|Publication number||US3539375 A|
|Publication date||Nov 10, 1970|
|Filing date||Mar 14, 1969|
|Priority date||Jun 1, 1966|
|Publication number||US 3539375 A, US 3539375A, US-A-3539375, US3539375 A, US3539375A|
|Inventors||Henry H Baum|
|Original Assignee||Ncr Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Referenced by (102), Classifications (14), Legal Events (1)|
|External Links: USPTO, USPTO Assignment, Espacenet|
H. H. BAUM Nov. 10, 1970 THERMO-RESPONS IVE RECORD SHEET 2 Sheets-Sheet 1 Original Filed June 1, 1966 FIG. I
I a (c) pgxxx x INFRA RED RADIATION HIS ATTORNEYS M m B m m 4/ m. w E NW N m a I Y B E m A m I I R E E mm III' 0A. SL P I L m m I R T F- A T m M A 2 n RI m T D N E EIIIIW' E G E R G 0 I w M AIIIV .H F m M m Lw O D N E H D.
Nov. 10, 1970 H. H. BAUM 3,539,375
THERMO-RESFONS IVE RECORD SHEET Original Filed June 1, 1966 2 Sheets-Sheet INFRA RED RADIATION COPY PARTICLES OF PHENOL AND CHROMOGENIC MATERMLS PLAIN PAPER PRESSURE PLATE |5oc SHEET 111 OR (SHEETS 1 a II) TRANSFERABLE MIRROR IMAGE ON REAR SURFACE (EITHER ONE OF THE REAC-J" TANTS OR BOTH) INVENTOR HENRY H. BAUM /f Max 1:
f Mi -p HIS ATTORNEYS PLAIN PAPER 0R (SUPPLIED WITH ONE OF THE REACTANTS) United States Patent US. Cl. 11736.2 8 Claims ABSTRACT OF THE DISCLOSURE In a temperature-responsive record material comprising a support sheet having crystal violet lactone and a phenolic arranged such that application of heat will produce a mark-forming reaction between the lactone and the phenolic, the improvement comprising disposing the lactone and phenolic in a matrix of polyvinyl alcohol.
This application is a continuation of application Ser. No. 554,565, filed June 1, 1966, now abandoned.
This invention is concerned with a temperature-responsive record material and more particularly an improved mark-forming system for use in a temperature-responsive record material.
In co-pending United States patent application Ser. No. 366,524, filed May 11, 1964, in the name of Henry H. Baum, and assigned to the assignee herein, a mark-forming temperature-responsive record material system is described which broadly involves the migration or transfer of a substantially colorless mark-forming component(s), particulate at room temperature but transferable and/ or vaporizable at elevated temperature from its support sheet to the site of a second substantially colorless markforming component to thereby produce a mark according to an applied temperature pattern. For example, the colorless mark-forming components described above may be arranged in juxtaposition in a single support sheet, this arrangement being commonly referred to as a selfcontained system. Application of heat to the sheet causes a migration of the liquefied or vaporized particulate material to a juxtapositioned mark-forming component to thereby produce a mark.
The mark-forming components generally comprise a basic chromogenic material in its colorless state and an acidic material, such as the diphenols, which react upon contact to produce a color.
An alternative form to the self-contained system is to dispose a component on one sheet and another component on a second support sheet, the components being placed in face-to-face relation, so that, upon application of heat, the liquefied and/or vaporized mark-forming component transfers to the loci of the other mark-forming component and thereat produces a mark. This latter system is generally referred to as a transfer system.
In the afore-described mark-forming systems, it has been found desirable to provide an overlay of polymer film on a sheet or sheets coated with one or both of the mark-forming components. For example, a protective coating comprising a polyvinyl alcohol-carboxymethylcellulose film has been found satisfactory.
It has now been found that a mark-forming system comprising a certain chromogenic material-namely, 3,3- bis(4-dimethylaminophenyl)-6-dimethyl phthalide (crystal violet lactone)and a diphenol, triphenol, or polymer thereof, capable of liquefying and/or vaporizing at the temperatures normally employed in thermographic processes, when distributed in a polyvinyl alcohol film, possesses unexpected properties which make it uniquely attractive as a temperature-responsive record material.
