Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/14—Styryl dyes
  • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/78—Ring systems having three or more relevant rings
  • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/10—The polymethine chain containing an even number of >CH- groups
• • 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

• ABSTRACT Disclosed are normally substantially colorless chromogenic l-hydroxy-1-(4-aminophenyl polymethine) naphthalan color precursor compounds having the following structural formula:
• each R represents either a hydrogen atom or a lower alkyl group having from one to five carbon atoms and wherein n is an integer from 1 to 3.
• the present invention relates to initially colorless chromogenic, color precursor compounds having particular utility in the field of carbonless copying.
• the compoundsof the present invention may be utilized, for example, in the production of self-marking impact papers of the transfer or manifolding type wherein a first marking ingredient is carried on one sheet of paper for reaction with a second marking ingredient normally carried on a mating sheet of paper.
• the invention relates to a family of chromogenic lhydroxy-l-(4-aminophenyl polymethine) naphthalan color precursor compounds having the following structural formula:
• each R represents either a hydrogen atom or a lower alkyl group having from 1 to 5 carbon atoms and wherein n is an integer from 1 to 3.
• the top sheet of paper upon which the impact or pressure is immediately applied, ordinarily has its back surface coated with microscopic capsules containing one of the reactive ingredients which produce a mark.
• a receiver sheet, placed in contact with such back face of the top sheet has its front surface coated with a material having a component reactive with the contents of the capsules so that when capsules are ruptured upon impact by stylus or machine key, the initially colorless or substantially colorless contents of the ruptured capsules react with a coreactant therefor on the receiver sheet and a mark forms on the receiver sheet corresponding to the mark impressed by the stylus or machine key.
• impact transfer papers are designated by the terms CB, CFB and CF, which stand respectively for coated back", coated front and back and coated front.
• the CB sheet is usually the top sheet and the one on which the impact impression is directly made;
• the CFB sheets are the intermediate sheets, each of which have a mark formed on the front surface thereof and each of which also transmits the contents of ruptured capsules from its back surface to the front of the next succeeding sheet;
• the CF sheet is the last sheet and is only coated on its front surface to have an image formed thereon.
• the CF sheet is not normally coated on its back surface as no further transfer is desired.
• carbonless impact transfer paper and the type with which the compounds of the present invention are preferably utilized, is the type illustrated, for example, in Green (507) and Macaulay (308) wherein microscopic capsules containing a liquid fill comprising a solution of an initially colorless chemically reactive color forming dye precursor arecoatedon the back surface of the sheet, and a dry coating of a co-reactant chemical for the dye precursor is coated on the front surface of a receiving sheet.
• color precursors disclosed in the patents referred to above are capable of undergoing an acidbase type reaction with an acidic material.
• Other previously known color precursors are the spiro-dipyran compounds disclosed in the patent to Harbort, U.S. Pat. No. 3,293,060 with specific reference being made to the disclosure of the 060 patent extending from column 11, line 32 through column 12, line 21.
• the color precursors disclosed in the patents listed above are initially generally colorless and capable of becoming highly colored when brought into contact with an acidic layer such as an acid-leached bentonite-type clay or an acid-reacting polymeric material, or the like.
• the color precursor materials disclosed above are dissolved in a solvent and the solube mentioned that the exact nature of the capsule itself is not critical as long as the same is capable of containing the color precursor and can be ruptured by the application of pressure in accordance with conventional carbonless copying procedures.
