EP0377406B1 - Pressure-sensitive or heat-sensitive recording material - Google Patents

Pressure-sensitive or heat-sensitive recording material Download PDF

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Publication number
EP0377406B1
EP0377406B1 EP89810944A EP89810944A EP0377406B1 EP 0377406 B1 EP0377406 B1 EP 0377406B1 EP 89810944 A EP89810944 A EP 89810944A EP 89810944 A EP89810944 A EP 89810944A EP 0377406 B1 EP0377406 B1 EP 0377406B1
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EP
European Patent Office
Prior art keywords
recording material
material according
substituted
lower alkyl
halogen
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EP89810944A
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German (de)
French (fr)
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EP0377406A1 (en
Inventor
Rox Dr. Phaff
Rudolf Zink
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Novartis AG
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Ciba Geigy AG
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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
    • 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
    • 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
    • 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

Definitions

  • the compounds of the formula (1) contain, as part of their structure, the backbone of, for example, a lactone, lactam, sulton, sultam or phthalan and these backbones are subject to - before, during or after the reaction of component (A) with components (B) - upon contact with the color developer (component (C)) presumably a ring opening or bond cleavage.
  • component (A) contains, as part of their structure, the backbone of, for example, a lactone, lactam, sulton, sultam or phthalan and these backbones are subject to - before, during or after the reaction of component (A) with components (B) - upon contact with the color developer (component (C)) presumably a ring opening or bond cleavage.
  • Components (A), (B) and (C) come into contact with one another by pressure or heating, depending on the recording material, and leave records on the carrier material.
  • the color is produced in accordance with the type of components (A) and (B), which represent the electron donor and form the chromogenic part.
  • the color formation is caused by component (C).
  • the desired colors e.g. yellow, orange, red, violet, blue, green, gray, black or mixed colors can be generated.
  • components (A) and (B) together with one or more conventional color formers e.g.
  • 3,3- (bis-aminophenyl -) - phthalides such as CVL, 3-indolyl-3-aminophenylaza- or -diazaphthalides, (3,3-bis-indolyl -) - phthalides, 3-aminofluoranes, 6-dialkylamino-2- dibenzylaminofluoranen, 6-dialkylamino-3-methyl-2-arylaminofluoranen, 3,6-Bisalkoxyfluoranen, 3,6-Bisdiarylaminofluoranen, Leukoauraminen, spiropyrans, spirodipyrans, benzoxazines, Chromenopyrazolen, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes used .
  • Substituents in the sense of Y1 and Y2 are easily removable substituents on the central (meso) carbon atom of the compound of formula (1), which thereby change into an anion.
  • substituents can be halogen atoms, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether groups, such as, for example, alkoxy, cycloalkoxy, aralkoxy, aryloxy or heteroaryloxy, and also acyloxy groups, for example of the formula correspond in which R 'is an organic radical, preferably unsubstituted or, for example, halogen or cyano substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl, Q' is -CO- or -SO2- and n is 1 or 2, preferably 1.
  • Y1 and Y2 are preferably a group of the formula R ′′ -CO-O-, where R ′′ is lower alkyl or phenyl.
  • Halogens such as e.g. Fluorine, bromine, iodine and especially chlorine.
  • Y1 and Y2 are bonded to one another, they advantageously form a 5- or preferably 6-membered heterocyclic ring, in particular cyclic ether, thioether, etherester or thioetherester groups, which preferably are fused, optionally e.g. have benzene rings substituted by halogen atoms.
  • Q1 preferably represents an oxygen atom, while Q2 preferably represents -SO2 or, above all, -CO-. If Q1 represents ⁇ NR or ⁇ N-NH-R, R is preferably hydrogen, methyl or phenyl.
  • A is preferably a benzene ring which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl, amino, lower alkylamino, di-lower alkylamino or lower alkylcarbonylamino.
  • Ring A may also contain a fused aromatic ring, preferably a benzene ring, and thus represents e.g. represents a naphthalene or phenanthrene ring.
  • the preferred 6-membered aromatic radicals represented by A are the 2,3-naphthalino, 1,2-naphthalino or 1,2-benzo radical, which is unsubstituted or by halogen, such as chlorine or bromine, nitro, lower alkyl, lower alkoxy, lower alkylthio or one as defined above optionally substituted amino group is substituted, the unsubstituted or substituted by 4 chlorine atoms 1,2-benzo radical is particularly preferred.