It is well known and not considered to be a part of this invention that basic chromogenic materials, such as crystal violet lactone, and acidic materials, such as attapulgite clay, inorganic and organic acids, and monomeric phenols, such as, for example, phenol, and cresols react to produce a color, as reported, for instance, by O. Fischer and F. Romer, Berichte der deutschen chemischen Gesellschaft, volume 42, pages 2934 and 2935 (1909). Moreover, single-sheet (self-contained) and manifold (transfer) sheet temperature-responsive systems which depend on the reaction of a basic chromogenic material and acidic particulate material are not novel, being disclosed in US. Pats. Nos. 2,172,507, issued July 5, 1955, on the application of Barrett K. Green, and 2,730,457, issued J an. 10, 1956, on the application of Barrett K. Green and Lowell Schleicher, for example.
As noted above, crystal violet lactone is the colorless chromogenic material. The diphenols, triphenols, or polymers thereof useful in this invention should have a low vapor pressure below degrees centigrade to prevent loss by evaporation during storage prior to use in the mark forming reaction but should liquefy and/or vaporize to a sufficient extent at the usual thermographic temperatures of 150 to 200 degrees centigrade.
Examples of suitable phenolic material are:
Structure Formula M.P., C. A (CH3)3COH 4-tertiary butylphenol 94 99 B O-O-OH -pheny phenol 166-167 C O-O-O-OH 4-hydroxydiphenyloxyde D a-Naphthol -9 E OH fl-Naphthol 119-122 F 011,0 0 til-OOH Methyl-bhydroxybenzoate-.- 126-128 Structure Formula M.P., C
U 110M011 4,4-cyclohexylidenediphenoL. 180
H2 HZ I i 1 i V V 4,4-cyclohexylidene bis 184 (Z-methylphenol) H1 Hg Hr- -H3 G1 on OH or Particularly useful, and the preferred phenolic mate rial for use with crystal violet lactone, is 4,4'-isopropylidenediphenol (Compound L).
The polyvinyl alcohol useful in this invention may be completely or partly hydrolyzed, it having been found that polyvinyl alcohol acetate is useful.
The preferred support sheet is paper because of its response to thermographic practices in terms of heat and light conductivity and its known properties as a record material. However, sheets or bands of film-like polymeric material, Woven material, or laminated materials may be used. Such a sheet or band may be impregnated or coated with the mark-forming components, such coating or impregnation fitting the proposed use as to depth of penetration of the components if penetration is involved, or with respect to the total or restricted location of the components as to the broad surface areas of the sheet, or with respect to amounts and kinds of components.
For the purposes of this disclosure, unless otherwise specified, it is to be considered that the support means is a thin, relatively opaque white paper sheet, and that any written or printed data to be used in conjunction therewith for control of recording be of a marking material that is raised in temperature relative to the supporting member when it is irradiated by infra-red radiation.
The particles of phenolic material should be as small in size as is consistent for the necessary resolution and coating propertiessuch as, say, around three microns in average largest particle dimensionand the particles of chromogenic material should be of similar dimensions, although the size is not critical if the optical effect is sufliciently good with respect to resolution. In respect to resolution, the particles preferably should be supplied in such quantity in an area to be served as to give no perception of individual existence. All of the named materials either are colorless (apparently white in powdered form) or have such small coloration in the unreacted' state as to be considered colorless.
The relative amounts of crystal violet lactone, phenolic material, and polyvinyl alcohol may vary, suitable ranges of crystal violet lactone being 1% to by weight, of phenolic material 45% to 94% by weight, and of polyvinyl alcohol 5% to 40% by weight. All weights are on a dry basis.
Where both mark-forming components are contained in the same sheet, they may be interspersed or arranged in layers, be one or both on a surface, partly within the sheet, or entirely within the sheet.
