US3723156A - Record material - Google Patents

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Publication number
US3723156A
US3723156A US3723156DA US3723156A US 3723156 A US3723156 A US 3723156A US 3723156D A US3723156D A US 3723156DA US 3723156 A US3723156 A US 3723156A
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US
United States
Prior art keywords
oil
metal
soluble
color
resin
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Expired - Lifetime
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English (en)
Inventor
B Brockett
R Miller
M Hinkle
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Appvion LLC
NCR Voyix Corp
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NCR Corp
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Publication of US3723156A publication Critical patent/US3723156A/en
Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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Expired - Lifetime legal-status Critical Current

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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
    • B41M5/124—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
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • Y10T428/31949—Next to cellulosic
    • Y10T428/31964—Paper
    • Y10T428/31967—Phenoplast

Definitions

  • Said record sheet material has a coating comprising an oil-soluble metal salt and an oilsolublephenol-formaldehyde novolak resin.
  • This invention relates to record material sheets bearing a coating of an oil-soluble metal salt and an oil-soluble phenol-formaldehyde novolak resin as a combination coreactant for colorless, chromogenic dye-precursor materials to develop a useful color therein.
  • Oil-soluble phenol-' formaldehyde novolak resins preferably those derived from the condensation of a para-substituted phenol with formaldehyde, have long been used, with great commercial success, in making acid-reactant record material sheets capable of developing color in oil solutions of base-reacting colorless, chromogenic dye-precursor materials.
  • Such resins and the use of them are disclosed in applications for United States patents, Ser. Nos.
  • the record sheet materials of this invention constitute a further improvement wherein both the metallic moiety and the acidic resin are oil-soluble and both are available for color-developing reaction in oil solution.
  • This improvement can be realized by providing on the sheet surface oil-soluble metal salts and oilsoluble phenol-formaldehyde resins.
  • an object of this invention is to realize improvements in the speed and intensity of print development as well an improvements in stability toward the environment of the coated developing agent prior to print color-development and of the dye color in the developed print without resorting to coatings of water-soluble metal salts together with the commonly-used novolak resins.
  • Novolak powder particles are commonly bound to paper with cooked starch binder and latex binders such as styrene-butadiene latexes, but novolaks in combination with Zinc chloride and other useful water-soluble metal salts cannot be successfully bound to paper with latexes and/or cooked starch binder, thereby necessitating the use of other binders such as poly(vinyl alcohol).
  • Adequate adhesion is difiicult to achieve with poly(vinyl alcohol) as the sole binder and furthermore such sheets do not give good printing characteristics with offset printing presses and inks.
  • the metal-modified resins of the above-cited co-pending application give greater improvement in the sheet properties than does the combination of oil-soluble metal salts and oil-soluble novolak resins of the present invention.
  • the combination of the present invention can be made more economically and does show performance advantage over the unmodified novolak resins of the known art.
  • the metal salts and phenol-formaldehyde resins provided herein react with basic chromogens, particularly with Crystal Violet lactone, to give more intense and more fade-resistant prints than do known-art resins alone.
  • the acid-reacting receiving sheets provided herein are also more stable to environmental influences prior to imaging use than are known-art receiving sheets.
  • the rate at which full color-intensity is realized when acid-reacting sheets are treated with oil solutions of base-reacting chromogens, a sheet-property known as print speed, is comparable for the sheets of this invention to sheets of good commercial quality.
  • the metal salts found useful herein for use with oilsoluble phenol-formaldehyde resins in pressure-sensitive copy-papers of the NCR Paper type include the oil-soluble salts of aluminum(III), barium(II), cadmium(II), calcium(II), cerium(III), cesium(I), cobalt(II), copper (III), indium(III), iron(II) and (III), lead (II), magnesiurn (II), manganese (II), molybdenum(V), nickel(II), sodium(I), strontium(II), tin(II), titanium(IV), vanadium(IV), zinc(ll), and zirconiurnflV).
