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
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/10—Amino derivatives of triarylmethanes
  • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
• • 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
  • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
• • 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
  • B41M5/3275—Fluoran compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems

Definitions

• leueoaurarnines leucomethyleneblues
• phthalides and fluorans are well known as color precursors. They are colorless or nearly colorless compounds, which may change to a certain coloring matter when they are brought into contact with acidic electronacceptor as explained below.
• 2-methyl-6-diethylamino-fluoran having the following formula is one of the well-known color precursors which are colorless compounds under ordinary condition but change to red coloring matters by opening their lactone ring when they are brought into contact with acidic electron-acceptor.
• the pressure-sensitive copying paper is usually prepared by coating a back side of one sheet of paper with a color precursor such as a leucoauramine or a fluoran, and coating a surface of another sheet of paper with an acidic electron-acceptor substance such as kaolin, bentonitc, activated clay, acid clay, aluminum silicate, attapulgite, metal oxides, metal chlorides, metal sulfates, organic acids such as phenols, aliphatic acids or tannic acid, or phenolic resins such as p-phenylphenolformaldehyde resin, p-cyclohexylphenylformaldehyde resin, etc.
• a color precursor such as a leucoauramine or a fluoran
• an acidic electron-acceptor substance such as kaolin, bentonitc, activated clay, acid clay, aluminum silicate, attapulgite, metal oxides, metal chlorides, metal sulfates, organic acids such as phenols,
• the pressure-sensitive copying paper is used by placing the coated papers upon one another so that the back side of the first paper may be faced to the surface ofthe second paper, and the back side of the second paper to the surface of the third paper and so on.
• pressure or impact to the papers by means of a pencil, a ball-point pen or a typewriter on the first paper, the material on the back side and the electron accep'torsubstances on the surface of the papers are brought into contact with each other, whereby the colorless pressure-sensitive material moves to' the electron-acceptor layer and undergoes color development and therefore colored images can be obtained.
• the aforesaid compound has defects that, when used as color precursor for pressure-sensitive copying paper, it stains capsules in undesired red color because it is slightly soluble in water or slightly acidic or alkaline water.
• an object of the present invention is to provide a novel chromogenic material without aforesaid defects.
• This object can be accomplished by providing a novel fluoran represented by the following formula (I), (ll), (lll), or (IV),
• R represents hydrogen atom.
• R, and R each represents hydrogen atom.
• a lower alkyl group, a lower alkyl group substituted by halogen atom, lower alkoxy group or hydroxyl group, benzyl group or a benzyl group substituted by lower alkvl group, lower alkoxy group, halogen atom or nitro group as substituent R R represents a general formula.
• R R and R each represents hydrogen atom, a lower alkyl group, a halogen atom, a lower alkyl group substituted by halogen atom, lower alkoxy group or hydroxyl group, or phenyl group which may be substituted by lower alkoxy group, lower alkyl group, halogen atom or nitro group;
• R represents hydrogen atom, a lower alkyl group or an acyl group;
• R and R each represents hydrogen atom or a lower alkyl group, R,, represents hydrogen atom, a lower alkyl group or benzyl group;
• R, and R each represents hydrogen atom, a lower alkyl group, a lower alkoxy group, halogen atom, nitro group, amino group, an amino group substituted by lower alkyl group, lower alkoxy carbonyl group, a lower alkanesulfonyl group or benzenesulfonyl group which may be substituted by at least one Ry,
• R represents a
• R represents R,,, or R,', R R, and R each represents R R or R,,,,; R, and R, each represents R phenyl group or a phenyl group substituted by R,; R (COL- OUR PRECURSOR NO.
• R and R each represents hydrogen atom, a lower alkyl, phenyl, halophenyl, methoxyphenyl or nitrophenyl); m is an integer of l to 4; A represents benzene or naphthalene nucleus, and Y, signifies phenyl, cyclohexyl, or benzyl group.
• lower alkyl group indicates that the number of carbon atoms is from 1 to 4.
• Acyl group represents a group R'-CO in which R is an alkyl group having l to 3 carbon atoms, or benzoyl group which may be substituted by an aliphatic group having I to 4 carbon atoms or by R,.
• fluoran compounds (I), (ll), (Ill) and (IV) show all sorts of dark colors, for example, deep red, dark green, dark blue-green, dark greenish black, or black according to the number, kind and position of substituents.
• the present fluoran compounds have no solubility and good stability in water, acids or alkalis.
• 2-(5f,6',7',8'-tetrahydro-2'- naphthylmethyl)amino-8-diethylamino-benz[clfluoran can be boiled with an alkali solution without being destroycd.