2,2'-thio bis (4,6-dich10rophenol The structural combination of elements in a number of forms illustrative of the invention is shown in the drawings which form part of this specification but which are not to be deemed to limit the claimed subject matter.
Of the drawings:
FIG. 1 is a schematic diagram of several constructions in cross-section of a sheet supplied with the mark-form ing components, (a) showing a sheet of paper having the mark-forming components coated on a surface in interspersion, (b) showing the chromogenic components distributed throughout a sheet of paper and the phenolic component on a surface, (c) showing the reverse of (b), and (d) showing both mark-forming components interspersed throughout the paper sheet.
FIG. 2 is a schematic showing in (a) two facing record sheet surfaces, each of the facing surfaces being coated with one of the mark-forming components, and showing how infra-red radiation is used in conjunction with a thermographic ink print to make a mark, view (a) showing two sheets stapled as a unit, and view (b) showing a folded sheet with a severance formation served with an interleaf sheet carrying one of the reactants. In FIG. 2, it is assumed that the chromogenic material is not rendered mobile by the temperatures used, but that the phenolic material is transferred.
FIG. 3 shows both mark-forming components on the rear surface of a sheet (Sheet III) bearing thermographically-responsive data on the front surface, so that heat engendered by infra-red radiation striking the data heats it, which heat turns the materials on the rear surface to a pattern of mobile fluid which may be transferred to a plain sheet of paper placed in contact therewith.
FIG. 4 shows an overlying sheet of paper having a mirror-image of data recorded in a pattern of one or both of the mark-forming components on the rear surface of a sheet, so that it may be passed to a plain sheet in a mobile fluid phase by a heat press; the plain sheet also may be supplied with one of the necessary reactants if it is missing, by intention, from the overlying sheet.
The following examples further illustrate the invention.
EXAMPLE I This example describes the preparation of a composition containing the mark-forming components and its coating onto a paper support sheet for use as a thermocopy sheet.
Preparation of crystal violet lactone dispersion- Component A Preparation of phenol dispersion-Component B An attritor was charged with 35 parts by weight of 4,4'-isopropylidine diphenol (Bisphenol A), 150 parts by weight of the polyvinyl alcohol solution described used to form Component A, and 65 parts by weight of water, and the system was ground for one hour. The particle size of the phenol after attrition was approximately one to three microns.
Coating composition Three parts by weight of Component A and 67 parts by weight of Component B were combined and coated on the paper at a weight of three to four pounds per ream (500 sheets inches by 38 inches). The composition of the dried paper coating was:
Percent by weight Crystal violet lactone 3 Bisphenol A 67 Polyvinyl alcohol EXAMPLE II This example describes the preparation of a markforming composition and its coating on a paper support sheet for use as a thermal print sheet; that is, direct hot type on the paper coating.
Components A and B were prepared as in Example I.
Preparation of talc dispersionComponent C A colloid mill was charged with parts by weight of talc having an average particle size before milling of approximately 10 microns, 150 parts by weight of a polyvinyl alcohol solution (as described in Component A of Example I), and 65 parts by weight of water.
Coating composition Three parts by weight of Component A, 27 parts by Weight of Component B, and parts by weight of Component C were combined and coated on paper at the Weight of four to five pounds (dry) per ream (500 sheets 25 inches by 38 inches). The composition of the dried paper coating was:
Percent by weight Crystal violet lactone 3 Bisphenol A 27 Polyvinyl alcoh 30 Talc 40 The function of the tale is to prevent sticking of the coating to the printing head.
If desired, compatible defoaming or wetting agents may be added to the aqueous dispersion. When tale is employed in the coating composition, it is desirable to have a coating weight of at least four pounds per ream; also, where the system is a transfer type, the heavier coating weight is used to advantage.
The use of the sheet of Examples 1 and II The sheet of Examples I and II may be used alone as a copy-receiving sheet by being served with a pattern of heat from front or back, as by a thermographicallyheated original document, by trace of a hot stylus, by hot type, or !by any other means giving a difierential heat pattern by conduction.
