US3732120A - Pressure-sensitive recording sheet - Google Patents

Pressure-sensitive recording sheet Download PDF

Info

Publication number
US3732120A
US3732120A US3732120DA US3732120A US 3732120 A US3732120 A US 3732120A US 3732120D A US3732120D A US 3732120DA US 3732120 A US3732120 A US 3732120A
Authority
US
United States
Prior art keywords
metal
resin
sheet
zinc
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Other languages
English (en)
Inventor
B Brockett
R Miller
M Hinkle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Appvion LLC
NCR Voyix Corp
National Cash Register Co
Original Assignee
NCR Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NCR Corp filed Critical NCR Corp
Application granted granted Critical
Publication of US3732120A publication Critical patent/US3732120A/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.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • 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

  • This invention relates to record material sheets bearing a coating of an oil-soluble metal salt of a phenol-formaldehyde novolak resin as a co-reactant 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 parasubstituted 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 receiving sheets of this invention constitute a further improvement wherein both the metallic moiety and the acidic resin are part of the same oil-soluble molecule and both are available for colordeveloping reaction in oil solution.
  • This improvement can be realized by providing on the sheet surface certain oil-soluble metal salts of phenol-formaldehyde resins.
  • Such salts are known, but not in the record material art. See United States Patent 2,760,852, which issued Aug. 28, 1956 on application of Donald R. Stevens et al., for a discussion of syntheses of phenol-formaldehyde-metal salts and their use as lubricating oil additives.
  • An object of this invention is to provide a metal-modified oil-soluble phenol-formaldehyde resin, for use in carbonless copypaper record materials, which give developed prints that are more resistant to fade than those developed by the known-art resins.
  • This object is realized by replacing part of the phenolic protons of an oil-soluble phenolformaldehyde resin with a metallic cation.
  • the fade-resistance of known-art resins is improved by replacement of part of the phenolic protons with metallic cations, the choice of which metal cation being of minor importance.
  • This object is best realized by replacing part of the phenolic protons of a phenol-formaldehyde resin with certain preferred cations, namely cadmium (III), zinc(II), and zirconium(II) to give metal-modified resin with enhanced fresh-print intensity.
  • metallic ions which give improved fade-resistance and similar (but not necessarily improved) fresh-print intensity to known-art unmodified resins when used to make metal-modified resins according to this invention include: vanadium(II), manganese(II), calcium(II), nickel(II), cobalt(II), strontium(H), aluminum(III), copper(III), and tin(II).
  • the weight percent of metal ion in useful metal resinates will vary depending on the metal chosen and the resin chosen. In general, only small amounts of metal ion need be introduced (about one percent by weight) to give appreciable improvement in print fade resistance and print intensity. If zinc(II) is chosen as the metal to replace one phenolic proton in each molecule of a commercial sample of paraphenylphenol-formaldehyde resin, having an average of three repeating units per molecule, a maximum of about 6 percent by weight of zinc can be readily introduced.
  • replaceable protons will be defined as readily replaceable protons, that is only about one phenolic proton per molecule of resin mixture.
  • weight percent range (1 to 6 percent) of zinc(II) in the zinc resinate derived from the specified para-phenylphenol-formaldehyde resin, represents a metal ion replacement of about 15 to percent of the replaceable protons.
  • the preferred range of proton replacement or metallization in a phenol-formaldehyde 3 novolak is about 30 to 100 percent of the replaceable protons.
  • this preferred range of proton replacement represents a metal resinate having a composition that includes about 2 to 6 weight percent of zinc(II).