• Solvents known to be useful in connection with dissolving color precursors include chlorinated biphenyls, vegetable oils (castor oil, coconut oil, cotton seed oil, etc.) esters (dibutyl adipate, dibutyl phthalate, butyl benzyl adipatc, benzyl octyl adipate, tricresyl phosphate, trioctyl phosphate, etc.), petroleum derivatives (petroleum spirits, kerosene, mineral oils, etc.), aromatic solvents (benzene, toluene, etc.), silicone oils, or combinations of the foregoing. Particularly useful are the alkylatcd naphthalene solvents disclosed in US. Pat. No. 3,805,463 to Konishi et al.
• the color precursors are conventionally contained in pressure rupturable microcapsules which are included in the back coatings of the sheets of carbonless copying manifolded sets.
• the acidic coating are generally utilized as from coatings with the color precursor material in a solvent therefor being transferred from an adjacent back coating to the acidic layer front coating upon rupture of the capsules which contain the color precursor material.
• each R represents either a hydrogen atom or a lower alkyl group having from I to 5 carbon atoms and n is an interger from I to 3.
• the present invention is directed to a family of normally substantially colorless chromogenic l-hydroxyl (4-aminophenyl polymethine) naphthalan color precursor compounds having the following structural formula:
• naphthalan compounds of the present invention wherein n I may be prepared by reacting one mol of a p-amino benzaldehyde compound with a hydroxy naphthalan compound in the presence of HCl and thereafter neutralizing the reaction product with a base in accordance with the following formula:
• hydroxy naphthalan compound is prepared by treating 1,8-naphthalide with cH -Mgl'in accordance with the following formula:
• n 2 a 3-(p-aminophenyl) propenal compound having the formula ,4 C .2 C R 0 may be used and for n 3, a S-(p-aminophenyl) pentadienal compound having the formula H H H may be used in lieu of the p-aminobenzaldehyde.
• EXAMPLE 1 100 gms of acenaphthenequinone were added to 500 ml of an aqueous solution containing 30 percent KOH by weight and the mixture was heated with constant stirring at 150C for about minutes. The reaction mixture was then diluted with distilled water and filtered and the filtrate was acidified with HCl. The white precipitate which formed was separated by filtration and was dissolved in an aqueous solution containing 10 percent Na CO by weight. This latter solution was treated with charcoal and the product was reprecipitated wich HCl. The reprecipitated solids were filtered and l 1 1 gms of 1,8-naphthaldehydic acid having a melting point of 165 to 170C were recovered.
• EXAMPLE ll 1 11 grams of 1,8-naphthaldehydic acid produced in accordance with EXAMPLE I were dissolved in 3330 ml of 30% KOH solution and 1 10 ml of formalin were added to the solution. The reaction mixture was heated to about 60C and was stirred at the temperature for about 3 /2 hours. After the first hour of stirring, an additional 55 ml of formalin were added. The reaction mixture was filtered, cooled and acidified with concentrated HCl. The white precipitate which formed after acidification was collected on a filter and was washed first with 600 ml of a 5% NaHCO solution and then with distilled water. The yield was 57 grams. 52.4 gms of this product were recrystallized several times from high boiling Ligroin and the yield was 42.5 gms of recrystallized 1,8-naphthalide.
• reaction mixture was refluxed using a heating mantle for about 30 minutes and then ml of water were added dropwise at a controlled rate to maintain a slow boil in the flask.
• the reaction mixture was placed in a separatory funnel and the insoluble Mgl(Ol-l) was removed.
• the remaining ether layer was dried with Na SO and the ether was evaporated using a steam bath to leave about 9.0 gms of an almost colorless oily product which was a hydroxy naphthalan compound having the following structural formula:
• EXAMPLE IV 2.00 grams (approximately 0.01 mole) of the hydroxy naphthalan product produced in accordance with EXAMPLE Ill and 1.50 grams (approximately 0.01 mole) of p-dimethylaminobenzaldehyde were dissolved in 10 ml of glacial acetic acid and then HCl gas was bubbled through the resultant solution for about 10 minutes until the color of the solution had become intensely brown. This brown solution was poured into 300 ml of water to present an intensely blue solution of the dye.
• EXAMPLE V 0.50 gm of the naphthalan product produced in accordance with EXAMPLE IV was admixed with 10.0 grams of R-300 solvent (a commercial product of Kureha Corporation of America which is a mixture of isomeric diisopropyl naphthalenes and is apparently generally disclosed in US. Pat. No. 3,806,463 to Konishi et al.) and this admixture was warmed slightly on a hot plate until a clear solution (solution A) was obtained. Thereafter solution A was allowed to cool to room temperature.