• the present fluoran compounds have good fast nesscs to light, moisture and sublimation.
• the obtained deep image on this recording sheet does not disappear or change in color by moisture or droplets of water, or by exposure to sun-light or by .heating.
• the recording sheet prepared with use of the present fluoran compound endures storage for a long period of time without the disappearance of the image on the documents and slips.
• the present fluoran compounds have high colordeveloping speed. Such color formation occurs just at once when the fluoran compounds in the form of crystals or a solution in the above-cited solvents are brought into contact with the acidic electron-acceptor. Then, the recording sheet prepared with use of the present fluoran compounds gives vivid deep images on the paper at the moment when a pressure or impact is applied onto the paper by means of a pencil, a ballpoint pen or a typewriter.
• the images on the recording sheet prepared with a mixture of the present fluoran compounds do not change in color owing to the same color-developing speeds caused by the same fluoran nucleus.
• the present fluoran compounds represented by the general formulas (I), (ll), (Ill) and (IV) may be prepared by the following methods.
• fluorans (I), (II), (III) and (IV) can be prepared by reacting a o-(2'- hydroxyl-4'-aminobenzoyl)-benzoic acid represented by the formula,
• R signify R R,, R,., R,, R, and R,, Z and m are defined above, with a compound represented by the formulas R R R OR I! wherein R and R represent R R,,, R,, R,,, R and R,.
• E stands for benzene, naphthalene or tetrahydronaphthalene nucleus.
• R" indicates hydrogen atom, a lower alkyl group or an acyl group, and R R, and Y are as defined above, to obtain a fluoran represented by the following formulas,
• the reaction may be effected at a temperatureof 0 to 300C for several hours or sometimes for a few days in the presence of a dehydrating-condensing agent.
• a dehydrating-condensing agent include sulfuric acid; phosphorous pentoxide; phosphoric acid; polyphosphoric acid; an hydrous metal halides such as anhydrous tin chloride or bromide, anhydrous zinc chloride or bromide, anhydrous aluminum chloride or bromide, anhydrous ferric chloride or bromide; phosphoric pentachloride or bromide; phosphorous trichloride or bromide; phosphorus oxychloride or oxybromide, and anhydrous hydrogen chloride or fluoride.
• reaction mixture is poured into ice or'water to separate solid, and if desired, the mixture is neutralized with a solution of an alkali such as caustic soda, potassium hydroxide an the like.
• an alkali such as caustic soda, potassium hydroxide an the like.
• the solid in order to convert the resulting solid to the pure fluoran compound represented by the formula (I), (ll), (Ill) or (IV) by purification, the solid may be'dissolved and heated in a solvent and then the mixture may be cooled or concentratedto obtain the fluoran compound (I), (ll), (lll) or (IV) as white crystals.
• aromatic hydrocar bon solvents such as benzene, xylene, etc.
• nuclear halogenated aromatic hydrocarbon solvents such as chlorobenzcne,v bromobenzene, dichlorobenzenes, trichlorobenzenes, etc.
• alcohols such as methanol, ethanol, etc.
• amide solvents such as dimethylfonnamide
• halogenated aliphatic hydrocarbon solvents such as chloroform,bromoform, methylchloroform, etc.
• ethers such as dimethyl ether, diethyl ether, etc.
• I i i a The purificationis often facilitated by the addition of an aliphatic amine such as dimethylamine, trimethylamine, diethylamine, triethylamine, etc.; an aliphatic aminoalcohol such as ethanolamine, propanolamine, ctc.; or a heterocyclic'basic'substance such as pyridine, picolinc. ctc. 1 i
• an aliphatic amine such as dimethylamine, trimethylamine, diethylamine, triethylamine, etc.
• an aliphatic aminoalcohol such as ethanolamine, propanolamine, ctc.
• a heterocyclic'basic'substance such as pyridine, picolinc. ctc. 1 i
• White crystals which separate on heating and then cooling in any one of these purification solvents or a mixture thereof, are filtered and washed with a'nonpolar solvent such as cyclohexane, nhexane, diethyl ether-to obtain a colorless compound.
• a'nonpolar solvent such as cyclohexane, nhexane, diethyl ether-to obtain a colorless compound.
• a'nonpolar solvent such as cyclohexane, nhexane, diethyl ether-to obtain a colorless compound.
• a dehydrating agent as explained above to obtain a fluoran compound.
• the third method is accomplished by the use of a fluoran compound prepared by the first or second methods.
