydrogenated castor oil and ethanolamine, 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 can be purchased as a fine powder under the quoted brand name from Glyco Chemicals, Inc., 417 Fifth Avenue, New York, New York, United States of America. Although Acra Wax C has been specified as preferred, any similar anti-blocking Wax or nontacky wax in powdered form can be used and will be specified in the claims as nontacky wax.

Small amounts of conventional materials such as wetting agents and defoamers can be employed in the record material of this invention.

Under processing conditions, separate dispersions of the colorless chromogenic material and bisphenol are made to reduce excessive discoloration of the wet color. Generally, the dye dispersion comprises crystal violet lactone and polyvinyl alcohol with small amounts of wetting agent and defoamer. The bisphenol dispersion comprises bisphenol, polyvinyl alcohol, clay, nontacky wax and a lubricant with small amounts of a wetting agent and defoamer.

Each dispersion can be comprised of 15 to 40 percent solids in water, preferably 20 to 30 percent. For example, for every 100 grams of dispersion there is 20 grams of dry solids and 80 grams of water. Generally, a period of time ranging from 8 to 24 hours is allowed to pass before the two dispersions are contacted with each other in order to reduce excessive discoloration of the wet color.

The amounts of material in the final formulation generally are as follows. Crystal violet lactone ranges from 3 to 9' percent by weight, bisphenol ranges from 39 to 41 percent by weight and polyvinyl alcohol ranges from 20 to 30 percent by weight. The final formulation also comprises about 20 weight percent filler, about 2 weight percent lubricant and about 2 weight percent release agent. Small amounts of a wetting and a defoamer also are present, generally less than 1 weight percent.

The particle size of the final formulation generally is in the range of 3 to 6 microns.

The support sheets that can be employed in this invention are those disclosed in the above-mentioned Baum disclosure.

The following example further illustrates the invention.

EXAMPLE In this embodiment, the substrate is bond paper of 13 pounds weight per ream of 5000 sheets 17 by 22 inches having a medium calendered surface.

The dye dispersion is as follows:

Percent solids (dry) CVL 68.8 Vinol 325 a 30.0 Surfynol 104 b 0.1 Nopco NDW 0.1

Vinol 325 is a polyvinyl alcohol produced by Air Reduction Chemical Co.

Surfynol 104: is a. surface active agent of d1tert1ary acetylenic glycol produced by Air Reduction Chemical Co.

Nopco NDW is a. deforming agent produced by Nopco Chemical Company.

The bisphenol dispersion is as follows:

a See footnote a to table above.

b See footnote b to table above.

" See footnote to table above.

d Klondyke clay is a conventional coating clay comprising mainly silicates, produced by Englehard Chemical Company.

The dispersions were made using conventional grinding equipment at about 20 percent solids and mixed in the above proportions. After 16 hours, the two dispersions were admixed in a ratio of 1 part dye dispersion per 4 10.67 parts reactive dispersion, resulting in the following formulation.

The final formulation can be used 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 hot type members as they are cooled. Further, the thermally sensitive reactants in combination with the filler, lubricant binder and binder to make it possible to produce a non-sticking thermally sensitive paper that is extremely stable to wide ambient conditions of temperature and humidity.

What is claimed is:

1. In a temperature-responsive record material comprising supported sheet material having a coating of finely divided solid crystal violet lactone and a finely divided bisphenol distributed in a binder of polyvinyl alcohol, wherein said finely divided materials are capable of liquefying or vaporizing at normal thermographic temperatures, the improvement comprising having a water insoluble filler at least partly reactive with the colorless chromogenic material and selected from the group consisting of titanium dioxide, zinc oxide, clays, water insoluble silicates and water insoluble carbonates, a lubricant of water insoluble stearate and a nontacky wax which will not melt and react with said crystal violet lactone and said bisphenol under normal storage conditions distributed in the coating wherein the coating contains 3 to 9 dry weight percent of said crystal violet lactone, 39 to 41 dry weight percent of said bisphenol, 20 to 30 dry weight percent of said polyvinyl alcohol, 20 dry weight percent of said filler, 2 dry weight percent of said lubricant and 2 dry weight percent of said wax.

2. The record material of claim 1 wherein said bis phenol is 4,4'-isopropylidenediphenol, said filler is a clay and said lubricant is zinc stearate.

