US3732120A - Pressure-sensitive recording sheet - Google Patents
Pressure-sensitive recording sheet Download PDFInfo
- 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
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- United States
- Prior art keywords
- metal
- resin
- sheet
- zinc
- oil
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- 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
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- 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
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- 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
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- 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.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Color Printing (AREA)
- Photoreceptors In Electrophotography (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US15283071A | 1971-06-14 | 1971-06-14 |
Publications (1)
Publication Number | Publication Date |
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US3732120A true US3732120A (en) | 1973-05-08 |
Family
ID=22544627
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US3732120D Expired - Lifetime US3732120A (en) | 1971-06-14 | 1971-06-14 | Pressure-sensitive recording sheet |
Country Status (19)
Country | Link |
---|---|
US (1) | US3732120A (ru) |
JP (1) | JPS5525998B1 (ru) |
AR (1) | AR200714A1 (ru) |
AT (1) | AT315210B (ru) |
BE (1) | BE784786A (ru) |
BR (1) | BR7202681D0 (ru) |
CA (1) | CA981988A (ru) |
CH (1) | CH563247A5 (ru) |
DE (1) | DE2228431C3 (ru) |
DK (1) | DK134311B (ru) |
ES (1) | ES402993A1 (ru) |
FR (1) | FR2141855B1 (ru) |
GB (1) | GB1348362A (ru) |
IT (1) | IT947925B (ru) |
NL (1) | NL151663B (ru) |
NO (1) | NO137533C (ru) |
SE (1) | SE373784B (ru) |
SU (1) | SU1056889A3 (ru) |
ZA (1) | ZA72742B (ru) |
Cited By (51)
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 |
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 |
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS625955U (ru) * | 1985-06-26 | 1987-01-14 | ||
JPS62107968U (ru) * | 1985-12-25 | 1987-07-10 | ||
JP6843260B2 (ja) | 2017-09-29 | 2021-03-17 | 本田技研工業株式会社 | 鞍乗り型電動車両 |
-
1971
- 1971-06-14 US US3732120D patent/US3732120A/en not_active Expired - Lifetime
-
1972
- 1972-02-04 ZA ZA720742A patent/ZA72742B/xx unknown
- 1972-02-09 CA CA134,365A patent/CA981988A/en not_active Expired
- 1972-02-25 IT IT2106472A patent/IT947925B/it active
- 1972-04-13 NO NO128272A patent/NO137533C/no unknown
- 1972-04-25 SE SE542772A patent/SE373784B/xx unknown
- 1972-05-02 BR BR268172A patent/BR7202681D0/pt unknown
- 1972-05-19 ES ES402993A patent/ES402993A1/es not_active Expired
- 1972-05-22 GB GB2387472A patent/GB1348362A/en not_active Expired
- 1972-05-25 JP JP5127372A patent/JPS5525998B1/ja active Pending
- 1972-06-10 DE DE2228431A patent/DE2228431C3/de not_active Expired
- 1972-06-12 NL NL7207992A patent/NL151663B/xx not_active IP Right Cessation
- 1972-06-12 AT AT502072A patent/AT315210B/de not_active IP Right Cessation
- 1972-06-13 DK DK293872A patent/DK134311B/da not_active IP Right Cessation
- 1972-06-13 BE BE784786A patent/BE784786A/xx not_active IP Right Cessation
- 1972-06-13 FR FR7221165A patent/FR2141855B1/fr not_active Expired
- 1972-06-13 SU SU721797541A patent/SU1056889A3/ru active
- 1972-06-14 CH CH888872A patent/CH563247A5/xx not_active IP Right Cessation
-
1974
- 1974-05-04 AR AR24179674A patent/AR200714A1/es active
Cited By (59)
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 |
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 |
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 |
---|---|
IT947925B (it) | 1973-05-30 |
AR200714A1 (es) | 1974-12-13 |
SE373784B (ru) | 1975-02-17 |
DE2228431A1 (de) | 1972-12-21 |
FR2141855B1 (ru) | 1980-04-25 |
FR2141855A1 (ru) | 1973-01-26 |
DK134311C (ru) | 1977-03-14 |
DE2228431C3 (de) | 1974-06-20 |
ZA72742B (en) | 1972-10-25 |
NL151663B (nl) | 1976-12-15 |
DK134311B (da) | 1976-10-18 |
BR7202681D0 (pt) | 1973-06-12 |
NL7207992A (ru) | 1972-12-18 |
DE2228431B2 (de) | 1973-11-22 |
JPS5525998B1 (ru) | 1980-07-10 |
AT315210B (de) | 1974-05-10 |
ES402993A1 (es) | 1975-12-16 |
CA981988A (en) | 1976-01-20 |
NO137533C (no) | 1978-03-15 |
GB1348362A (en) | 1974-03-13 |
NO137533B (no) | 1977-12-05 |
CH563247A5 (ru) | 1975-06-30 |
SU1056889A3 (ru) | 1983-11-23 |
BE784786A (fr) | 1972-10-02 |
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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 |