• a fluoran compound prepared by the first or second methods is prepared by the first or second methods.
• amino s'ubstituent of the fluoran nucleus is treated with (wherein R,, R Rm, Rh, Y E, Z and m are as defined above), which has at least one hydrogen atom in the an alkylating agent,'an acylating agentora sulfonylating agent as explained below in the presence or absence of a dehydrating agent or a dehydrohalogenating agent.
• reaction is properly carried out at 0 200C for (wherein R,, R R,, R Y., Z, m and E are as defined several hours or sometimes for a few days, if desired, above, and X each signifys a residue of the alkylating, in the presence of a solvent such as benzene, toluene, 3o acylating or sulfonylating agent such as halogen atom, xylene, chloroform, l,2 dichloroethane, ether, dioxhydroxy group, 80,", POff', etc.)
• a solvent such as benzene, toluene, 3o acylating or sulfonylating agent such as halogen atom, xylene, chloroform, l,2 dichloroethane, ether, dioxhydroxy group, 80,", POff', etc.
• acylating alkylating and sulfonylati.
• Acetic anhydride Propionic anhydride
• Butyric anhydride Propionic anhydride
• Crotonic anhydride ing agents which may be used in the above-mentioned reaction include:
• Oxiranes m-Nitrobenzoic anhydride Ethyleneoxide p-Bromobenzoic anhydride m-Methylbenzoic anhy- Propyleneoxide dride Z-Ethyloxirane p-Methoxybenzoic anhydride l5 2.2-Dimethyloxirane 2.
• Acetyl chloride Propionyl chloride 2,3-Dimethyloxirane 2,2-Diethyl-3-methyloxirane Acryloyl chloride 2,2-Diphenyloxirane Methacryloyl chloride 2-(4'-Nitrophenyl)-oxirane Acetyl bromide 2-Phenyloxirane 2-(2'-Chlorophenyl)-oxirane Butyryl bromide t 9.
• Sulfonylating agents Propiolyl bromide Methanesulfonyl chloride Crotonyl bromide Ethanesulfonyl chloride Benzoyl chloride Propanesulfonyl chloride m-Chlorobcnzoyl chloride Butanesulfonyl chloride p-Nitrobenzoyl chloride Benzenesulfonyl chloride m-Bromobenzoyl chloride p-Toluenesulfonyl chloride p-Methylbenzoyl chloride m-Toluenesulfonyl chloride m-Methoxybenzoyl chloride p-Chlorobenzenesulfonyl chloride Benzoyl bromide l o-Chlorobenzenesulfonyl chloride m-Nitrobenzenesulfohyl chloride o-Nitrobenzenesulfony
• Methanesulfonyl bromide Ethanesulfonyl bromide Benzenesulfonyl bromide p-Toluenesulfonyl bromide p-Chlorobenzenesulfonyl bromide p-Nitrobenzenesulfonyl bromide p-Methoxybenzenesulfonyl bromide 10. Miscellaneous p-Chlorobenzoyl bromide m-Nitrobenzoyl bromide m-Methylbenzoyl bromide -o-Methoxybenzoyl bromide- Also, as'the alkylating agent, the following compounds are preferable.
• esters Dimethyl sulfate Diethyl sulfate Dipropyl sulfate Trimethyl phosphate Triethyl phosphate Methyl benzenesulfonate Methyl p-toluenesulfonate Propyl p-toluenesulfonate Methoxyethyl p-toluenesulfonate Methoxypropyl p-toluenesulfonate Methyl methanesulfonate Propylmethanesulfonate 4.
• Lower alkyl halides Methyl chloride Ethyl bromide Propyl chloride c o 8 Butyl chloride 5.
• Benzyl halides l 55 t 3 Benzyllchloride m-Nitrobenzyl chloride p-Chlorobenzyl chloride m-Bromobenzyl chloride 6O p-Methylbenzyl chloride m-Methoxybenzyl chloride Bcnzyl bromide C p-Nitrobcnzyl bromide l o-Bromobcnzyl bromide C1-C3 m-Methylbenzyl bromide o-Methoxybenzyl bromide 6. Allyl halides: C1Cl l2 Allyl chloride U men; s
• CiCH B l0 CH3 Br I ClCH n CiCH B l0 CH3 Br I ClCH n:
• aromatic hydrocarbon solvents such as benzene, xylene, etc.; halogenated aliphatic hydrocarbon solvents such as chloroform, bromoform, methylchloroform, etc.; halogenated aromatic hydrocarbon solvents such as chlorobenzene, bromobenzene, dichlorobenzenes, etc.; alcohol solvents such as methanol, ethanol, propanol, etc.', ether solvents such as diethyl ether, dimethylene glycol, dimethyl ether, diethylene glycol, etc.; sulfoxide solvents such as dimethyl sulfoxide, 'diethyl 'sulfoxide, etc.; and amide solvents such as N,N'-dimethylformamide, dimethylacetamide, N-methylpyrrolidone may be used.
