US3916070A - Pressure-sensitive copying paper containing lactone compound of pyridine carboxylic acid - Google Patents

Pressure-sensitive copying paper containing lactone compound of pyridine carboxylic acid Download PDF

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Publication number
US3916070A
US3916070A US451400A US45140074A US3916070A US 3916070 A US3916070 A US 3916070A US 451400 A US451400 A US 451400A US 45140074 A US45140074 A US 45140074A US 3916070 A US3916070 A US 3916070A
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US
United States
Prior art keywords
alpha
carboxylic acid
pyridine
lactone
methyl
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
US451400A
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English (en)
Inventor
Minoru Ozutsumi
Yoshihide Miyazawa
Katsuichi Motohashi
Taiji Watanabe
Sadao Ishige
Keiso Saeki
Akio Watanabe
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.)
Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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 Hodogaya Chemical Co Ltd filed Critical Hodogaya Chemical Co Ltd
Application granted granted Critical
Publication of US3916070A publication Critical patent/US3916070A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • 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
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • the present invention relates to a pressure-sensitive copying paper using as a color former a pyridinecarboxylic acid lactone represented by the following general formula;
  • a and A which may be the same or different, each-represents a pyrrolyl, indolyl, carbazolyl, acridinyl, phenothiazinyl, thienyl, thianaphthenyl, julolidinyl or tetrahydroquinolyl group and
  • Y represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a halogen atom or a phenyl group, with the proviso that A and A both cannot simultaneously be an indolyl group or a pyrrolyl group.
  • pressure-sensitive copying paper comprises the combination of an upper sheet (or transfer sheet) having coated on the back surface thereof minute microcapsules containing dissolved therein an electron donative substantially colorless organic compound capable of undergoing color reaction, i.e., color former, and a lower sheet paper (or receiving sheet) having coated on the surface thereof a color developer.
  • Pressure-sensitive copying paper systems comprising the aforesaid transfer sheet and a receiving sheet and an intermediate sheet are also known.
  • the middle sheet is usually coated, on opposite surfaces, with a layer of micro-capsules containing a color former solution and with a layer of a solid acid and a stances such as acid clay, attapulgite, zeolite, bentonite; solid organic acids such as succinic acid, tannic acid, benzoic acid; and acidic polymers such as phenolformalin polymer, phenol-acetylene polymer, residual acid group-containing styrene-maleic anhydride polymer, salicylic acid-formalin polymer.
  • organic solvent for dissolving the color for mer there are, such as ethylene glycol, chlorobenzenes, diphenyl ,chloride diethyl phth'alateitrioctyl phosphate, alkylnaphthalenes and naphthylalkyl alcohols.
  • the thus formed color is excellent in light resistance.
  • pressure-sensitive copying paper using the novel color former in combination with a known color former or formers immediately forms an optional color when brought into contact with the color developer.
  • the thus formed color undergoes little change in hue with the lapse of time after color formation.
  • the starting material pyridine-carboxylic acid
  • reaction mixture is cooled to room temperature and the above-described inert solvent is removed by decantation.
  • a and Y are the same as defined in the formula (I) and a 3-( heterocyclic-carbonyl)-pyridinecarboxylic acid-(2) represented by the following formula;
  • the above obtained isomer mixture may be separated into each of the isomers thereby obtaining a highly purified Z-(heterocyclic-carbonyl)-pyridinecarboxylic acid-(3) or 3-(heterocyclic-carbonyl)-pyridine-carboxylic acid-(2), or (heterocyclic-carbonyl)- pyridine-carboxylic acids in which two isomers are present in various proportions can be obtained by 1) dissolving the mixture in dilute aqueous sodium hydroxide.