References Cited UNITED STATES PATENTS 3,539,375 11/1970 Baum 117--36.8 3,442,682 5/ 1969 Fukawa 117-368 3,147,134 9/1964 Clark 117-369 3,076,721 2/ 1963 Coles et al 11736.9

MURRAY KATZ, Primary Examiner US. Cl. X.R.

US3674535A 1970-07-15 1970-07-15 Heat-sensitive record material Expired - Lifetime US3674535A (en)

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JP (1) JPS5518635B1 (en)
CA (1) CA968142A (en)
DE (1) DE2132900B2 (en)
DK (1) DK128196B (en)
FR (1) FR2101624A5 (en)
GB (1) GB1294430A (en)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4990142A (en) * 1972-12-26 1974-08-28
JPS5273047A (en) * 1975-12-15 1977-06-18 Tomoegawa Paper Co Ltd Heat sensitive recording paper
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4054684A (en) * 1974-12-03 1977-10-18 La Cellophane Composition for forming colored images, new recording material and process using same
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
US4246318A (en) * 1979-04-09 1981-01-20 Appleton Papers Inc. Thermally-responsive record material
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
US4287264A (en) * 1980-03-07 1981-09-01 Labelon Corporation Heat sensitive coating
US4439512A (en) * 1975-12-05 1984-03-27 La Cellophane Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same
US4523207A (en) * 1983-03-30 1985-06-11 Ncr Corporation Multiple copy thermal record sheet
US4567019A (en) * 1977-05-11 1986-01-28 Graphic Controls Corporation Color reversing compositions
US4851384A (en) * 1985-05-02 1989-07-25 The Wiggins Teape Group Limited Record material
US4853256A (en) * 1986-08-14 1989-08-01 Ncr Corporation Two ply thermal paper and method of making
US5006863A (en) * 1987-07-06 1991-04-09 Ncr Corporation Multiple copy thermal imaging
US5284816A (en) * 1992-11-19 1994-02-08 Eastman Kodak Company Two-sided thermal printing system
US5601867A (en) * 1995-06-22 1997-02-11 The United States Of America As Represented By The Secretary Of The Navy Method and apparatus for generating fingerprints and other skin prints
US6294502B1 (en) 1998-05-22 2001-09-25 Bayer Aktiengesellschaft Thermally-responsive record material
US20040001000A1 (en) * 2002-06-28 2004-01-01 Redlin Gregory George Thermal imaging paper laminate
WO2004030922A1 (en) 2002-10-02 2004-04-15 General Data Company, Inc. Thermosensitive recording material and method of making and using same
US20040169071A1 (en) * 2003-02-28 2004-09-02 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
US20070199671A1 (en) * 2006-02-03 2007-08-30 Hook Kevin J Formulations for high speed print processing
EP2120228A2 (en) 2008-05-14 2009-11-18 Avery Dennison Corporation Organisation Dissolvable thermal direct adhesive label and label assembly including the same
US20100266322A1 (en) * 2009-04-17 2010-10-21 Timothy Croskey Apparatus and method for destroying confidential medical information on labels for medicines
US8343437B2 (en) 2008-06-04 2013-01-01 Jp Laboratories, Inc. Monitoring system based on etching of metals
US8500895B2 (en) 2006-05-22 2013-08-06 Marken-Imaje Corporation Methods of marking and related structures and compositions
US9034790B2 (en) 2013-03-14 2015-05-19 Appvion, Inc. Thermally-responsive record material
WO2015094630A1 (en) 2013-12-18 2015-06-25 Appvion, Inc. Thermal recording materials
US9448182B2 (en) 2004-11-08 2016-09-20 Freshpoint Quality Assurance Ltd. Time-temperature indicating device

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
US4363664A (en) * 1980-01-25 1982-12-14 Sterling Drug Inc. Novel compositions and processes