• aromatic hydrocarbon solvents such as benzene, xylene, etc.
• halogenated aliphatic hydrocarbon solvents such as chloroform, bromoform
• the pressure-sensitive recording systems generally comprise color-forming compounds on and/or withinone or more sheet supports, the color-forming compo-.
• nents being isolated from one another by a pressurerupturable barrierqwhere the color-forming compo nents are disposed on separate sheets as disclosed in U.S. Pat. No. 2,712,507, the record material referred to as a "transfer” or "couplet” system.
• a solution of a chromogenic material is held in rupturable microscopic capsules coated onto one surface of a transfer sheet, while an adjacent receiving sheet is sensitized with an acidic material. i.e., an electron acceptor.
• acidic materials are activated acid clay and acid clays, such as attapulgite, zeolite, bentonite, kaolin and silica.
• monomeric phenols or acid reactant polymeric materials such as phenolic polymers, phenol acetylene polymers, maleic acid-rosin resins. have been suggested either alone or in combination with acid clays.
• a non-volatile oil containing a chromogenic material dissolved therein is protected by encapsulation with coacerva'te film of a water-soluble polymer.
• the resulting coating composition containing dispersed capsules are coated on one side of a sheet, and coating composition of said electron acceptors is coated on the other side of the sheet.
• a coating liquid containing both of the capsules chromogenic material and acidic material is applied on one side of a sheet or alternatively, a coating containing capsules is first applied on one side of a sheet and the second coating containing the electronacceptor is applied thereon.
• the record material is referred to as self contained" system and develops image color where the pressure is applied.
• Japanese Pat. No. 511,757 (corresponds to U.S. Pat. application Ser. No. 392,404,tiled on Aug. 27, 1964) discloses a recording; sheet, in which minute capsules containing liquid solvent are coated on one surface of a sheet support and both of the chromogenic material and the acidic polymer are coated on or impregnated in same sheet or other sheet in solid condition.
• thermo-responsive record sheet as a markforming system utilizing an electron donor-acceptor color-forming reaction.
• Japanese Pat. Pub. No. l4039/ 1970 (corresponds to U.S. Pat. application Ser. No. 554,565 filed on June 1, 1966) discloses a temperature-responsive recordmaterial comprising a supporting sheet material having crystal violet lactone and a phenolic material solid at room temperature but capableof liquefying and/or vaporizing at normal thermographic temperatures, said lactone and phenolic material being further capable of producing a mark-forming reaction upon reactive contact.
• novel compounds of our invention are widely usedfor above-mentioned. mark-forming system as a colorless chromogenic compound, i.e., electron donor,
• the resulting compound formed dark reddish brown color on contacting with silica gel when used as a material for pressure-sensitivecopying paper.
• The'image having excellent fastnesses to moisture, sublimation and alkali was produced.
• diethylaminobenzlclfluoran was prepared from N,N- bis-(B-methoxyethyll-4-amino l naphthol and 2-(2'- hydroxy-4EdiethylaminobenzoylJ-benzoic acid. This derivative having a melting point'of l95.3 to 196.3C formed dark green color on silica gel.

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• 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)
• Heat Sensitive Colour Forming Recording (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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• 1971
  • 1971-12-27 JP JP47001074A patent/JPS5033891B2/ja not_active Expired
• 1972
  • 1972-02-10 JP JP47014663A patent/JPS5125170B2/ja not_active Expired
  • 1972-02-24 JP JP47019187A patent/JPS5125172B2/ja not_active Expired
  • 1972-04-13 JP JP47037433A patent/JPS5127164B2/ja not_active Expired
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  • 1972-10-27 US US301490A patent/US3901918A/en not_active Expired - Lifetime
  • 1972-10-27 GB GB4972772A patent/GB1408200A/en not_active Expired
  • 1972-10-30 FR FR7238460A patent/FR2161937B1/fr not_active Expired
  • 1972-10-30 NL NL7214690A patent/NL7214690A/xx unknown
  • 1972-10-30 DE DE2253161A patent/DE2253161A1/de active Pending
  • 1972-10-30 IT IT53699/72A patent/IT966700B/it active

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