US3804855A - Naphthalide compounds - Google Patents

Naphthalide compounds Download PDF

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Publication number
US3804855A
US3804855A US00237000A US23700072A US3804855A US 3804855 A US3804855 A US 3804855A US 00237000 A US00237000 A US 00237000A US 23700072 A US23700072 A US 23700072A US 3804855 A US3804855 A US 3804855A
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US
United States
Prior art keywords
naphthalide
compounds
mark
color
diethylaminophenyl
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
US00237000A
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English (en)
Inventor
S Farber
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.)
WTA Inc
NCR Voyix Corp
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
Priority to US00237000A priority Critical patent/US3804855A/en
Priority to CA162,246A priority patent/CA1003420A/en
Priority to GB1175673A priority patent/GB1368938A/en
Priority to JP3047073A priority patent/JPS5619275B2/ja
Priority to DE2313679A priority patent/DE2313679C2/de
Application granted granted Critical
Publication of US3804855A publication Critical patent/US3804855A/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
Assigned to WTA INC. reassignment WTA INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: APPLETON PAPERS INC., A CORPORTION OF DE
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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • each R is hydrogen, an alkyl radical having 1 to carbon atoms, phenyl or benzyl and each R is hydrogen or an alkyl radical having 1 to 5 carbon atoms.
  • This invention relates to colorless, but colorable compounds.
  • the compounds can be synthesized from 1,8- naphthoic anhydride.
  • the compounds are used in pressure-sensitive record material and in mark-forming manifold systems.
  • the unreacted mark-forming components (the colorless, but colorable compound and the acidic material) and a liquid solvent in which each of the mark-forming components is soluble is disposed on or within a sheet support material.
  • the liquid solvent is present in such form that is maintained isolated by a pressure-rupturable barrier from at least one of the mark-forming components until the application of pressure causes a breach of the barrier in the area delineated by the pressure pattern. The application of pressure brings the mark-forming components into reactive contact, thereby producing a distinctive mark.
  • an object of this invention is to provide colorless, but colorable naphthalide compounds.
  • each R is hydrogen, an alkyl radical having 1 to 5 carbon atoms, phenyl or benzyl and each R is hydrogen or an alkyl radical having 1 to 5 carbon atoms.
  • each R is hydrogen, methyl, ethyl or phenyl and each R is methyl or ethyl.
  • the colors developed from these compounds are blues, blue-greens, purples, and the like.
  • the naphthalide and liquid solvent are encapsulated in microscopic capsules which are coated on base sheet record material.
  • base sheet record material In close contact with the base sheet record material is a sensitized undersheet.
  • the base sheet yields the naphthalide under pressure of writing against the sensitized undersheet in a pattern of droplets corresponding to the written matter, in accordance with the disclosure of such a capsule-bearing sheet in U.S. Pat. No. 2,712,507 which issued July 5, 1955, on the application of Barrett K. Green.
  • U.S. Pat. No. 2,712,507 also discloses a preferred method of forming the capsules.
  • Other preferred methods for preparing solvent-containing microscopic capsules are disclosed in U.S. Pat. No. 2,800,457 which issued July 23, 1957, on the application of Barrett K. Green and Lowell Schleicher and in U.S. Pat. No. 3,041,289, which issued on June 26, 1962, on the application of Bernard Katchem and Robert E. Miller.
  • the encapsulated droplets are released by the rupture of capsules in writing operations.
  • the naphthalide liquid droplets are transferred in the pattern of the data configuration to the top of the underlying sheet is coated or impregnated with at least one material which is an acid reactant with respect to the naphthalide and produces color with any such component that is reactive therewith.
  • Representative acidic coating materials are, on one hand, oil-insoluble minerals or inorganic particulate solid material, represented by kaolin, attapulgite, silica gel, zeolites, and the like, and, on the other hand, organic polymeric acidic materials, such as acid-reacting phenolic resins of oil-soluble characteristics.
  • the record member consists of a base sheet or web member either of fibrous construction such as paper, or of continuous structure, such as films of organic polymer material, carrying the color reactant in an exposed state with respect to applied liquid.
  • the acid reactant when of particulate nature, is arranged in intimate juxtaposition to form an apparently unbroken liquid receptive surface, yet substantially each particle individually is available for contact with applied liquid.
  • oil-soluble organic polymeric materials suitable for use in this invention together with appropriate solvents to be used therewith, acid-reaction phenol-aldehyde and phenol-acetylene polymers, maleic acid-rosin resins partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, carboxy polymethylene (Carbopol 934), and wholly or partially hydrolyzed vinyl methyl ether-maleic anhydride copolymer are specified as typical of the reactive acidic polymeric materials.
  • acid-reaction phenol-aldehyde and phenol-acetylene polymers maleic acid-rosin resins partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers
  • carboxy polymethylene (Carbopol 934) carboxy polymethylene
  • vinyl methyl ether-maleic anhydride copolymer are specified as typical of
  • phenol-aldehyde polymers found useful are members of the type commonly referred to as novolaks, which are characterized by solubility in common organic solvents and which are, in the absence of cross-linking agents, permanently fusible.
  • Another group of useful phenol polymeric materials are alkylphenol-acetylene resins, likewise soluble in common organic solvents and possessing permanent fusibility in the absence of being treated by cross-linking material.