  • 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 para-phenylphenol-formaldehyde resin together with zinc chloride) so that it may be used in a variety of ways including particulate coating on a sheet, solution coating on a sheet, said coatings in combination with encapsulated oily solvents provided in or near said coatings for dissolution and transfer of said color-developing agent in use, and coatings of oily solution droplets of resin isolated and contained by organic, hydrophilic, polymeric film material as microcapsules or dried emulsion films.
  • an object of this invention is to realize improvements in the speed and intensity of print development as well as 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 difficult to achieve with poly(vinyl alcohol) as the sole binder and furthermore such sheets do not give good printing characteristics with off-set printing presses and inks.
  • metal resinates are greatly advantageous over known-art resins.
  • metal resinates tested and found useful for decreasing print fade should be noted inasmuch as they include metals from Periodic Groups I-A and B, I I-A and B, III-A and B, IV-A and B, V-B, VI-B, VII-B, and VIII.
  • metal-modified resins in enhancing color-production, in chromogenic dye-precursors such as CVL, is inversely related to the chelating-ability of the metal ion used to make the metal-modified resin.
  • metals that form very stable chelates with acetylacetone, having stability constant logs (log Kstabimy corrected to zero ionic strength) greater than about 5.5 do not generally enhance CVL color-production when used to make metalmodified resins.
  • the metals of more unstable metal acetylacetone chelates, having ionization constant logs less than about 5.5 will generally be found to enhance a CVL-resin color intensity in solution.
  • Such metallic ions and resins modified therewith are designated herein as color-enhancing metals and color-enhancing metalmodified resins. That is to say, solutions of CVL and metal-modified resin will generally show higher optical densities as the stability constants of the chelates of the chosen metals and acetylacetone decrease. However, it should be noted that there will be wide variance among the oil-solubilities of these color-enhancing metal-modified resins which Will affect the maximum concentration of the colored species attainable in the chosen oil. In any chosen record-material system, the most useful metals will be those color-enhancing metals whose metal resinates are readily soluble in the liquid vehicle droplets used in the record material system capsules. For a metal to be useful as a metal-modified resin in a record material copy sheet, the metal must be a color enhancer and the metal-modified resin must be readily soluble in the oil droplets included in the copy paper.
  • oily, colorless, chromogenic dye-precursor inks used in the carbonless copy-paper field are solutions of solid, colorless, basic, chromogenic dye-precursor materials in oily vehicles having a dielectric constant of about 5 or less.
  • Halogen-substituted aromatic hydrocarbons, alkylated aromatic hydrocarbons and dialkyl phthalates are typical of the oils used as ink vehicles.
  • the metal-modified resins of this invention are designed to operate and do operate well in developing oily dyeprecursor 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.
  • the metal-modified 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 so-limited in use.
  • a color-developing system comprising oil-soluble dye precursor material, oil-soluble polymeric resin co-reactant material and mutual-solvent oil.
  • FIG. 2 of the Miller- Phillips application shows a number of such arrangements.
  • any and all of the metal-modified resins of this invention may be coated on paper, as particulate material or as a printed solution residue, or included among the fibers of a fibrous substrate such as paper, or dissolved in oil and encapsulated as solution droplets prior to being coated on paper so as to operate in all of the record-material constructions of the Miller-Phillips applications FIG. 2.
  • the metal-modified resins of this invention are oil-soluble and are grindable to a fine powder, and are encapsulatable as fine oil-solution droplets. So
  • Example 3 The preparations of both kinds of metalmodified resin transfer sheets are taught in Example 3: transfer sheets having coated on a surface oil-soluble meal-modified resin particles together with microcapsules containing an inert oily solvent and transfer sheets having surface coatings of microcapsules containing oilsolution droplets of a metal-modified resin.