  • oil-soluble metal resinates tested and found useful herein should be noted inasmuch as they include metals from P riodic Groups I-A and B, IIA and B, III-A and B, I -A and B, VB, VI-B, VII-B, and VIII.
  • Eligible anions of the useful metal salts include acetylacetonate, hexafluoroacetylacetonate, benzoate, naphthenate, salicylate, Z-ethylhexanoate, abietate, oleate, and
  • the candidate anion should confer on the metal salt ready solubility in the oily solvents used as the core-material in encapsulated chromogenic inks in carbonless copy-papers.
  • oils in use are hydrocarbons such as parafiin oils, aromatic oils such as xylene and alkylated biphenyls, high molecular weight esters such as dioctyl adipate and dioctyl phthalate, halocarbons such as trichlorobiphenyl, and aromatic ethers such as diphenyl oxide.
  • the metalmodified resins of this invention are designed to operate and do operate well in developing oily dye-precursor inks of the type described.
  • the oily vehicle preferred herein is one of low volatility, such as chlorinated or alkylated biphenyl, which leaves an essentially wet print on the paper surface rather than a more volatile one such as xylene that readily evaporates to leave a dry print.
  • the enhancement of print intensity by the metal-modified resins of this invention is considerably greater in wet prints than in dry prints. Rapid and substantial solubility is required to give satisfactory print speed in use.
  • the metal salt anion should have a carbon content of at least four carbon atoms and preferably six or more carbon atoms. Metal salts of anions of less than four carbon atoms will operate to enhance color intensity and/or fade resistance provided they are still oil-soluble.
  • a further object of this invention is to make a colordeveloping agent for basic-chromogens that is completely oil-soluble (unlike acidic clays and the combination agents exemplified by paraphenylphenol-f'ormaldehyde resin together with zinc chloride and other water-soluble metal salts) so that it may be used in a variety of ways including particulate coating on a sheet, solution coating on a sheet and coating as encapsulated droplets of an oil solution
  • the selected oil-soluble novolak and the selected oil-soluble metal salt may be dissolved in oil for encapsulation or for coating as a solution residue on substrate sheets.
  • both the selected novolak and the selected metal salt are dissolved in oil in mutual solution, at least some, that is appreciable amounts, of metal resinate material is formed in the solution, depending in part on the selection of the oil and the two colordeveloping materials.
  • zinc naphthenate and para-phenylphenol -formaldehyde resin in 1,2,4-trimethylbenzene readily form the zinc resinate in solution.
  • metal salts in enhanching acidic resin color-production, in chromogenic dye-precursors such as CVL, is inversely related to the chelating ability of the metal in the metal salt.
  • metals that form very stable chelates with acetylacetone, having stability constant logs (log Kstabmty corrected to zero ionic strength) greater than about 5.5 do not enhance CVL color-production when used in conjunction with acidic resins.
  • the metals of more unstable metal-acetylacetone chelates, having stability constant logs less than about 5.5, will be found to enhance CVL-resin color intensity in solution.
  • Such metallic ions are designated herein as color-enhancing metals.
  • solutions of CVL, metals salts and no o ak. resin will show higher optica de sities as the stability constants of the chelates of the chosen metals and acetylacetone decrease.
  • the most useful metal salts will be those of color-enhancing metals which are readily soluble in the liquid vehicle droplets used in the record material system capsules.
  • the metal For a metal to be useful as a colorenhancer with a novolak resin in a record material copy sheet, the metal must be a color enhancer and must be present as a metal salt which is readily soluble, in the presence of the chosen novolak, in the oil droplets included in the copy paper.
  • the metal salts and novolak resins of this invention are viewed as being coated on a receiving sheet for the receipt and development of color in liquid dye-precursor materials, but they are not solimited in use.
  • a color-developing system comprising oil-soluble dye-precursor material, oil-soluble polymeric resin coreactant material and mutual-solvent oil.
  • FIG. 2 of the Miller-Phillips application shows a number of such arrangements.