  • Particularly important components (A) for the color reactant system according to the invention correspond to the formula wherein A1 is an optionally substituted by halogen, cyano, lower alkyl, lower alkylthio, lower alkoxy or di-lower alkylamino and Y3 and Y4 independently of one another, halogen or acyloxy, such as lower alkylcarbonyloxy or benzoyloxy and especially chlorine or bromine.
  • the lactone compounds in which Y3 and Y4 are halogen atoms such as bromine or especially chlorine and the ring A1 is an unsubstituted or substituted by halogen, lower alkyl, lower alkoxy or di-lower alkylamino are preferred.
  • Lactone compounds of the formula are of particular interest wherein the ring B is unsubstituted or substituted by lower alkyl, di-lower alkylamino or 1 to 4 chlorine atoms and Y5 and Y6 are bromine or especially chlorine.
  • Compounds of formula (1) in which Y1 and Y2 are linked are e.g. prepared by reacting alkali metal salts of salicylic acid, its esters or core substitution products with halides of o-phthalic acid or their core substitution products (according to DE-PS 400790).
  • Specific examples of the compounds of the formulas (1) to (3) include 3,3-dichlorophthalide, 3,3-dibromophthalide, 3,3,5-trichlorophthalide, 3,3,5,6-tetrachlorophthalide, 3,3-difluoro-4,5,6,7-tetrachlorophthalide, 3,3,4,5,6,7-hexachlorophthalide, 3,3-dibromo-4,5,6,7-tetrachlorophthalide, 3,3,4,7-tetrachlorophthalide, 3,3,6,7-tetrachlorophthalide, 3,3,4,5,7-pentabromo-6-acetyloxy-phthalide, 3,3-diethoxy-phthalide, 3,3-diethoxy-4,5,6,7-tetrachlorophthalide, 3,3-diethoxy-6,7-dichlorophthalide, 3,3-dimethoxy-4,7-dichlorophthalide, 3,3-dimethoxyphthalide, 3,3-dimethoxy-4,5
  • EP-A-0 373 110 discloses a pressure- or heat-sensitive recording material similar to that in the present invention, however component (A) at the 3-position has a substituent and which can be removed as an anion has a monocyclic or polycyclic aromatic or heteroaromatic radical.
  • EP-A-0 373 110 belongs to the prior art under Article 54 (3) (4) EPC.
  • components (B) used according to the invention which form chromogenic compounds with component (A), are preferably mono- or polycyclic aromatic or heteroaromatic compounds which supplement a system of conjugated double bonds and, if necessary, auxochromic substituents, such as e.g. Amino groups, substituted amino groups such as di-lower alkylamino, hydroxyl groups, ether groups such as alkoxy, thio groups or mercapto groups such as alkylthio.
  • auxochromic substituents such as e.g. Amino groups, substituted amino groups such as di-lower alkylamino, hydroxyl groups, ether groups such as alkoxy, thio groups or mercapto groups such as alkylthio.
  • Such compounds expediently come from the series of unsubstituted, C- and / or N-substituted anilines, diarylamines, naphthylamines, N-substituted aminophenylethylene compounds, N-substituted aminophenylstyrene compounds, acylacetarylamides, monohydric or polyhydric phenols, phenol ethers, 3-naphthenoic acid aminophenol acid, naphthyl enoltholethene acid, naphthyl enoltholethene acid, naphthyl enoltholetholeic acid, naphthyl enoltholetholeic acid, naphthyl acid, naphthyl enoltholetholeic acid, naphthyl acid, naphthyl enoltesquee, naphthyl acid, naphthyl enoltholetholeic acid, , Aminopyrazo
  • V represents hydrogen, halogen, lower alkyl, C1-C12 alkoxy, C1-C12 acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, benzyl or benzyloxy substituted by halogen, cyano, lower alkyl or lower alkoxy, or the group -NT1T2.
  • T1 and T2 independently of one another, each represent hydrogen, lower alkyl, C5-C10 cycloalkyl, unsubstituted or substituted by halogen, cyano, lower alkyl or lower alkoxy, or acyl having 1 to 8 carbon atoms and T1 also unsubstituted or by halogen, cyano, lower alkyl or lower alkoxy substituted phenyl.
  • m is 1 or 2.
  • Z1 means hydrogen, unsubstituted or substituted by halogen, hydroxyl, cyano or lower alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 12 carbon atoms or unsubstituted or substituted by halogen, cyano, lower alkyl or lower alkoxy benzyl.