  • the metal-modified resins of this invention may be applied to substrate sheets in many different ways including being: (1) applied to a sheet from a printing solution as taught in the aforementioned Miller-Phillips application and in United States 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 U.S. 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 U.S. Pat.
  • Methods of making the useful metal resinate salts of this invention include reaction of an oil-soluble phenolaldehyde resin, preferably a para-substituted-phenol-formaldehyde novolak resin, with a desired metal hydroxide or oxide.
  • a water soluble intermediate metal resinate may be made by treatment of the resin with a strong aqueous base, such as aqueous sodium hydroxide for instance, to give an aqueous solution of sodium resinate, followed by treatment of the sodium resinate solution with an aqueous solution of a salt of a desired metal, zinc chloride for instance, to bring about a precipitation of the desired metal resinate, zinc resinate in this instance.
  • a preferred method involves the reaction of an oilsoluble phenol-aldehyde novolak melt with a desired metal carboxylate or enolate.
  • This method is exemplified in Example 1 where a novolak is melted and treated with zinc hydroxy benzoate powder to give zinc resinate plus benzoic acid.
  • zinc acetylacetonate is used in place of zinc hydroxy benzoate, zinc resinate is similarly formed together with free acetylacetone in the hot melt reaction.
  • a metal salt may be added to a phenol-formaldehyde reaction mixture at the time of resin manufacture.
  • a particularly convenient method is to simply dissolve the chosen novolak and a carboxylate or enolate of the chosen metal in an encapsulatable oil.
  • the novolaks used in this invention are sufliciently acidic to compete for the metal ions and act as metal resinates even in the presence of the added metal salt anion.
  • EXAMPLE 1 Useful metal resinates A mixture of two kilograms of p-phenylphenolformaldehyde resin with 400 grams of zinc hydroxy benzoate was heated and stirred for one hour, under a helium blanket, at elevated temperatures. The temperature was gradually raised from room temperature to about 200 to 220 degrees centigrade over a period of about 45 minutes and then allowed to cool to about degrees centigrade over the next fifteen minutes. At the end of the reaction time the hot zinc resinate was poured from the reaction vessel and allowed to cool and harden. The hardened resin was ground under water in an attritor to give a fine powder suitable for coating as particulate matter on a paper sheet. The zinc content of this resinate (after discarding and disregarding a small amount of oil-insoluble inorganic sludge present in the reaction product) was found to be 5.0 percent, by Weight.
  • a hot melt of one kilogram of p-phenylphenol-formaldehyde resin at 160 degrees centigrade was agitated and treated with 100 grams of zinc acetylacetonate which was added slowly. Following the addition, the agitated melt was held at the elevated temperature for ten minutes, poured and allowed to harden.
  • air knife coater air-pressure 2.75 pounds/square inch
  • dried by a 12-second pass through a high-velocity-air 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.
  • the CF test sheet of this invention used to obtain the test data in the table following these examples was made according to the procedure of this example with a slight variation in the dry formulation: zinc-modified resin (12.0), kaolin clay (60.0), silica gel (3.0), calcium carbonate (9.0), styrene-butadiene latex binder (7.5), cooked starch binder (8.5).
  • the dry formulation was made up to 30 percent solids and coated as before to give a 5 pound per specified ream dry coat weight.
  • EXAMPLE 3 Metal-modified resin transfer sheets
  • the coating slurry of Example 2 was coated at 4 pounds coat weight per specified ream on a paper sheet surface which already carried a coat (2.5 pounds per specified ream) of oil-containing rnicrocapsules bound thereto with cooked starch binder.
  • the rnicrocapsules were made according to the procedure of B. K. Green and L. Schleicher (US. Pat. 2,800,457) with gelatin-gum arabic walls and with isopropyl-biphenyl droplets as the core material.
  • the so-made copy sheets was mated with a second sheet of paper (which had been dipped in a 2 percent solution of CVL in alcohol and dried to leave a residue of CVL thereon) with the coated face of the copy sheet opposing said second sheet.
  • a copy of the writing appeared on the second sheet as a result of the oil transfer of the metal modified resin from the coated surface of the copy sheet to the CVL- containing sheet.