  • metal salts and novolak resins of this invention may be coated on paper or dissolved in oil and encapsulated as solution droplets prior to being coated on paper so as to operate in the record-material constructions of the Miller-Phillips applications FIG. 2.
  • the metal salts and novolak resins of this invention are oil-soluble, are grindable to a fine powder, and are encapsulatable as fine oil-solution droplets either separately or together. So they are adaptable for use in any of the ways Miller and Phillips envisioned and taught that oil-soluble polymeric resin co-reactants could be used.
  • the metal salts and novolak resins of this invention may be (1) applied to a sheet from a printing solution as taught in the aforementioned Miller-Phillips application and in US. Pat. No. 3,466,184 which issued Sept 9, 1969 on the application of Richard G. Bowler and Robert E. Miller, (2) applied as a substratum below the surface of a fibrous record material as taught and claimed in US. Pat. No. 3,466,185 which issued Sept. 9, 1969 on the application of John E. G. Taylor, (3) applied as a particulate, finely ground powder as taught in the aforementioned Miller-Phillips application or in combination with an oil-adsorbent coating-clay such as kaolin as taught and claimed in US. Pat. No.
  • oil-soluble novolak resins together with oil-soluble metal salts offers somewhat more versatility in mode of aplication to a substrate sheet than does the use of the metal resinates described in the aforementioned co-pending application of this date.
  • a solution of a novolak resin may be applied to a sheet as encapsulated droplets together with finely ground particles of an oil-soluble metal salt which may be interspersed with the resin-containing microcapsules or coated on a dye-sensitized receiving sheet to be used in conjunction with the resin-containing microcapsule-coated sheet.
  • the selection of the metal of the metal salt for use herein is of little consequence as far as improving fade resistance of the developed print is concerned. Selection for good print intensity is more important. Some metals found to work well in improving print intensity as metal resinates do not work well as oil-soluble metal salts mixed with resins and vice versa. Furthermore, mixtures of metal salt and phenolic resin appear to be more limited than metal resinates in their application to different base-reacting chromogenic dyes.
  • the mixtures described herein serve to improve the prints made with Crystal Violet lactone (CVL) and its structural analogs (namely color-blocked 4,4 diaminodiphenylmethane derivatives) more markedly than prints made with base-reacting chromogenic fluoran dyes.
  • This selectivity with respect to useful dyes suggests that at least part of the beneficial effects observed with the resin-salt mixtures described herein is due to direct chemical reaction between the chromogenic dye and the metal salt, rather than chemical combination between the resin and the metal salt to make a metal resinate which then reacts with the chromogenic dye, as one would suppose on the assumption of strict analogy between the resin-salt mixture and the above discussed metal resinates.
  • both the colorless chromogenic dye-precursor materials and the metal salts of this invention can be dissolved in oil together, without substantial coloration, and be encapsulated and coated onto paper sheets for use as transfer sheets with standard phenolic resin-containing receiving sheets.
  • Zinc salicylate and any other metal salt that gives some degree of colordevelopment with CVL in oil solution can be used for the metal-salt over-print preparation and for the preparation of microcapsules containing droplets of oil solution of CVL and metal salt material, but these materials are not preferred because color-development therein with acidic novolak resin material gives a dark-blue print on a light-blue background.
  • Preferred for use in constructions where CVL and metal salts actually come into oilsolution contact prior to color-development-use are the following zinc(II) salts: acetylacetonate, caprylate, laurate, 2-ethylhexanoate, oleate, abietate, and naphthenate, which give little or no observable coloration when dissolved in oily CVL solutions.
  • Useful weights of materials for the practice of this invention fall within the range of one part of metal ion as an oil-soluble metal salt to one to twenty parts of an oil-soluble phenol-formaldehyde novolak resin. Weights in this range of the color-developing co-reactant materials in combination operate well to develop chromogenic dyeprecursor materials such as Crystal Violet lactone present to the extent of one-half to ten parts. A good practical combination of color-forming reactants is ten parts of resin to one part of metal ion to one part of chromogenic dye-precursor.