• R-300 solvent a commercial product of Kureha Corporation of America which is a mixture of isomeric diisopropyl naphthalenes and is apparently generally disclosed in US. Pat. No. 3,806,463 to Konishi et al.
• dePont de Nemours which is a polyvinyl alcohol with 87 to 89% hydrolysis and a viscosity of 35 to 45 cps in a 4% aqueous solution at 20C) were placed in a semimicro Waring blender and then solutions A and B were mixed together at room temperature and the resultant solution was added to the Elvanol solution in the blender. The blender was activated and high shear agitation was continued for about 2 minutes until an emulsion having a dispersed phase particle size of about 2 to microns was obtained.
• the aqueous solution containing the Elvanol polyvinyl alcohol formed the continuous phase and the solution containing the R-300 solvent, the l-hydroxy-l-(4- dimethylaminophenyl polymethine) naphthalan and terephthaloyl chloride formed the dispersed phase.
• the emulsion was then transferred to a suitable container such as a beaker and was stirred with a variable speed mechanical stirrer at 300 to 500 rpm while an aqueous .solution containing 0.93 gms of diethylene triamine,
• microcapsules containing the l-hydroxy-l-(4-dimethylaminophenyl polymethine) naphthalan compound was then brought into contact with an acid-leached clay coating on the surface of another sheet of paper and when an impression was made on the reverse side of the sheet coated with microcapsules a corresponding light violet colored reproduction of such impression immediately appeared on the acid-leached clay coatmg.
• the compounds of the present invention are useful generally in the production and generation of colored marks and it is not critical to the present invention that the same be utilized in a copying system or in a microencapsulated form.
• a l-hydroxy-l-(4-aminophenyl polymethine) naphthalan compound having the following structural formula:
• each R represents either a hydrogen atom or a lower alkyl group having from 1 to 5 carbon atoms and wherein n is an integer from 1 to 3.
• a method for preparing a naphthalan compound as set forth in claim 1 comprising reacting one molar 5 equivalent of a p-aminobenzaldehyde compound with one molar equivalent of a hydroxy naphthalan compound having the following structural formula:
• a method for preparing a naphthalan compound as set forth in claim 1 comprising reacting one molar equivalent of a S-(p-aminophenyl) pentadienal compound with one molar equivalent of a hydroxy naphthalan compound having the following structural formula:
• p-dime- LII comprises utilizing, as said color precursor compound, a naphthalan compound as set forth in claim 1.
• a pressure-sensitive recording system comprising a layer of microcapsules containing a substantially colorless color precursor compound and a layer of an electon-acceptor material, the improvement which comprises utilizing, as said color precursor compound, a naphthalan compound as set forth in claim 2.
• a pressure-sensitive recording system comprising a layer containing a substantially colorless color precursor compound and a layer of an electron-acceptor material, the improvement which comprises utilizing, as said color precursor compound, a naphthalan compound as set forth in claim 1.
• a pressure-sensitive recording system comprising a layer containing a substantially colorless color precursor compound and a layer of an electron-acceptor material, the improvement which comprises utilizing, as said color precursor compound, a naphthalan compound as set forth in claim 2.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Color Printing (AREA)

Priority Applications (10)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (9)

Cited By (5)

Citations (4)

Family Cites Families (1)

• 1974
  • 1974-11-21 US US525990A patent/US3928685A/en not_active Expired - Lifetime
• 1975
  • 1975-10-14 ZA ZA00756477A patent/ZA756477B/xx unknown
  • 1975-11-10 DE DE19752550367 patent/DE2550367A1/de active Pending
  • 1975-11-13 AU AU86574/75A patent/AU8657475A/en not_active Expired
  • 1975-11-13 JP JP50136744A patent/JPS5174021A/ja active Pending
  • 1975-11-20 FR FR7535464A patent/FR2291977A1/fr active Granted
  • 1975-11-20 NL NL7513598A patent/NL7513598A/xx not_active Application Discontinuation
  • 1975-11-20 BE BE162033A patent/BE835766A/xx unknown
  • 1975-11-20 IT IT52311/75A patent/IT1052340B/it active
• 1976
  • 1976-12-22 JP JP15481676A patent/JPS52152314A/ja active Pending

Patent Citations (4)

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