  • a pyridine-carboxylic acid lactone represented by the above formula (I) is produced as follows. 1.0 MOI of a mixture of isomers represented by the formulae (IV) and (V) and 0.9 to 1.5 mols of a heterocyclic compound represented by the formula (III) are added to concentrated sulfuric acid, acetic anhydride or polyphosphoric acid, and the reaction mixture is heated to a temperature of 50 to 130C for 2 to hours followed by cooling to room temperature. Then, the reaction product is poured into ice-water followed by adding thereto a dilute aqueous solution of sodium hydroxide to make the solution weakly acidic or neutral.
  • reaction product was worked up in the same manner as described in Preparation Example 2 to give 4.5 g of an isomer mixture comprising 2-[julolidinecarbonyl-(6')]-pyridine-carboxylic acid-(3) and 3- [julolidine-carbonyl-(6')]-pyridine-ca rboxylic acid-(2) as pale yellow colored crystals having a melting point of 228 to 239C.
  • An isomer mixture comprising 2-[1-methylpyrrolecarbonyl-(2)]-pyridine-carboxylic acid-(3) and 3-H- methylpyrrole-carbonyl-(2)] pyridine-caraboxylic acid-(2);
  • An isomer mixture comprising Z-[acridine-carbonyl- (2)]-pyridine-carboxylic acid-(3) and B-[acridinecarbonyl-(2')]-pyridine-carboxylic acid-(2);
  • An isomer mixture comprising 2-[phenothiazinecarbonyl-(3)]-pyridine-carboxylic acid-(3) and 3- [phenothiazine-carbonyl-(3)]-pyridine-carboxylic acid-(2);
  • An isomer mixture comprising methylphenothiazine-carbonyl-(3')]-pyridinecarboxylic acid-(3) and 3-[10'-methyl-phenothiazinecarbonyl(3)]-pyridine-carboxylic acid-(2);
  • An isomer mixture comprising 2-(2-thenoyl)-pyridine-carboxylic acid-(3) and 3-(2'-thenoyl)-pyridinecarboxylic acid-(2);
  • An isomer mixture comprising Z-[thianaphthenecarbonyl-(2)]-pyridine-carboxylic acid-(3) and 3- [thianaphthene-carbonyl-(2)]-pyridine-carboxylic acid-(2); or
  • An isomer mixture comprising 2-[ l '-methyl-2,3,4- trihydroxyquinoline-carbonyl-(6')]-pyridinecarboxylic acid-(3) and 3-[] '-methyl-2',3',4'- trihydroxyquinoline-carbonyl-(6)]-pyridinecarboxylic acid-(2).
  • reaction product 1n order to produce pressure-sensitive copying pa was worked up in the same manner as described in pers using pyridine-carboxylic acid lactones repre- Preparation Example 2 to obtain 3.0 g of an isomer sented by the formula (1) as a color former, there may mixture (color former No. 18) represented by the forbe employed the methods well known in the art as demulae; scribed in U.S. Pat. Nos. 2,800,457 and 2,800,458, in which phenomenon of complex coacervation is utilized C S to produce microcapsules.
  • trioctyl phosphate alkylnaphthalene, naphthylalkyl ald cohol, etc.
  • EXAMPLE 1 2.0 Grams of Color former Nos. l3 were taken up as pale yellow-colored crystals having a melting 130111t and treated as follows. Each color former was dissolved of to in 100 g of naphthylalkyl alcohol, and 20 g of gum ara- PREPARATION EXAMPLE 7 (Color Former bio and 160 g of water were added thereto at a temper- 19 21) ature of 50C to emulsify. To this emulsion were added 20 g of acid-treated gelatin and 160 g of water and, In the Same manner as described in Preparation under stirring, acetic acid was added thereto to adjust ample 2 except that 4'methyl'quihohhlc ahhydrlde, the pH to 5.
  • the syscarboxylic acid-(3) and 3-[1,2'-dimethylindoletem was cooled to 10C and, after adding thereto dilute carbonyl-(3')]-4-methyl-pyridine-carboxylic acid-(2); aqueous sodium hydroxide to adjust the pH to 9, it was An isomer mixture comprising 2-[1,2'- allowed to stand for 5 to 6 hours to thereby complete dimethylindole-carbonyl-( 3 -4-chloro-pyridineencapsulation.
  • the resulting microcapsule-containing liquid was applied to a paper by a coating method such as rollcoating, air knifecoating, etc. After drying, there was obtained a colorless coated paper (upper sheet paper).
  • a colorless coated paper (upper sheet paper).
  • this upper sheet paper was intimately superposed on a lower sheet paper having coated thereon an active clay'substance as a color developer and a localized pressure was applied to the assembly by handwriting, a purple color was immediately formed on the lower sheet paper at the pressed area. The color density of developed purple was high.
  • a pressure-sensitive copying paper comprising on a support a layer of an encapsulated color former and on the same or different support a layer of an electron