  • paper-coating slurry of 30 percent solids content was prepared by mixing the following ingredients:
  • Bond paper (33 pound base stock) was coated on an air knife coater (air-pressure 2.75 pounds/square inch) and dried, by a l2-second pass through a high-velocityair oven at an average temperature of about degrees Fahrenheit, to give a dry-coat weight of 4 pounds per ream of 500 sheets (25 by 38 inches) having a total area of 3,300 square feet.
  • a solution of zinc salt such as zinc acetylacetonate in a volatile organic solvent such as acetone
  • a solution of zinc salt can be applied to the kaolin clay particles which can then be dried to give a free flowing powder of kaolin particles having the zinc salt adsorptively held thereon.
  • the zinc salt-coated kaolin particles can then be applied to the sheet in place of the Zinc acetylacetonate and kaolin clay in the above paper-coating slurry.
  • This latter method is particularly useful for non-crystalline zinc salts that are difficult to grind, such as zinc naphthenate, Zinc oleate and zinc Z-ethylhexanoate.
  • microcapsules were made with core material of para-phenylphenol-formaldehyde resin (17 percent in xylene), according to the method of Robert G. Bayless and Donald D. Emrick taught and claimed in US. patent application Ser. No. 701,124, filed Ian. 29, 1968.
  • the above slurry was coated onto paper sheets and dried to give a dry-coat weight of 4.5 pounds per specified ream.
  • the so-coated sheets were used as transfer sheets against receiving sheets, sensitized by being dipped into a 1.5 percent solution of CVL in acetone and dried.
  • the transfer-receiving sheet couples gave good transfer prints that were remarkably fade-resistant.
  • EXAMPLE 3 CVL-metal salt coated receiving (CF) sheets.
  • a paper coating slurry was prepared by mixing 203 parts of the CVL-coated calcium carbonate particles prepared above with 20 parts of 35 percent aqueous sodium silicate, 200 parts of 5 percent aqueous poly(vinyl alcohol) solution and sufiicient water to give a final solids content of 30 percent.
  • the paper-coating slurry of this example was coated as in Example 1 onto bond paper stock at 2.0 pounds per ream.
  • the so-coated sheets were then overprinted with a benzene solution containing one percent zinc as the naphthenate salt, to give a CVL-metal salt coated CF sheet which readily gave satisfactory prints when written on with a percent solution of paraphenylphenol-formaldehyde resin in dioctyl phthalate.
  • the resin solution was supplied either by pen or from an overlying CB sheet having resin solution droplets encapsulated and coated thereon.
  • a pressure-sensitive record sheet material comprising supporting web material having adhesively bound on at least one surface thereof at least three color-forming reactants, one of which is an acid-colorable, colorless, chromogenic dye-precursor material, a second of which is an oil-soluble phenol-formaldehyde novolak resin and a third of which is an oil-soluble water-insoluble metal salt, and oily solvent droplets capable of dissolving said colorforming reactants in mutual solution, wherein said oily solvent droplets are held in a contained condition by hydrophilic organic polymeric film material, isolated from at least one of said color-forming reactants, provided that when the oily solvent droplets are not isolated from said resin material, said droplets are isolated from said other color-forming reactants.
  • the record sheet material of claim 2 wherein the zinc(II) salt has an anion selected from the group consisting of acetylacetonate, hexafluoroacetylacetonate, benzoate, naphthenate, salicylate, 2-ethylhexanoate, abietate, oleate and palmitate.
  • a pressure-sensitive record sheet material comprising supporting web material having adhesively bound on a surface thereof oil-soluble phenol-formaldehyde novolak resin material, microscopic droplets of oil, an oil-soluble water-insoluble metal salt and a substantially colorless acid-colorable chromogenic dye-precursor material, wherein said oil droplets are held in an isolated and contained condition by hydrophilic, organic, polymeric, film material, and wherein said resin material is present on said web material as a particulate coating or a solution residue coating.
  • said chromogenic dye-precursor material is Crystal Violet lactone and said metal salt is a zinc(II) salt selected from the group consisting of acetylacetonate, caprylate, laurate, Z-ethylhexanoate, oleate, abietate and naphthenate and wherein said dye-precursor material and said metal salt are dissolved together in said oil droplets.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US3723156D 1971-06-14 1971-06-14 Record material Expired - Lifetime US3723156A (en)