If the heavier coating is used, the sheet may be used reversely for a transfer sheet to produce multiple copies on unsensitized surfaces of any sort, such as bond paper, newsprint, cloth, film, and the like, as long as the pattern of heat is present to control the transfer.
EXAMPLE III The sheet of Examples I and II, having a coating of four to six pounds per ream, was prepared as specified, and the data to be recorded was printed on the uncoated side. The coated side was placed against plain paper to form a record pair, which was then subjected to a light source of infra-red wave length, so that the radiation directly struck the printing. A copy of the recorded data appeared on the plain paper. This could be repeated until the coating was exhausted. Moreover, the coated sheet could be used as an intermediate master sheet wherein the heavier coated sheet is written on with thermographic ink directly on the coated side. A piece of plain paper is placed in contact with the coated side of the sheet to form a pair, and the pair is subjected to infra-red radiation. This puts a colored mirror-image of the recorded data on the plain paper. This plain sheet then may be used over and over again against successive sheets of plain paper, and each pair is subjected to a hot press to transfer the colored image in direct reading form.
EXAMPLE IV To form a transfer-type thermally-responsive record material, a sheet was coated with, for example, Component A of Example I to a weight of /2 pound to 1 /2 pounds per ream, and a second sheet was coated with Component B of Example I to a weight of 4 to 5 pounds per ream; the sheets being placed in face-to-face relation, hereafter called Sheet I and Sheet II, respectively.
Use of Sheets I and II together In this instance of use, Sheets I and II (Fig. 2a) are placed in face-to-face relation, and the phenolic material only may be transferred to the sheet containing the crystal violet lactone if the right amount of heat is used. For instance, the original data is pre-recorded on the uncoated side of the Sheet II to provide thermographic-responsive representation of the data. On heating of the data with infra-red radiation, while the coated sides are in contact, the copy appears .on the coated surface of Sheet 1. Of course, Sheet I, particularly when heavily coated, may act as a master sheet, as described above. It has been found that the mark-forming system of the invention (that is, crystal violet lactone, the described phenolic material, and polyvinyl alcohol) as compared with other systems, including merely the substitution of a film-forming polymer for polyvinyl alcohol, has considerably improved wet stability and print stability. Wet stability is the resistance to coloration during preparation and drying of the applied mark-forming components.
What is claimed is:
1. In a mark-forming unit for use as a temperatureresponsive record material comprising a supporting sheet material having finely divided solid crystal violet lactone and a finely divided phenolic material solid at room temperature but capable of liquefying and/or vaporizing at normal thermographic temperatures, said lactone and phenolic material being further capable of producing a mark-forming reaction upon reactive contact, the improvement which comprises having the lactone and the phenolic material distributed in a binder matrix of polyvinyl alcohol.
2. The unit of claim 1 wherein the phenolic material is 4,4'-isopropylidenediphenol.
3. The unit of claim 1 wherein the polyvinyl alcohol matrix of lactone and the phenolic material is disposed on a single support sheet.
4. The unit of claim 3 wherein the matrix of lactone and phenolic material is a coating on the support sheet.
5. The unit of claim 4 wherein the phenolic material is 4,4- isopropylidenediphenol.
6. The unit of claim 1 wherein the lactone is disposed on the surface of a support sheet within a matrix of polyvinyl alcohol and the phenolic material is disposed on the surface of a second sheet within a matrix of polyvinyl alcohol.
7. The unit of claim 6 wherein the phenolic material is 4,4'-isopropylidenediphenol.
8. The unit of claim 1 wherein the relative amount of polyvinyl alcohol to crystal violet lactone and phenolic material is 5% to 40%, by weight.