  • Example II (C) A metal-modified resin solution was encapsulated according to the procedure of Example II (C) of United States Pat. No. 3,341,466, which issued Sept. 12, 1967 on the application of Carl Brynko et al.
  • the core material in this case was prepared by dissolving in 50 parts of 1,2,4 trimethylbenzene, parts of para-phenylphenolformaldehyde resin and a solution of 14.5 parts of zinc naphthenate in parts of a low-volatility hydrocarbon solvent, and dispersing the oily solution in an aqueous vehicle to give droplets of about 3.5 micron average diameter.
  • 1-(2- pyridylazo) 2 naphthol is a colorimetric indicator genmark was produced by the above transfer sheet.
  • 1-(2- pyridylazo) 2 naphthol is a colorimetric indicator generally used for the detection of zinc(II).
  • EXAMPLE 4 Self-contained copy-sheets
  • Self-contained pressure-sensitive sheets that is single sheets which contain all the color-producing elements, namely metal-modified resin, chromogenic dye-precursor material, and isolated solvent capable of dissolving both the co-reactants, were produced by coating a metal-modified resin slurry (according to Example 2) over a commercial NCR Paper CB sheet capsular coating or alternatively by coating the metal-modified resin-containing capsules, of this example, directly on the CVL-sensitized sheet of this example.
  • the following table presents comparable data on a known-art, resin-sensitized receiving sheet, a CF sheet, of good commercial quality and a metal-modified resinsensitized CF sheet of this invention, for use with various capsular transfer sheets, CB sheets, which yield colorless, liquid dye-precursor inks under imaging pressure.
  • TI stands for "Typewriter Intensity" and is equal to times the ratio of the reflectance of a printed character divided by the background reflectance. A Tl value of 100 indicates no discernible print and a lower I value indicates a darker or more intense print. Column (1) gives TI values read 20 minutes after printing.
  • the Phillips-Hem CF Sheet is a kaolin-phenolic CF sheet prepared according to United States Patent 721 with 5.5 parts of kaolin to one part of paraphenylphenol-iormaldehyde resin at a dry coat
  • the CF Sheet of This Invention is a sheet of Example 2, prepared from the zinc-modified resin of Example 1, having 5.0 weight percent zinc(II), in the resin or about 90 to 100% of its available protons replaced with ARO sheet having 3.3 pounds/ream of rnicrocapsules containing chlorinated biphenyl-high boiling alkane ream of rnicrocapsules containing diphenyl oxide-high boiling alkane (2:1) 3.5 pounds/ream of rnicrocapsules containing dioctyl adlpate-alkylated benzene (2:1) 2.6 pounds/ream oi rnicrocapsules containing dioctyl
  • the typewriter intensities presented give a measure of several properties of the CF sheets, being compared. These are:
  • a pressure-sensitive record sheet material comprising supporting web material having adhesively bound on a surface thereof a coating which includes at least two color-forming reactants, one an oil-soluble metal salt of a phenol-formaldehyde novolak resin, and another a colorless, chrornogenie dye-precursor material reactively colorable by said novolak resin salt, an oily solvent droplets capable of dissolving said color-forming reactants in mutual solution, wherein said oily solvent droplets are isolated from at least one of said, color-forming reactants and are held in 21 contained condition by hydrophilic organic polymeric film material.
  • metal of the metal salt is selected from the group consisting of aluminum, barium, cadmium, calcium, cerium, cesium, cobalt, copper, indium, magnesium, manganese, molybdenum, nickel, lead, sodium, strontium, tin, titanium, vanadium, zinc and zirconium.
  • metal of the metal salt is selected from the group consisting of aluminum, cadmium, calcium, cobalt, copper, manganese, nickel, strontium, tin, vanadium, zinc, and zirconium.
  • novolak resin is a para-substituted phenol-formaldehyde resin.
  • novolak resin is a para-phenylpehnol-formaldehyde resin.
  • novolak resin is a para-phenylphenol-formaldehyde resin.
  • metal of the metal salt is selected from metal ions that form chelates' wtih acetylacetone having stability constant logs (log K corrected to zero ionic strength) no greater than 5.5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
US3732120D 1971-06-14 1971-06-14 Pressure-sensitive recording sheet Expired - Lifetime US3732120A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15283071A 1971-06-14 1971-06-14