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Color Printing (AREA)
US451400A 1973-03-15 1974-03-15 Pressure-sensitive copying paper containing lactone compound of pyridine carboxylic acid Expired - Lifetime US3916070A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP48029468A JPS49118514A (en, 2012) 1973-03-15 1973-03-15

Publications (1)

Publication Number Publication Date
US3916070A true US3916070A (en) 1975-10-28

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Family Applications (1)

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US451400A Expired - Lifetime US3916070A (en) 1973-03-15 1974-03-15 Pressure-sensitive copying paper containing lactone compound of pyridine carboxylic acid

Country Status (5)

Country Link
US (1) US3916070A (en, 2012)
JP (1) JPS49118514A (en, 2012)
BE (1) BE812406A (en, 2012)
DE (1) DE2412640C3 (en, 2012)
GB (1) GB1425547A (en, 2012)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002631A (en) * 1973-07-24 1977-01-11 Hodogaya Chemical Co., Ltd. Tetrahydroquinoline or jujolidine derivative of a lactone compound of pyridine-carboxylic acid
US4046941A (en) * 1972-09-27 1977-09-06 Sanko Chemical Company Ltd. Support sheet with sensitized coating of organic acid substance and organic high molecular compound particulate mixture
US4096314A (en) * 1975-06-06 1978-06-20 Kores Holding Zug Ag Pressure-sensitive transfer sheet
DE3008494A1 (de) * 1979-03-05 1980-09-18 Appleton Paper Inc Chromogene lactonverbindungen, verfahren zu ihrer herstellung und ihre verwendung in druckempfindlichen oder waermeempfindlichen aufzeichnungsmaterialien
US4232887A (en) * 1979-03-05 1980-11-11 Appleton Papers Inc. Lactone compounds containing an indolizine radical
US4379721A (en) * 1980-03-14 1983-04-12 Spezial-Papiermaschinenfabrik August Alfred Krupp Gmbh & Co. Pressure sensitive recording materials
US4480002A (en) * 1980-12-12 1984-10-30 Mitsui Toatsu Chemicals, Incorporated Dyestuff-containing microscopic capsule suspension for record materials
US4508897A (en) * 1981-12-23 1985-04-02 Ciba Geigy Corporation Preparation of chromogenic azaphthalides
US4587343A (en) * 1983-05-09 1986-05-06 Ciba-Geigy Corporation Chromogenic 3,3-bisindolyl-4-azaphthalides
US4668790A (en) * 1981-12-23 1987-05-26 Ciba-Geigy Corporation Chromogenic dihydrofuropyridinones
US4675407A (en) * 1985-01-15 1987-06-23 Ciba-Geigy Corporation Ring-substituted 4-azaphthalides
US5004813A (en) * 1986-10-28 1991-04-02 Ciba-Geigy Corporation Chromogenic phthalides and azaphthalides
US20050075420A1 (en) * 2003-10-06 2005-04-07 Terry Stovold Invisible ink
US20050165131A1 (en) * 2003-10-06 2005-07-28 Terry Stovold Invisible ink
US20080113862A1 (en) * 2003-10-06 2008-05-15 Nocopi Technologies, Inc. Invisible Ink And Scratch Pad