References Cited UNITED STATES PATENTS MURRAY KATZ, Primary Examiner US. Cl. X.R.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2770534 *||May 10, 1953||Nov 13, 1956||Printing Arts Res Lab Inc||Method and material for making overlay masks|
|US2972547 *||Aug 5, 1957||Feb 21, 1961||Antioch College||Acyl hydrazine compositions and methods of producing color therewith|
|US3121650 *||Jul 28, 1960||Feb 18, 1964||Minnesota Mining & Mfg||Right-reading reproduction of printed originals|
|US3239366 *||Nov 21, 1961||Mar 8, 1966||Ncr Co||Thermotransfer sheet material and copying systems utilizing same|
|US3244548 *||Aug 31, 1961||Apr 5, 1966||Burroughs Corp||Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking|
|US3322557 *||May 11, 1964||May 30, 1967||Ncr Co||Thermo-copy system|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3715226 *||Mar 1, 1971||Feb 6, 1973||Ncr||Mark-forming record materials|
|US3816838 *||Dec 22, 1971||Jun 11, 1974||Kanzaki Paper Mfg Co Ltd||Method of making recordings in a recording sheet material|
|US3912831 *||Dec 3, 1973||Oct 14, 1975||Ishii Hirokazu||Recording material|
|US3937864 *||Sep 4, 1973||Feb 10, 1976||Mitsubishi Paper Mills, Ltd.||Heat-sensitive recording sheets having improved stability|
|US3950600 *||Jul 8, 1974||Apr 13, 1976||Ing. C. Olivetti & C., S.P.A.||Thermosensitive element, and its employ in the thermographic reproduction or record systems|
|US3984605 *||Jun 23, 1975||Oct 5, 1976||Mitsubishi Paper Mills, Ltd.||Heat sensitive recording material containing decolorizing agent|
|US3988501 *||Aug 22, 1974||Oct 26, 1976||Ing. C. Olivetti & C., S.P.A.||Thermosensitive element for thermographic reproduction or registration systems|
|US4004065 *||Dec 24, 1974||Jan 18, 1977||General Company, Ltd.||Coated heat sensitive recording member|
|US4032690 *||Jan 24, 1975||Jun 28, 1977||Mitsubishi Paper Mills, Ltd.||Thermosensitive recording material|
|US4115613 *||Dec 22, 1976||Sep 19, 1978||Process Shizai Co., Ltd.||Heat-sensitive recording materials and recording process of using the same|
|US4165741 *||Jun 30, 1978||Aug 28, 1979||Process Shizai Co., Ltd.||Heat-sensitive recording materials and recording process of using the same|
|US4246318 *||Apr 9, 1979||Jan 20, 1981||Appleton Papers Inc.||Thermally-responsive record material|
|US4255491||Jul 17, 1979||Mar 10, 1981||Fuji Photo Film Co., Ltd.||Heat-sensitive recording paper|
|US4263047 *||Sep 11, 1979||Apr 21, 1981||Fuji Photo Film Co., Ltd.||Color developing ink|
|US4277186 *||May 1, 1979||Jul 7, 1981||Pentel Kabushkik Kaisha||Printing and displaying apparatus|
|US4283458 *||Jul 17, 1979||Aug 11, 1981||Fuji Photo Film Co., Ltd.||Heat-sensitive recording paper containing a novel electron accepting compound|
|US4287264 *||Mar 7, 1980||Sep 1, 1981||Labelon Corporation||Heat sensitive coating|
|US4321309 *||May 27, 1980||Mar 23, 1982||Sanyo-Kokusaku Pulp Co., Ltd.||Heat-sensitive recording material|
|US4339492 *||Jun 5, 1980||Jul 13, 1982||Sanyo-Kokusaku Pulp Co., Ltd.||Heat-sensitive recording material|
|US4363664 *||Jan 25, 1980||Dec 14, 1982||Sterling Drug Inc.||Novel compositions and processes|
|US4370370 *||Jun 8, 1981||Jan 25, 1983||Ricoh Company, Ltd.||Thermosensitive recording adhesive label|