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Application Number Priority Date Filing Date Title
US15307971A 1971-06-14 1971-06-14

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US (1) US3723156A (enExample)
JP (1) JPS557397B1 (enExample)
AR (1) AR193729A1 (enExample)
AT (1) AT321957B (enExample)
AU (1) AU455353B2 (enExample)
BE (1) BE784787A (enExample)
CA (1) CA961266A (enExample)
DE (1) DE2228430C3 (enExample)
DK (1) DK135751B (enExample)
ES (1) ES402992A1 (enExample)
FR (1) FR2141856B1 (enExample)
GB (1) GB1348961A (enExample)
IT (1) IT947926B (enExample)
NL (1) NL168761C (enExample)
NO (1) NO136961C (enExample)
SE (1) SE379502B (enExample)
ZA (1) ZA72743B (enExample)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4851715A (enExample) * 1971-11-01 1973-07-20
US3896255A (en) * 1972-07-14 1975-07-22 Fuji Photo Film Co Ltd Recording sheet
US3906141A (en) * 1973-08-15 1975-09-16 Ibm Printing system
US3952132A (en) * 1972-11-21 1976-04-20 Fuji Photo Film Co., Ltd. Recording sheet
US3970769A (en) * 1973-10-12 1976-07-20 Fuji Photo Film Co., Ltd. Recording sheet and method for the production thereof
US3983292A (en) * 1971-08-27 1976-09-28 Sanko Chemical Company Ltd. Pressure sensitive recording papers
US3996405A (en) * 1973-01-24 1976-12-07 Ncr Corporation Pressure-sensitive record material
FR2318033A1 (fr) * 1975-07-15 1977-02-11 Minnesota Mining & Mfg Encre sensibilisatrice pour formation d'images latentes
US4022936A (en) * 1975-04-28 1977-05-10 Ncr Corporation Record material
US4025490A (en) * 1974-11-11 1977-05-24 The Mead Corporation Method of producing metal modified phenol-aldehyde novolak resins
US4027065A (en) * 1975-04-28 1977-05-31 Ncr Corporation Pressure-sensitive record material
US4166644A (en) * 1977-06-21 1979-09-04 Ncr Corporation Pressure-sensitive record material containing urea-formaldehyde resin pigment
US4188456A (en) * 1977-12-23 1980-02-12 Ncr Corporation Pressure-sensitive recording sheet
US4197346A (en) * 1978-10-10 1980-04-08 Appleton Papers Inc. Self-contained pressure-sensitive record material and process of preparation
US4235769A (en) * 1978-01-26 1980-11-25 Mitsui Toatsu Chemicals, Inc. Color-developing phenolic-aldehyde composition for pressure-sensitive recording sheet material and process for the preparation thereof
US4303719A (en) * 1980-07-29 1981-12-01 Vassiliades Anthony E Chromogenic copy system
DE3112195A1 (de) * 1980-03-28 1982-01-14 Mitsui Toatsu Chemicals, Inc., Tokyo "farbentwickler fuer druckempfindliche aufzeichnungsfolien"
US4337968A (en) * 1978-11-17 1982-07-06 The Standard Register Company Sensitized record sheet
US4372583A (en) * 1980-07-29 1983-02-08 Vassiliades Anthony E Chromogenic copy system and method
US4379897A (en) * 1980-03-28 1983-04-12 Mitsui Toatsu Chemicals, Inc. Color-developer for pressure-sensitive sheets
US4400492A (en) * 1980-04-04 1983-08-23 Mitsui Toatsu Chemicals, Inc. Color-developer for pressure-sensitive recording sheets
US4882211A (en) * 1988-08-03 1989-11-21 Moore Business Forms, Inc. Paper products with receptive coating for repositionable adhesive and methods of making the products
US5017546A (en) * 1988-04-20 1991-05-21 Brinkman Karl M Alkyl salicylate developer resin for carbonless copy paper and imaging use
US5443629A (en) * 1991-11-27 1995-08-22 Alex Wilson Coldstream, Ltd. Latent image ink

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1567906A (en) 1976-01-19 1980-05-21 Ici Ltd Solvent compositions
DE2731418C3 (de) * 1977-07-12 1987-10-22 Feldmühle AG, 4000 Düsseldorf Farbreaktives Aufzeichnungsmaterial und Verfahren zu seiner Herstellung