Publications (1)

Publication Number Publication Date
US3732120A true US3732120A (en) 1973-05-08

Family

ID=22544627

Family Applications (1)

Application Number Title Priority Date Filing Date
US3732120D Expired - Lifetime US3732120A (en) 1971-06-14 1971-06-14 Pressure-sensitive recording sheet

Country Status (19)

Country Link
US (1) US3732120A (enrdf_load_html_response)
JP (1) JPS5525998B1 (enrdf_load_html_response)
AR (1) AR200714A1 (enrdf_load_html_response)
AT (1) AT315210B (enrdf_load_html_response)
BE (1) BE784786A (enrdf_load_html_response)
BR (1) BR7202681D0 (enrdf_load_html_response)
CA (1) CA981988A (enrdf_load_html_response)
CH (1) CH563247A5 (enrdf_load_html_response)
DE (1) DE2228431C3 (enrdf_load_html_response)
DK (1) DK134311B (enrdf_load_html_response)
ES (1) ES402993A1 (enrdf_load_html_response)
FR (1) FR2141855B1 (enrdf_load_html_response)
GB (1) GB1348362A (enrdf_load_html_response)
IT (1) IT947925B (enrdf_load_html_response)
NL (1) NL151663B (enrdf_load_html_response)
NO (1) NO137533C (enrdf_load_html_response)
SE (1) SE373784B (enrdf_load_html_response)
SU (1) SU1056889A3 (enrdf_load_html_response)
ZA (1) ZA72742B (enrdf_load_html_response)

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864146A (en) * 1971-06-16 1975-02-04 Kanzaki Paper Mfg Co Ltd Sensitized record sheet material
DE2438741A1 (de) * 1973-08-15 1975-02-27 Ibm Drucksystem
US3924027A (en) * 1972-09-27 1975-12-02 Sanko Chemical Co Ltd Process for the production of sensitized sheet material
US3950309A (en) * 1971-10-29 1976-04-13 Hitachi Chemical Co., Ltd. Novel thermosetting resins and process for preparing the same comprising reacting a novolak with a titanic acid ester
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
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
US4034128A (en) * 1975-05-05 1977-07-05 The Mead Corporation Production of a color developing record sheet containing metal-modified novolak resin particles
US4051303A (en) * 1972-08-15 1977-09-27 Fuji Photo Film Co., Ltd. Recording sheet
US4060262A (en) * 1976-03-24 1977-11-29 The Standard Register Company Record material
US4096314A (en) * 1975-06-06 1978-06-20 Kores Holding Zug Ag Pressure-sensitive transfer sheet
DE2854318A1 (de) * 1977-12-23 1979-07-19 Appleton Paper Inc Farbentwicklerzubereitung und sie enthaltendes aufzeichnungsmaterial
US4165103A (en) * 1978-05-31 1979-08-21 Ncr Corporation Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developing agent
US4165102A (en) * 1978-05-31 1979-08-21 Ncr Corporation Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developer
US4173684A (en) * 1977-09-06 1979-11-06 The Mead Corporation Production of novel metal modified novolak resins and their use in pressure sensitive papers
US4226962A (en) * 1977-09-06 1980-10-07 The Mead Corporation Production of novel metal modified novolak resins and their use in pressure sensitive papers
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
US4348234A (en) * 1979-03-20 1982-09-07 Ciba-Geigy Corporation Coating compositions for the production of a recording material
US4379897A (en) * 1980-03-28 1983-04-12 Mitsui Toatsu Chemicals, Inc. Color-developer for pressure-sensitive sheets