  • Z2 means hydrogen, lower alkyl or phenyl and Z2 'means lower alkyl, cyclohexyl, benzyl or phenyl.
  • the benzene nucleus D is unsubstituted or substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, amino, mono-lower alkylamino or di-lower alkylamino.
  • a V is preferably in the ortho position to the connection point.
  • -NR1R2 is preferably in the para position to the junction.
  • Lower alkyl, lower alkoxy and lower alkylthio are in the definition of components (A) and (B) those groups or group components which have 1 to 6, in particular 1 to 4, carbon atoms.
  • groups are ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or hexyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy or methylthio, ethylthio, propylthio or butylthio.
  • Halogen means for example fluorine, bromine or preferably chlorine.
  • Acyl is especially formyl, lower alkylcarbonyl, e.g. Acetyl or propionyl, or benzoyl.
  • Further acyl residues can be lower alkylsulfonyl, e.g. Be methylsulfonyl or ethylsulfonyl and phenylsulfonyl.
  • Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
  • substituents R, R1, R2 and Z1 represent alkyl groups, they can be straight-chain or branched.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, isooctyl, n-nonyl, isononyl or n-dodecyl.
  • alkyl radicals in R1, R2 and Z1 are substituted, it is primarily cyanoalkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl each preferably with a total of 2 to 8 carbon atoms, such as e.g. 2-cyanoethyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2,3-dihydroxypropyl, 2-hydroxy-3-chloropropyl, 3-methoxypropyl, 4-methoxybutyl or 4-propoxybutyl.
  • cycloalkyl in the meaning of R, R1, R2, T1 and T2 are cyclopentyl, cycloheptyl or preferably cyclohexyl.
  • the cycloalkyl radicals can contain one or more C1-C4 alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.
  • the acyloxy radical in V is, for example, formyloxy, lower alkylcarbonyloxy, e.g. Acetyloxy or propionyloxy, or benzoyloxy.
  • V can be a straight-chain or branched group, e.g. Methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, amyloxy, 1,1,3,3-tetramethylbutoxy, n-hexyloxy, n-octyloxy or dodecyloxy.
  • the pair of substituents (R1 and R2) together with the common nitrogen atom represents a heterocyclic radical
  • this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino, piperazino, N-alkylpiperazino, such as N-methylpiperazino, N-phenylpiperazino or N-alkylimidazolino.
  • Preferred saturated heterocyclic radicals for -NR1R2 are pyrrolidino, piperidino or morpholino.
  • V can advantageously be hydrogen, halogen, lower alkyl, e.g. Methyl, benzyloxy, C1-C8 alkoxy, primarily lower alkoxy, e.g. Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy, or the group -NT1T2, where one of the radicals T1 and T2 is preferably C1-C8 acyl or lower alkyl and the other is hydrogen or lower alkyl.
  • the acyl radical in this case is especially lower alkylcarbonyl, e.g. Acetyl or propionyl.
  • V is preferably acetylamino, dimethylamino, benzyloxy or especially lower alkoxy and especially ethoxy or hydrogen.
  • R1 and R2 in the meaning of phenalkyl advantageously have a total of 7 to 9 carbon atoms and are generally ⁇ -methylbenzyl, phenethyl, phenisopropyl or primarily benzyl, which can preferably also be ring-substituted.
  • Preferred substituents in the benzyl group of the R, T and Z radicals, in the phenyl group of R1, R2 and T1 and in the benzyloxy group of V are e.g. Halogen, methyl or methoxy.
  • araliphatic or aromatic radicals examples include p-methylbenzyl, o- or p-chlorobenzyl, 2,5-dimethylbenzyl, o- or p-tolyl, xylyl, 2,6-dimethylphenyl, o-, m- or p-chlorophenyl , o- or p-methoxyphenyl, o- or p-chlorobenzyloxy or o- or p-methylbenzyloxy.
  • the substituents R1 and R2 are preferably cyclohexyl, benzyl, tolyl, phenethyl, cyano-lower alkyl e.g. ⁇ -cyanoethyl or primarily lower alkyl, e.g. Methyl, ethyl or n-butyl.
  • -NR1R2 is also preferably pyrrolidinyl.
  • the indole substituent Z1 is preferably hydrogen, benzyl, acetyl, propionyl or especially C1-C8-alkyl, such as methyl, ethyl, n-butyl or n-octyl.
  • Z2 is preferably phenyl or especially methyl.
  • Z2 ' is preferably lower alkyl.