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3983292A (en) * 1971-08-27 1976-09-28 Sanko Chemical Company Ltd. Pressure sensitive recording papers
JPS4851715A (enExample) * 1971-11-01 1973-07-20
US3896255A (en) * 1972-07-14 1975-07-22 Fuji Photo Film Co Ltd Recording sheet
US3952132A (en) * 1972-11-21 1976-04-20 Fuji Photo Film Co., Ltd. Recording sheet
US3996405A (en) * 1973-01-24 1976-12-07 Ncr Corporation Pressure-sensitive record material
US3906141A (en) * 1973-08-15 1975-09-16 Ibm Printing system
US3970769A (en) * 1973-10-12 1976-07-20 Fuji Photo Film Co., Ltd. Recording sheet and method for the production thereof
US4025490A (en) * 1974-11-11 1977-05-24 The Mead Corporation Method of producing metal modified phenol-aldehyde novolak resins
US4022936A (en) * 1975-04-28 1977-05-10 Ncr Corporation Record material
US4027065A (en) * 1975-04-28 1977-05-31 Ncr Corporation Pressure-sensitive record material
FR2318033A1 (fr) * 1975-07-15 1977-02-11 Minnesota Mining & Mfg Encre sensibilisatrice pour formation d'images latentes
US4166644A (en) * 1977-06-21 1979-09-04 Ncr Corporation Pressure-sensitive record material containing urea-formaldehyde resin pigment
US4188456A (en) * 1977-12-23 1980-02-12 Ncr Corporation Pressure-sensitive recording sheet
US4235769A (en) * 1978-01-26 1980-11-25 Mitsui Toatsu Chemicals, Inc. Color-developing phenolic-aldehyde composition for pressure-sensitive recording sheet material and process for the preparation thereof
US4197346A (en) * 1978-10-10 1980-04-08 Appleton Papers Inc. Self-contained pressure-sensitive record material and process of preparation
US4337968A (en) * 1978-11-17 1982-07-06 The Standard Register Company Sensitized record sheet
DE3112195A1 (de) * 1980-03-28 1982-01-14 Mitsui Toatsu Chemicals, Inc., Tokyo "farbentwickler fuer druckempfindliche aufzeichnungsfolien"
US4379897A (en) * 1980-03-28 1983-04-12 Mitsui Toatsu Chemicals, Inc. Color-developer for pressure-sensitive sheets
US4400492A (en) * 1980-04-04 1983-08-23 Mitsui Toatsu Chemicals, Inc. Color-developer for pressure-sensitive recording sheets
US4303719A (en) * 1980-07-29 1981-12-01 Vassiliades Anthony E Chromogenic copy system
US4372583A (en) * 1980-07-29 1983-02-08 Vassiliades Anthony E Chromogenic copy system and method
US5017546A (en) * 1988-04-20 1991-05-21 Brinkman Karl M Alkyl salicylate developer resin for carbonless copy paper and imaging use
US4882211A (en) * 1988-08-03 1989-11-21 Moore Business Forms, Inc. Paper products with receptive coating for repositionable adhesive and methods of making the products
US5443629A (en) * 1991-11-27 1995-08-22 Alex Wilson Coldstream, Ltd. Latent image ink

Also Published As

Publication number Publication date
AT321957B (de) 1975-04-25
NO136961B (no) 1977-08-29
DE2228430A1 (de) 1972-12-21
DE2228430C3 (de) 1981-07-09
FR2141856A1 (enExample) 1973-01-26
AR193729A1 (es) 1973-05-22
DE2228430B2 (de) 1973-11-22
BE784787A (fr) 1972-10-02
ES402992A1 (es) 1975-12-16
FR2141856B1 (enExample) 1977-12-23
JPS557397B1 (enExample) 1980-02-25
NL7207993A (enExample) 1972-12-18
NO136961C (no) 1977-12-07
DK135751B (da) 1977-06-20
GB1348961A (en) 1974-03-27
AU455353B2 (en) 1974-11-07
AU4073072A (en) 1973-10-11
NL168761C (nl) 1982-05-17
NL168761B (nl) 1981-12-16
ZA72743B (en) 1972-10-25
IT947926B (it) 1973-05-30
CA961266A (en) 1975-01-21
SE379502B (enExample) 1975-10-13
DK135751C (enExample) 1977-11-21

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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