US4396705A (en) * 1980-09-19 1983-08-02 Hitachi, Ltd. Pattern forming method and pattern forming apparatus using exposures in a liquid
US4400492A (en) * 1980-04-04 1983-08-23 Mitsui Toatsu Chemicals, Inc. Color-developer for pressure-sensitive recording sheets
US4585837A (en) * 1983-03-29 1986-04-29 Hitco Resoles containing zirconium metal atoms
US4839457A (en) * 1987-03-20 1989-06-13 Mitsubishi Petrochemical Co., Ltd. Developing composition and a sheet for pressure-sensitive copy paper
US4853364A (en) * 1988-02-05 1989-08-01 The Mead Corporation Developer composition comprising phenol resins and vinylic or acrylic resins
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
US4908301A (en) * 1988-03-23 1990-03-13 Olin Corporation Color-self-developing, microcapsular toner particles
US5015549A (en) * 1988-03-23 1991-05-14 Olin Corporation Composition and electrophotographic use of microcapsular photoactive toner particles
US5102856A (en) * 1990-11-07 1992-04-07 The Standard Register Company High solids self-contained printing ink
US5350729A (en) * 1993-03-02 1994-09-27 The Mead Corporation Developer sheet with structured clays and process thereof
US5443629A (en) * 1991-11-27 1995-08-22 Alex Wilson Coldstream, Ltd. Latent image ink
US5709738A (en) * 1996-06-06 1998-01-20 Moore Business Forms Inc Coating composition for ink jet printing
US5783353A (en) * 1994-06-10 1998-07-21 Cycolor, Inc. Self-contained imaging assembly
US6030740A (en) * 1998-03-12 2000-02-29 Cycolor, Inc. Two-sided imaging material
US6037094A (en) * 1998-10-23 2000-03-14 Cycolor, Inc. Photosensitive material employing microcapsules and superabsorbent polymer
US6080520A (en) * 1999-05-26 2000-06-27 Cycolor, Inc. Imaging system having opaque support
US6127084A (en) * 1998-10-23 2000-10-03 Cycolor, Inc. Photosensitive material employing microcapsules containing a hygroscopic polymer in the internal phase
US6514909B1 (en) 2000-02-24 2003-02-04 The Mead Corporation Dual layer self-contained paper incorporating hollow spherical plastic pigment
US6638678B2 (en) 2001-11-20 2003-10-28 Hsbc Bank Usa Method for improving sensitometric response of photosensitive imaging media employing microcapsules
US6740465B2 (en) 2000-06-01 2004-05-25 Sipix Imaging, Inc. Imaging media containing heat developable photosensitive microcapsules
US20040169071A1 (en) * 2003-02-28 2004-09-02 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
US20040214134A1 (en) * 2003-04-22 2004-10-28 Appleton Papers Inc. Dental articulation kit and method
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
US6964836B2 (en) 2002-03-15 2005-11-15 Eastman Kodak Company Photosensitive microcapsules containing a synthetic viscosity modifier in the continuous phase
US20060063125A1 (en) * 2003-04-22 2006-03-23 Hamilton Timothy F Method and device for enhanced dental articulation
US20080248950A1 (en) * 2007-04-04 2008-10-09 Ibrahim Katampe Ink and Developer System
WO2015017494A1 (en) 2013-07-31 2015-02-05 P.H. Glatfelter Company Tamper evident documents and inks
US10718089B2 (en) 2014-06-13 2020-07-21 Papierfabrik August Koehler Se CF paper