  • the benzene ring D is preferably not further substituted. If D contains substituents, these are especially halogen, lower alkyl, e.g. Methyl, tert-butyl, lower alkoxy or di-lower alkylamino such as dimethylamino.
  • components (B) are 2-amino-4-methoxytoluene, N, N-dimethylaniline, N, N-diethylaniline, N-phenylpyrrolidine, N-3-ethoxyphenylpyrrolidine, N-phenylmorpholine, m-phenetidine, 3-ethoxy-N, N-dimethylaniline, 3-ethoxy-N, N-diethylaniline (N, N-diethyl-m-phenetidine), 3-ethoxy-N, N-dibutylaniline, 3-n-butoxy-N, N-di-n-butylaniline, 1,3-bisdimethylaminobenzene, 3-acetylamino-N, N-dimethylaniline, N-methyl-N-4-methylphenylaniline, 4-ethoxy-diphenylamine, N-methyl-diphenylamine, N, N-dibenzylaniline, N-phenyl-tolui
  • Preferred components (B) are also phthalide and especially fluoran compounds which have at least one primary amino group or an amino group monosubstituted by lower alkyl, cyclohexyl or benzyl. These phthalide and fluoran compounds are described for example in FR-A-1 553 291, GB-A-1 211 393, DE-A-2 138 179, DE-A-2 422 899 and EP-A-138 177.
  • components (B) are: 2-amino-3-chloro-6-diethylaminofluoran 2-amino-6-dibutylaminofluoran 6-amino-3-chlorofluorane 2-amino-6-diethylaminofluoran 2-methylamino-6-dimethylaminofluoran 2-ethylamino-6-diethylaminofluoran 2-methylamino-6-diethylaminofluoran 2-n-butylamino-6-diethylaminofluoran 2-n-octylamino-6-diethylaminofluoran 2 sec butylamino-6-diethylaminofluoran 2-benzylamino-6-diethylaminofluoran 2,3-dimethyl-6-ethylaminofluoran 2,3,7-trimethyl-6-ethylaminofluoran 2,3,7-trimethyl-6-ethylamino-5 '(6')
  • component (A) and component (B) can be used either individually or in the form of a combination of two or more of them.
  • two components (B) used are identical, symmetrically substituted polycyclic chromogenic compounds are generally formed. If, on the other hand, two different components (B) are used, they provide asymmetrically substituted chromogenic compounds.
  • Inorganic or organic color developers known for recording materials and capable of attracting electrons can be used as component (C).
  • Typical examples of inorganic developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
  • active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite
  • activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
  • Preferred inorganic color developers are Lewis acids, e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.
  • Lewis acids e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.
  • Solid organic acids suitably aliphatic dicarboxylic acids, such as e.g. Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid as well as alkylphenol acetylene resin, maleic acid rosin resin, carboxypolymethylene or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether can be used.
  • aliphatic dicarboxylic acids such as e.g. Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid as well as alkylphenol acetylene resin, maleic acid rosin resin, carboxypolymethylene or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether can be used.
  • Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be replaced by halogen atoms, carboxyl groups, alkyl radicals, aralkyl radicals, such as ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, Aryl radicals, acyl radicals, such as arylsulfonyl or alkoxycarbonyl radicals, or aralkoxycarbonyl radicals, such as benzyloxycarbonyl, can be substituted.
  • phenols suitable as component (C) are 4-tert-butylphenol, 4-phenylphenol, methylene-bis (p-phenylphenol), 4-hydroxydiphenyl ether, ⁇ -naphthol, ⁇ -naphthol, 4-hydroxybenzoic acid methyl ester or benzyl ester , 2,4-dihydroxybenzoic acid methyl ester, 4-hydroxydiphenyl sulfone, 4'-hydroxy-4-methyldiphenyl sulfone, 4'-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-acetophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxydiphenyl, 2, 4-dihydroxydiphenyl sulfone, 4,4'-cyclohexylidene diphenol, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4-bis- (4-hydroxy
  • Preferred components (C) are zinc salicylates, zinc-modified phenolic resins (novolak resins) or, above all, active clays.
  • the developers can also be used in a mixture with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, such as 2- (2'-hydroxyphenyl) benzotriazoles, benzophenones, cyanoacrylates, salicylic acid phenyl esters.