  • the phenolic polymer materials useful in practicing this invention are characterized by the presence of free hydroxyl groups and by the absence of groups, such as methylol, which tend to promote infusibility or cross-linking of the polymer, and by their solubility in organic solvents and relative insolubility in aqueous media.
  • a laboratory method useful in the selection of suitable phenolic resins is a determination of the infrared radiation absorption pattern of a candidate material. It has been found that phenoic resins showing an absorption in the 3200-3500 cm.- region (which is indicative of the free hydroxyl groups) and not having an absorption in the 1600-1700 cm:- region are suitable. The latter absorption region is indicative of the desensitization of the hydroxyl groups and consequently makes such groups unavailable for reaction with the chromogenic material to be specified.
  • the liquid solvent portion of this invention is capable of dissolving the mark-forming components.
  • the solvent can be volatile or nonvolatile, and a single or multiple component solvent which is wholly or partly volatile can be used.
  • volatile solvents useful with the naphthalide and acidic polymer mark-forming components specified are toluene, petroleum distillate, perchloroethylene, and xylene.
  • nonvolatile solvents are highboiling-point petroleum fractions and chlorinated diphenyls.
  • the solvent forming the vehicle to a large extent should be chosen so as to be capable of dissolving at least 1%, on a weight basis, of the naphthalic, preferably in excess of 2%, and a larger amount of polymeric material-up, say or moreto form an efficient reaction.
  • the solvent should be capable of dissolving an excess of the polymeric material, so as to provide every opportunity for maximum coloration at a reaction site.
  • a further criterion of the selected solvent is that it must not interfere with the mark-forming reaction.
  • the presence of the solvent may interfere with the mark-forming reaction or diminish the intensity of the mark, in which case the solvent chosen should be sufficiently vaporizable to assure its leaving the reaction site after having, through solution, brought the mark-forming components into intimate admixture, so that the markforming reaction proceeds.
  • the polymeric mark-forming component(s) chosen must be acidic relative to the naphthalide compound and reactive with the naphthalide material to eflfect the distinctive color formation or color change.
  • Kaolin is generally known and used in the papermaking industry as China clay and is outstandingly preferable as a particulate oil-insoluble and water-insoluble mineral material of acid characteristisc necessary to color the naphthalides of this invention.
  • a white kaolin is used, and, because of its whiteness, its plate-like particle form, which gives it unparallel coating properties in aqueous slurries, its universal abundance in supply, its historical general usage in the papermaking and paper converting industries, and its low cost, it is an ideal material.
  • Other types of particulate and substantially colorless waterand oil-insoluble minerals of the necessary acid properties are deemed equivalents of kaolin, some being bentonites.
  • Attapulgite can be used in this invention as an efficient colorless mineral reactant material to color the naphthalide of this invention that react on contact in an electron-donor-acceptor reaction, and, by reason of its high oil absorbency, is doubly useful as an absorbent reactant coating on paper to form color with such compounds dissolved in oil as may be applied to it.
  • compositions of the mark-forming materials into their supporting sheets.
  • An example of the compositions which can be coated onto the surface of an underlying sheet of a two-sheet system to react with the capsule coating on the underside of an overlying sheet is as follows:
  • Coating composition Percent by weight Phenolic polymer mixture 17 Paper coating kaolin (white 57 Calcium carbonate 12 Styrene butadiene latex 4 Ethylated starch 8 Gum arabic 2 unduly.
  • EXAMPLE VII A comparison was made between the 3-(4-diethylaminophenyl) 3 (1,2-dimethy1indol-3-yl) naphthalide prepared in Example II and a most frequently employed color reactant, namely 3,3-bis(4-dimethylaminophenyl)- G-dimethylamino-phthalide. This latter compound is more commonly known as crystal violet lactone or CVL.
  • Prints were made on paper sheets sensitized with 80-20 Resin (80 parts by weight paratertiary-butylphenol and 20 parts by weight para-chlorophenol). Reflectance intensities were obtained on the fresh prints and on the prints after 4 hours'exposure in a daylight fluorescence box.
  • the reflectance values in the following table represent a ratio of the intensity of color to the intensity of the background. A value of 1.000 would indicate a white color. If the reflectance value increases with time, the print fades. Compounds which exhibit good fade resistance will demonstrate smaller increases in R with the passage 1 of time.
  • the obtained reflectance values were:
  • naphthalide compound of this invention is more fade resistant than the most frequently employed color reactant, crystal violet lactone.
  • X is and the compound is 3-(4-diethylaminophenyl)-3-(1,2- dimethylindol-3-yl) naphthalide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Color Printing (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00237000A 1972-03-22 1972-03-22 Naphthalide compounds Expired - Lifetime US3804855A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US00237000A US3804855A (en) 1972-03-22 1972-03-22 Naphthalide compounds
CA162,246A CA1003420A (en) 1972-03-22 1973-01-29 Naphthalide compounds
GB1175673A GB1368938A (en) 1972-03-22 1973-03-12 Chromogenic naphthalide compounds
JP3047073A JPS5619275B2 (enrdf_load_stackoverflow) 1972-03-22 1973-03-15
DE2313679A DE2313679C2 (de) 1972-03-22 1973-03-20 Chromogene Naphthalidverbindungen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00237000A US3804855A (en) 1972-03-22 1972-03-22 Naphthalide compounds