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS625955U (enrdf_load_html_response) * 1985-06-26 1987-01-14
JPS62107968U (enrdf_load_html_response) * 1985-12-25 1987-07-10
CN111148689B (zh) 2017-09-29 2021-08-20 本田技研工业株式会社 跨骑型电动车辆

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864146A (en) * 1971-06-16 1975-02-04 Kanzaki Paper Mfg Co Ltd Sensitized record sheet material
US3983292A (en) * 1971-08-27 1976-09-28 Sanko Chemical Company Ltd. Pressure sensitive recording papers
US3950309A (en) * 1971-10-29 1976-04-13 Hitachi Chemical Co., Ltd. Novel thermosetting resins and process for preparing the same comprising reacting a novolak with a titanic acid ester
US4051303A (en) * 1972-08-15 1977-09-27 Fuji Photo Film Co., Ltd. Recording sheet
US3924027A (en) * 1972-09-27 1975-12-02 Sanko Chemical Co Ltd Process for the production of sensitized sheet material
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
DE2438741A1 (de) * 1973-08-15 1975-02-27 Ibm Drucksystem
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
US4027065A (en) * 1975-04-28 1977-05-31 Ncr Corporation Pressure-sensitive record material
US4082713A (en) * 1975-05-05 1978-04-04 The Mead Corporation Production of a color developing record sheet containing metal-modified novolak resin particles
US4034128A (en) * 1975-05-05 1977-07-05 The Mead Corporation Production of a color developing record sheet containing metal-modified novolak resin particles
US4096314A (en) * 1975-06-06 1978-06-20 Kores Holding Zug Ag Pressure-sensitive transfer sheet
US4060262A (en) * 1976-03-24 1977-11-29 The Standard Register Company Record material
US4173684A (en) * 1977-09-06 1979-11-06 The Mead Corporation Production of novel metal modified novolak resins and their use in pressure sensitive papers
US4226962A (en) * 1977-09-06 1980-10-07 The Mead Corporation Production of novel metal modified novolak resins and their use in pressure sensitive papers
US4188456A (en) * 1977-12-23 1980-02-12 Ncr Corporation Pressure-sensitive recording sheet
FR2412413A1 (fr) * 1977-12-23 1979-07-20 Appleton Paper Inc Composition developpant une couleur destinee a un support d'enregistrement
DE2854318A1 (de) * 1977-12-23 1979-07-19 Appleton Paper Inc Farbentwicklerzubereitung und sie enthaltendes aufzeichnungsmaterial
US4165102A (en) * 1978-05-31 1979-08-21 Ncr Corporation Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developer
US4165103A (en) * 1978-05-31 1979-08-21 Ncr Corporation Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developing agent
EP0005975A1 (en) * 1978-05-31 1979-12-12 Appleton Papers Inc. Process for preparing zinc-modified phenol-aldehyde novolak resins and heat or pressure-sensitive recording material carrying a resin so prepared
US4337968A (en) * 1978-11-17 1982-07-06 The Standard Register Company Sensitized record sheet
US4348234A (en) * 1979-03-20 1982-09-07 Ciba-Geigy Corporation Coating compositions for the production of a recording material
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
US4396705A (en) * 1980-09-19 1983-08-02 Hitachi, Ltd. Pattern forming method and pattern forming apparatus using exposures in a liquid
US4585837A (en) * 1983-03-29 1986-04-29 Hitco Resoles containing zirconium metal atoms
US4839457A (en) * 1987-03-20 1989-06-13 Mitsubishi Petrochemical Co., Ltd. Developing composition and a sheet for pressure-sensitive copy paper
US4853364A (en) * 1988-02-05 1989-08-01 The Mead Corporation Developer composition comprising phenol resins and vinylic or acrylic resins
US5015549A (en) * 1988-03-23 1991-05-14 Olin Corporation Composition and electrophotographic use of microcapsular photoactive toner particles
US4908301A (en) * 1988-03-23 1990-03-13 Olin Corporation Color-self-developing, microcapsular toner particles
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
US5102856A (en) * 1990-11-07 1992-04-07 The Standard Register Company High solids self-contained printing ink
US5443629A (en) * 1991-11-27 1995-08-22 Alex Wilson Coldstream, Ltd. Latent image ink
US5350729A (en) * 1993-03-02 1994-09-27 The Mead Corporation Developer sheet with structured clays and process thereof
US5783353A (en) * 1994-06-10 1998-07-21 Cycolor, Inc. Self-contained imaging assembly
US5916727A (en) * 1994-06-10 1999-06-29 Cycolor, Inc. Self-contained imaging assembly
US5709738A (en) * 1996-06-06 1998-01-20 Moore Business Forms Inc Coating composition for ink jet printing
US6030740A (en) * 1998-03-12 2000-02-29 Cycolor, Inc. Two-sided imaging material
US6037094A (en) * 1998-10-23 2000-03-14 Cycolor, Inc. Photosensitive material employing microcapsules and superabsorbent polymer
US6127084A (en) * 1998-10-23 2000-10-03 Cycolor, Inc. Photosensitive material employing microcapsules containing a hygroscopic polymer in the internal phase
US6080520A (en) * 1999-05-26 2000-06-27 Cycolor, Inc. Imaging system having opaque support
US6514909B1 (en) 2000-02-24 2003-02-04 The Mead Corporation Dual layer self-contained paper incorporating hollow spherical plastic pigment
US6740465B2 (en) 2000-06-01 2004-05-25 Sipix Imaging, Inc. Imaging media containing heat developable photosensitive microcapsules
US6638678B2 (en) 2001-11-20 2003-10-28 Hsbc Bank Usa Method for improving sensitometric response of photosensitive imaging media employing microcapsules
US6964836B2 (en) 2002-03-15 2005-11-15 Eastman Kodak Company Photosensitive microcapsules containing a synthetic viscosity modifier in the continuous phase
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
US20040214134A1 (en) * 2003-04-22 2004-10-28 Appleton Papers Inc. Dental articulation kit and method
US6932602B2 (en) 2003-04-22 2005-08-23 Appleton Papers Inc. Dental articulation kit and method
US20060063125A1 (en) * 2003-04-22 2006-03-23 Hamilton Timothy F Method and device for enhanced dental articulation
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
US20080248950A1 (en) * 2007-04-04 2008-10-09 Ibrahim Katampe Ink and Developer System
WO2015017494A1 (en) 2013-07-31 2015-02-05 P.H. Glatfelter Company Tamper evident documents and inks
US10718089B2 (en) 2014-06-13 2020-07-21 Papierfabrik August Koehler Se CF paper