|US4439512 *||Nov 18, 1982||Mar 27, 1984||La Cellophane||Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same|
|US4444844 *||Jun 4, 1982||Apr 24, 1984||Ricoh Co., Ltd.||Thermosensitive recording material|
|US4477676 *||Jul 6, 1982||Oct 16, 1984||The Hilton-Davis Chemical Co.||4-(3-Indolyl)-2,3-dichloro-4-oxo-2-butenoic acids|
|US4482378 *||Jun 15, 1982||Nov 13, 1984||Societe Anonyme: Aussedat-Rey||Color developers and thermographic record compositions containing them|
|US4514745 *||Jul 30, 1984||Apr 30, 1985||Kanzaki Paper Manufacturing Co. Ltd.||Heat-sensitive recording material|
|US4523207 *||Mar 30, 1983||Jun 11, 1985||Ncr Corporation||Multiple copy thermal record sheet|
|US4535190 *||Mar 23, 1984||Aug 13, 1985||Sanko Kaihatsu Kagaku Kenkyusho||Phenolic compounds and a heat-sensitive recording material containing the same|
|US4536219 *||Jul 13, 1983||Aug 20, 1985||Societe Anonyme: Aussedat-Rey||Thermographic recording compositions|
|US4542395 *||Nov 5, 1984||Sep 17, 1985||Sanko Kaihatsu Kagaku Kenkyusho||Heat-sensitive recording material|
|US4558335 *||Mar 11, 1982||Dec 10, 1985||Yoshitomi Pharmaceutical Industries, Ltd.||Thermoresponsive recording sheet|
|US4596997 *||Jan 31, 1985||Jun 24, 1986||Nippon Kayaku Kabushiki Kaisha||Phenolic compound, preparation thereof and recording material employing same|
|US4666949 *||Jan 31, 1986||May 19, 1987||Matsui Shikiso Chemical Co., Ltd.||Thermochromic polyurethane foam|
|US4717710 *||Jan 3, 1985||Jan 5, 1988||Matsui Shikiso Chemical Co. Ltd.||Thermochromic composition|
|US4745046 *||May 14, 1986||May 17, 1988||Polaroid Corporation||Thermal imaging method|
|US4826550 *||Nov 21, 1986||May 2, 1989||Matui Shikiso Chemical Co., Ltd.||Process for preparing molded product of thermochromic polyvinyl chloride|
|US4853256 *||Mar 11, 1988||Aug 1, 1989||Ncr Corporation||Two ply thermal paper and method of making|
|US5006863 *||Feb 8, 1989||Apr 9, 1991||Ncr Corporation||Multiple copy thermal imaging|
|US5087602 *||Aug 28, 1990||Feb 11, 1992||Mitsubishi Paper Mills Limited||Recording material|
|US5135437 *||Jun 24, 1991||Aug 4, 1992||Schubert Keith E||Form for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same|
|US5137494 *||Mar 16, 1990||Aug 11, 1992||Schubert Keith E||Two-sided forms and methods of laying out, printing and filling out same|
|US5154668 *||Mar 22, 1990||Oct 13, 1992||Schubert Keith E||Single paper sheet forming a two-sided copy of information entered on both sides thereof|
|US5197922 *||Nov 13, 1989||Mar 30, 1993||Schubert Keith E||Method and apparatus for producing two-sided carbonless copies of both sides of an original document|
|US5224897 *||Jun 29, 1992||Jul 6, 1993||Linden Gerald E||Self-replicating duplex forms|
|US5246906 *||Jul 17, 1992||Sep 21, 1993||Oji Paper Co., Ltd.||Thermosensitive recording material|
|US5248279 *||Dec 16, 1991||Sep 28, 1993||Linden Gerald E||Two-sided, self-replicating forms|
|US5256618 *||Oct 2, 1992||Oct 26, 1993||Oji Paper Co., Ltd.||Thermosensitive recording material|
|US5284816 *||Nov 19, 1992||Feb 8, 1994||Eastman Kodak Company||Two-sided thermal printing system|
|US5310611 *||Sep 30, 1992||May 10, 1994||Oki Electric Industry Co., Ltd.||Thermoreversible recording material, thermoreversible recording medium and recording method|