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4990142A (en) * 1972-12-26 1974-08-28
JPS556077B2 (en) * 1972-12-26 1980-02-13
US4054684A (en) * 1974-12-03 1977-10-18 La Cellophane Composition for forming colored images, new recording material and process using same
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4439512A (en) * 1975-12-05 1984-03-27 La Cellophane Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same
JPS557160B2 (en) * 1975-12-15 1980-02-22
JPS5273047A (en) * 1975-12-15 1977-06-18 Tomoegawa Paper Co Ltd Heat sensitive recording paper
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
US4246318A (en) * 1979-04-09 1981-01-20 Appleton Papers Inc. Thermally-responsive record material
US4287264A (en) * 1980-03-07 1981-09-01 Labelon Corporation Heat sensitive coating
US4523207A (en) * 1983-03-30 1985-06-11 Ncr Corporation Multiple copy thermal record sheet
US4851384A (en) * 1985-05-02 1989-07-25 The Wiggins Teape Group Limited Record material
US4853256A (en) * 1986-08-14 1989-08-01 Ncr Corporation Two ply thermal paper and method of making
US5006863A (en) * 1987-07-06 1991-04-09 Ncr Corporation Multiple copy thermal imaging
US5284816A (en) * 1992-11-19 1994-02-08 Eastman Kodak Company Two-sided thermal printing system
US5601867A (en) * 1995-06-22 1997-02-11 The United States Of America As Represented By The Secretary Of The Navy Method and apparatus for generating fingerprints and other skin prints
US6294502B1 (en) 1998-05-22 2001-09-25 Bayer Aktiengesellschaft Thermally-responsive record material
US20050134464A1 (en) * 2002-06-28 2005-06-23 Appleton Papers, Inc. Thermal imaging paper laminate
US20040001000A1 (en) * 2002-06-28 2004-01-01 Redlin Gregory George Thermal imaging paper laminate
US7183928B2 (en) 2002-06-28 2007-02-27 Appleton Papers Inc. Thermal imaging paper laminate
US6937153B2 (en) 2002-06-28 2005-08-30 Appleton Papers Inc. Thermal imaging paper laminate
WO2004030922A1 (en) 2002-10-02 2004-04-15 General Data Company, Inc. Thermosensitive recording material and method of making and using same
WO2004030921A2 (en) 2002-10-02 2004-04-15 General Data Company, Inc. Direct thermal imaging on plastic film john finger
US20040169071A1 (en) * 2003-02-28 2004-09-02 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US7108190B2 (en) 2003-02-28 2006-09-19 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
US9448182B2 (en) 2004-11-08 2016-09-20 Freshpoint Quality Assurance Ltd. Time-temperature indicating device
US20070199671A1 (en) * 2006-02-03 2007-08-30 Hook Kevin J Formulations for high speed print processing
US7708861B2 (en) 2006-02-03 2010-05-04 Rr Donnelley Formulations for high speed print processing
US8500895B2 (en) 2006-05-22 2013-08-06 Marken-Imaje Corporation Methods of marking and related structures and compositions
US9767714B2 (en) 2008-05-14 2017-09-19 Avery Dennison Corporation Dissolvable thermal direct adhesive label and methods of assembly and use of the same
US20090286032A1 (en) * 2008-05-14 2009-11-19 Priscilla Franklin Dissolvable thermal direct adhesive label and label assembly including the same
US9418576B2 (en) 2008-05-14 2016-08-16 Avery Dennison Corporation Dissolvable thermal direct adhesive label and label assembly including the same
EP2120228A2 (en) 2008-05-14 2009-11-18 Avery Dennison Corporation Organisation Dissolvable thermal direct adhesive label and label assembly including the same
EP3293493A1 (en) 2008-06-04 2018-03-14 G Patel A monitoring system based on etching of metals
US8343437B2 (en) 2008-06-04 2013-01-01 Jp Laboratories, Inc. Monitoring system based on etching of metals
US20100266322A1 (en) * 2009-04-17 2010-10-21 Timothy Croskey Apparatus and method for destroying confidential medical information on labels for medicines
US9034790B2 (en) 2013-03-14 2015-05-19 Appvion, Inc. Thermally-responsive record material
US9126451B2 (en) 2013-12-18 2015-09-08 Appvion, Inc. Thermal recording materials
WO2015094630A1 (en) 2013-12-18 2015-06-25 Appvion, Inc. Thermal recording materials

Also Published As

Publication number Publication date Type
CA968142A1 (en) grant
DE2132900B2 (en) 1976-06-10 application
JPS5518635B1 (en) 1980-05-20 grant
CA968142A (en) 1975-05-27 grant
DK128196B (en) 1974-03-18 grant
FR2101624A5 (en) 1972-03-31 application
GB1294430A (en) 1972-10-25 application
DE2132900A1 (en) 1972-02-10 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