Publications (1)

Publication Number Publication Date
US3804855A true US3804855A (en) 1974-04-16

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ID=22891915

Family Applications (1)

Application Number Title Priority Date Filing Date
US00237000A Expired - Lifetime US3804855A (en) 1972-03-22 1972-03-22 Naphthalide compounds

Country Status (5)

Country Link
US (1) US3804855A (enrdf_load_stackoverflow)
JP (1) JPS5619275B2 (enrdf_load_stackoverflow)
CA (1) CA1003420A (enrdf_load_stackoverflow)
DE (1) DE2313679C2 (enrdf_load_stackoverflow)
GB (1) GB1368938A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862128A (en) * 1971-12-02 1975-01-21 Polaroid Corp Naphthalide indicator dyes
US3954799A (en) * 1971-01-21 1976-05-04 Polaroid Corporation Protonated indole phthalides and naphthalides
US6489892B2 (en) 2000-05-18 2002-12-03 Spectra Systems Corporation Use of evaporatively activated color change for verifying the integrity of an object, such as a data storage medium or a gaming token

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1467898A (en) * 1974-04-09 1977-03-23 Ciba Geigy Ag Heterocyclic substituted lactone compounds their manufacture and use
US4020056A (en) * 1975-04-10 1977-04-26 Ncr Corporation Di-vinyl phthalides color formers
US4022771A (en) * 1975-04-10 1977-05-10 Ncr Corporation Aminophenyl lactone compounds containing an ethyleno group
US4189171A (en) * 1977-03-01 1980-02-19 Sterling Drug Inc. Marking systems containing 3-aryl-3-heterylphthalides and 3,3-bis(heteryl)phthalides
JPS5690031A (en) * 1979-12-21 1981-07-21 Sumitomo Chem Co Ltd Preparation of aromatic aldehyde

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954799A (en) * 1971-01-21 1976-05-04 Polaroid Corporation Protonated indole phthalides and naphthalides
US3862128A (en) * 1971-12-02 1975-01-21 Polaroid Corp Naphthalide indicator dyes
US6489892B2 (en) 2000-05-18 2002-12-03 Spectra Systems Corporation Use of evaporatively activated color change for verifying the integrity of an object, such as a data storage medium or a gaming token
WO2001087714A3 (en) * 2000-05-18 2004-07-08 Spectra Systems Corp Visual indicator for verification of an object

Also Published As

Publication number Publication date
GB1368938A (en) 1974-10-02
DE2313679C2 (de) 1982-06-03
DE2313679A1 (de) 1973-10-04
JPS5619275B2 (enrdf_load_stackoverflow) 1981-05-06
JPS4914213A (enrdf_load_stackoverflow) 1974-02-07
CA1003420A (en) 1977-01-11

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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

AS Assignment

Owner name: WTA INC., DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:APPLETON PAPERS INC., A CORPORTION OF DE;REEL/FRAME:005699/0768

Effective date: 19910214