Also Published As

Publication number Publication date
DK134311C (enrdf_load_html_response) 1977-03-14
ZA72742B (en) 1972-10-25
AT315210B (de) 1974-05-10
FR2141855A1 (enrdf_load_html_response) 1973-01-26
DE2228431A1 (de) 1972-12-21
AR200714A1 (es) 1974-12-13
NL151663B (nl) 1976-12-15
SE373784B (enrdf_load_html_response) 1975-02-17
GB1348362A (en) 1974-03-13
DK134311B (da) 1976-10-18
NL7207992A (enrdf_load_html_response) 1972-12-18
NO137533B (no) 1977-12-05
DE2228431B2 (de) 1973-11-22
SU1056889A3 (ru) 1983-11-23
BR7202681D0 (pt) 1973-06-12
BE784786A (fr) 1972-10-02
JPS5525998B1 (enrdf_load_html_response) 1980-07-10
IT947925B (it) 1973-05-30
CA981988A (en) 1976-01-20
CH563247A5 (enrdf_load_html_response) 1975-06-30
DE2228431C3 (de) 1974-06-20
FR2141855B1 (enrdf_load_html_response) 1980-04-25
NO137533C (no) 1978-03-15
ES402993A1 (es) 1975-12-16

Similar Documents

Publication Publication Date Title
US3732120A (en) Pressure-sensitive recording sheet
US3723156A (en) Record material
US3663256A (en) Mark-forming record material
US4197346A (en) Self-contained pressure-sensitive record material and process of preparation
US4165103A (en) Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developing agent
US4165102A (en) Method of preparing zinc-modified phenol-aldehyde novolak resins and use as a color-developer
US4199619A (en) Process for preparing an acceptor coated sheet for use in a pressure sensitive copying system
US4234212A (en) Recording sheet
US3516845A (en) Record sheet sensitized with salt modified kaolin-phenolic material
US4453744A (en) Pressure-sensitive or heat-sensitive recording material
CH644551A5 (de) Chromogene zusammensetzung.
US3703397A (en) Mark-forming record materials and process for their use
US4567496A (en) Pressure-sensitive recording sheets
US4418942A (en) Microcapsule sheet for pressure-sensitive recording paper
US5009919A (en) Finger-printing systems & method
US3732141A (en) Pressure-sensitive record material
US5017546A (en) Alkyl salicylate developer resin for carbonless copy paper and imaging use
CA1088307A (en) Record material
EP0017386B1 (en) Self-contained pressure sensitive recording paper
US3721576A (en) Mark forming record materials and process for their use
GB2217034A (en) Colour developer for heat or pressure-sensitive recording materials.
US3715226A (en) Mark-forming record materials
JPH0546320B2 (enrdf_load_html_response)
JPH0546319B2 (enrdf_load_html_response)
US3746563A (en) Pressure sensitive record sheet employing alkyl or halo substituted tetrahalofluorans

Legal Events

Date Code Title Description
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