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4211872A (en) * 1978-12-11 1980-07-08 Hung William M Substituted furopyridinones and furopyrazinones
US4243250A (en) * 1979-06-14 1981-01-06 Sterling Drug Inc. Carbonless duplicating systems
US4337340A (en) 1979-06-14 1982-06-29 Sterling Drug Inc. Processes for preparing substituted furopyridinones and furopyrazinones
JPS56151597A (en) * 1980-04-28 1981-11-24 Yamamoto Kagaku Gosei Kk Recording material
CH652733A5 (de) * 1983-04-07 1985-11-29 Ciba Geigy Ag Verfahren zur herstellung von 4-azaphthalidverbindungen.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3703397A (en) * 1969-01-21 1972-11-21 Ncr Co Mark-forming record materials and process for their use
US3736168A (en) * 1970-05-15 1973-05-29 Hodogaya Chemical Co Ltd Pressure-sensitive phthalide compound copying papers
US3775424A (en) * 1971-12-06 1973-11-27 Ncr Furo(3,4-b)pyridine-7(5h)-ones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3703397A (en) * 1969-01-21 1972-11-21 Ncr Co Mark-forming record materials and process for their use
US3736168A (en) * 1970-05-15 1973-05-29 Hodogaya Chemical Co Ltd Pressure-sensitive phthalide compound copying papers
US3775424A (en) * 1971-12-06 1973-11-27 Ncr Furo(3,4-b)pyridine-7(5h)-ones

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046941A (en) * 1972-09-27 1977-09-06 Sanko Chemical Company Ltd. Support sheet with sensitized coating of organic acid substance and organic high molecular compound particulate mixture
US4002631A (en) * 1973-07-24 1977-01-11 Hodogaya Chemical Co., Ltd. Tetrahydroquinoline or jujolidine derivative of a lactone compound of pyridine-carboxylic acid
US4096314A (en) * 1975-06-06 1978-06-20 Kores Holding Zug Ag Pressure-sensitive transfer sheet
DE3008494A1 (de) * 1979-03-05 1980-09-18 Appleton Paper Inc Chromogene lactonverbindungen, verfahren zu ihrer herstellung und ihre verwendung in druckempfindlichen oder waermeempfindlichen aufzeichnungsmaterialien
US4232887A (en) * 1979-03-05 1980-11-11 Appleton Papers Inc. Lactone compounds containing an indolizine radical
US4242513A (en) * 1979-03-05 1980-12-30 Appleton Papers Inc. Lactone compounds containing a heterocyclic radical
US4379721A (en) * 1980-03-14 1983-04-12 Spezial-Papiermaschinenfabrik August Alfred Krupp Gmbh & Co. Pressure sensitive recording materials
US4480002A (en) * 1980-12-12 1984-10-30 Mitsui Toatsu Chemicals, Incorporated Dyestuff-containing microscopic capsule suspension for record materials
US4508897A (en) * 1981-12-23 1985-04-02 Ciba Geigy Corporation Preparation of chromogenic azaphthalides
US4668790A (en) * 1981-12-23 1987-05-26 Ciba-Geigy Corporation Chromogenic dihydrofuropyridinones
US4587343A (en) * 1983-05-09 1986-05-06 Ciba-Geigy Corporation Chromogenic 3,3-bisindolyl-4-azaphthalides
US4705776A (en) * 1983-05-09 1987-11-10 Ciba-Geigy Corporation Recording material containing chromogenic 3,3-bisindolyl-4-azaphthalides
US4675407A (en) * 1985-01-15 1987-06-23 Ciba-Geigy Corporation Ring-substituted 4-azaphthalides
US5004813A (en) * 1986-10-28 1991-04-02 Ciba-Geigy Corporation Chromogenic phthalides and azaphthalides
US5071986A (en) * 1986-10-28 1991-12-10 Ciba-Geigy Corporation Chromogenic phthalides and azaphthalides
US20050075420A1 (en) * 2003-10-06 2005-04-07 Terry Stovold Invisible ink
US20050165131A1 (en) * 2003-10-06 2005-07-28 Terry Stovold Invisible ink
US20080113862A1 (en) * 2003-10-06 2008-05-15 Nocopi Technologies, Inc. Invisible Ink And Scratch Pad
US8053494B2 (en) 2003-10-06 2011-11-08 Nocopi Technologies, Inc. Invisible ink and scratch pad

Also Published As

Publication number Publication date
DE2412640C3 (de) 1978-11-30
JPS49118514A (en, 2012) 1974-11-13
DE2412640A1 (de) 1974-09-26
DE2412640B2 (de) 1978-04-06
GB1425547A (en) 1976-02-18
BE812406A (fr) 1974-07-01

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