|US5312796 *||May 14, 1992||May 17, 1994||Oji Paper Co., Ltd.||Thermosensitive recording material|
|US5314859 *||Nov 13, 1992||May 24, 1994||Oji Paper Co., Ltd.||Thermosensitive recording material|
|US5340537 *||Apr 16, 1993||Aug 23, 1994||Big Three Industries, Inc.||Temperature indicating compositions|
|US5395288 *||Sep 24, 1993||Mar 7, 1995||Linden; Gerald E.||Two-way-write type, single sheet, self-replicating forms|
|US5444036 *||Jan 7, 1994||Aug 22, 1995||New Oil Paper Co., Ltd.||Thermosensitive recording material|
|US5446010 *||Apr 12, 1994||Aug 29, 1995||New Oji Paper Co., Ltd.||Thermosensitive recording material|
|US5449657 *||Mar 7, 1994||Sep 12, 1995||New Oji Paper Co., Ltd.||Thermosensitive recording material|
|US5601867 *||Jun 22, 1995||Feb 11, 1997||The United States Of America As Represented By The Secretary Of The Navy||Method and apparatus for generating fingerprints and other skin prints|
|US5840652 *||Feb 19, 1997||Nov 24, 1998||Sanko Kaihatsu Kagaku Kenkyusho||Sulfonyl compound and thermalsensitive recording medium using the same|
|US5985526 *||Jun 19, 1998||Nov 16, 1999||Eastman Kodak Company||Imaging process based on change of optical covering power|
|US6040470 *||Sep 10, 1998||Mar 21, 2000||Sanko Kaihatsu Kagaku Kenkyusho||Sulfonyl compound and thermalsensitive recording medium using the same|
|US6280322||Feb 27, 1995||Aug 28, 2001||Gerald E. Linden||Single sheet of paper for duplicating information entered on both surfaces thereof|
|US6294502||May 14, 1999||Sep 25, 2001||Bayer Aktiengesellschaft||Thermally-responsive record material|
|US6937153||Jun 28, 2002||Aug 30, 2005||Appleton Papers Inc.||Thermal imaging paper laminate|
|US7108190||Feb 28, 2003||Sep 19, 2006||Appleton Papers Inc.||Token array and method employing authentication tokens bearing scent formulation information|
|US7183928||Jan 18, 2005||Feb 27, 2007||Appleton Papers Inc.||Thermal imaging paper laminate|
|US7635662||Mar 2, 2001||Dec 22, 2009||Chemipro Kasei Kaisha, Ltd.||Compound for color-producing composition, and recording material|
|US7704667||Jan 30, 2008||Apr 27, 2010||Zink Imaging, Inc.||Dyes and use thereof in imaging members and methods|
|US7791626||Jan 30, 2008||Sep 7, 2010||Zink Imaging, Inc.||Print head pulsing techniques for multicolor printers|
|US7807607||Dec 23, 2008||Oct 5, 2010||Zink Imaging, Inc.||Color-forming compounds and use thereof in imaging members and methods|
|US7807738||Oct 21, 2009||Oct 5, 2010||Chemipro Kasei Kaisha, Ltd.||Compound for color-producing composition, and recording material|
|US7808674||May 28, 2008||Oct 5, 2010||Zink Imaging, Inc.||Image stitching for a multi-head printer|
|US7829497||May 12, 2006||Nov 9, 2010||Zink Imaging, Inc.||Thermal imaging members and methods|
|US7830405||Jun 23, 2005||Nov 9, 2010||Zink Imaging, Inc.||Print head pulsing techniques for multicolor printers|
|US7897541||Dec 13, 2005||Mar 1, 2011||Oji Paper Co., Ltd.||Thermosensitive recording medium|
|US8062993||Mar 11, 2005||Nov 22, 2011||Api Corporation||Developer mixture for thermal recording materials and thermal recording materials|
|US8072644||Sep 1, 2010||Dec 6, 2011||Zink Imaging, Inc.||Image stitching for a multi-head printer|
|US8098269||Sep 1, 2010||Jan 17, 2012||Zink Imaging, Inc.||Print head pulsing techniques for multicolor printers|
|US8164609||Nov 5, 2010||Apr 24, 2012||Zink Imaging, Inc.||Print head pulsing techniques for multicolor printers|
|US8283286||Aug 22, 2008||Oct 9, 2012||Nicca Chemical Co., Ltd.||Thermosensitive recording material|
|US8343437||Jun 4, 2009||Jan 1, 2013||Jp Laboratories, Inc.||Monitoring system based on etching of metals|
|US8345307||Dec 6, 2011||Jan 1, 2013||Zink Imaging, Inc.||Image stitching for a multi-head printer|
|US8372782||Oct 5, 2009||Feb 12, 2013||Zink Imaging, Inc.||Imaging system|
|US8377844||Aug 3, 2009||Feb 19, 2013||Zink Imaging, Inc.||Thermally-insulating layers and direct thermal imaging members containing same|
|US8497227||Jul 28, 2008||Jul 30, 2013||Nicca Chemical Co., Ltd.||Diphenylsulfone bridged compound, color forming substance for thermal recording and thermal recording material|
|US8500895||Apr 24, 2007||Aug 6, 2013||Marken-Imaje Corporation||Methods of marking and related structures and compositions|
|US8502846||Mar 19, 2012||Aug 6, 2013||Zink Imaging, Inc.||Print head pulsing techniques for multicolor printers|
|US8722574||Apr 27, 2012||May 13, 2014||Zink Imaging, Inc.||Thermal imaging members and methods|
|US9034790||Mar 14, 2013||May 19, 2015||Appvion, Inc.||Thermally-responsive record material|
|US20010044553 *||Mar 2, 2001||Nov 22, 2001||Kazuo Kabashima||Novel compound for color-producing composition, and recording material|
|US20040169071 *||Feb 28, 2003||Sep 2, 2004||Appleton Papers Inc.||Token array and method employing authentication tokens bearing scent formulation information|
|US20040251309 *||Jun 10, 2003||Dec 16, 2004||Appleton Papers Inc.||Token bearing magnetc image information in registration with visible image information|
|US20050134464 *||Jan 18, 2005||Jun 23, 2005||Appleton Papers, Inc.||Thermal imaging paper laminate|
|DE2237288A1 *||Jul 28, 1972||Feb 15, 1973||Mitsubishi Paper Mills Ltd||Hitzeempfindliches material und thermische aufzeichnungsfolie|
|DE3021782A1 *||Jun 10, 1980||Dec 18, 1980||Sanyo Kokusaku Pulp Co||Waermeempfindliches aufzeichnungsmaterial|
|EP0131631A1 *||Jan 17, 1983||Jan 23, 1985||Yoshitomi Pharmaceutical Industries, Ltd.||Heat-sensitive recording paper|
|EP0192328A1||Jan 17, 1986||Aug 27, 1986||Imperial Chemical Industries Plc||Chromogenic compounds|
|EP0358193A2 *||Sep 6, 1989||Mar 14, 1990||Kanzaki Paper Manufacturing Co., Ltd.||Heat sensitive recording material|
|EP2120228A2||May 14, 2009||Nov 18, 2009||Avery Dennison Corporation Organisation||Dissolvable thermal direct adhesive label and label assembly including the same|
|WO2000014058A1||Sep 3, 1999||Mar 16, 2000||Asahi Chemical Ind||Novel color-developing compound and recording material|
|WO2004030921A2||Oct 2, 2003||Apr 15, 2004||Gen Data Co Inc||Direct thermal imaging on plastic film john finger|
|WO2004030922A1||Oct 2, 2003||Apr 15, 2004||Gen Data Co Inc||Thermosensitive recording material and method of making and using same|
|WO2011044049A1||Oct 4, 2010||Apr 14, 2011||Zink Imaging, Inc.||Multicolour thermal imaging material|
|U.S. Classification||503/214, 503/217, 428/913, 430/964, 430/495.1, 503/219, 430/200, 503/225, 503/226|
|Cooperative Classification||B41M5/3335, Y10S430/165, Y10S428/913|
|Feb 18, 1983||AS||Assignment|
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