  • pigments are: talc, titanium dioxide, aluminum oxide, Aluminum hydroxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, eg urea-formaldehyde condensates (BET surface 2-75 m2 / g) or melamine-formaldehyde condensation products
  • component (C) The mixing ratio of component (C) to components (A) and (B) depends on the type of three components, the type of color change, the pressure or the color reaction temperature and of course also on the desired color concentration. However, satisfactory results are obtained when the color developing component (C) is used in an amount of 0.1 to 100 parts by weight per part of the components (A) and (B).
  • both component (A) and component (B) are preferably dissolved together or separately in an organic solvent and the solutions obtained are expediently encapsulated by processes such as e.g. in the U.S. Patents 2,712,507, 2,800,457, 3,016,308, 3,429,827 and 3,578,605 or in British Patents 989,264, 1,156,725, 1,301,052 or 1,355,124.
  • Microcapsules formed by interfacial polymerization such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
  • the encapsulation is usually required to separate components (A) and (B) from component (C) and thus prevent early activation.
  • the latter can also be achieved by incorporating components (A) and (B) into foam, sponge or honeycomb structures.
  • suitable solvents are preferably non-volatile solvents, for example halogenated benzene, diphenyls or paraffin, such as, for example, chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters such as dibutyl adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl adipate, trichloroethyl phosphate, trioctyl phosphate, tricresyl phosphate; aromatic ethers such as benzylphenyl ether; Hydrocarbon oils, such as paraffin oil or kerosene, for example derivatives of diphenyl alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl, Naphthalene or terphenyl, dibenzyltoluene, partially hydrogenated
  • Mixtures of various solvents in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
  • Microcapsules containing components (A) and (B) can be used to produce pressure-sensitive copying materials of various known types.
  • the different systems differ essentially in the arrangement of the capsules, the color reactants and the carrier material.
  • An arrangement is advantageous in which encapsulated components (A) and (B) are present in the form of a layer on the back of a transfer sheet and the electron acceptor (component (C)) in the form of a layer on the front of a receiver sheet.
  • Another arrangement of the components is that the microcapsules containing components (A) and (B) and the developer (component (C)) are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
  • the capsule mass which contains components A and B
  • further capsules which contain conventional color formers. Similar results are obtained if components A and B are encapsulated together with one or more of the conventional color formers.
  • the capsules are preferably attached to the carrier by means of a suitable binder.
  • this binder is mainly paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, Methyl cellulose, dextrin, starch, starch derivatives or polymer latices.
  • the latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.
  • the paper used is not only normal paper made from cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers.
  • the substrate can also be a plastic film.
  • the carbonless material preferably also consists of a capsule-free layer containing components (A) and (B) and a color-developing layer which, as color developer (component (C)), comprises at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.
  • component (C) comprises at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.
  • the ternary color image system comprising components (A), (B) and (C) used according to the invention is also suitable for producing a heat-sensitive recording material for thermography, components (A), (B) and (C) being heated together to form a color in Come into contact and leave records on the carrier material.
  • the heat-sensitive recording material generally contains at least one layer support, components (A), (B) and (C) and optionally also a binder and / or wax. If desired, activators or sensitizers can also be present in the recording material.
  • Thermoreactive recording systems include, for example, heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, for example in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, such as, for example, electrocardiographs.
  • the imaging (marking) can also be done manually with a heated spring.
  • Another device for generating markings using heat is laser beams.
  • thermoreactive recording material can be constructed such that components (A) and (B) are dissolved or dispersed in a binder layer and in a second layer the developer (component (C)) is dissolved and dispersed in the binder. Another possibility is that all components are dispersed in the same layer.
  • the layer or layers are softened or fused in specific areas by means of heat, whereupon the desired color develops immediately in the heated parts.
  • Fusible, film-forming binders are preferably used to produce the heat-sensitive recording material. These binders are normally water soluble, while components (A), (B) and (C) are insoluble in water. The binder should be able to disperse all components at room temperature and fix them on the substrate.
  • Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.
  • hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.
  • water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
  • the preferred arrangement is one in which all of the components are contained in a layer in a water-soluble binder.
  • the material can be provided with an additional protective layer.
  • Such protection Layers usually consist of water-soluble and / or water-insoluble resins, which are conventional polymer materials or aqueous emulsions of these polymer materials.
  • water-soluble polymer materials are polyvinyl alcohol, starch, starch derivatives, cellulose derivatives, such as methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose or ethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, polyacrylamide / acrylic acid ester copolymers, acrylamide / acrylic acid ester / methacrylic acid / copolymeric acid-alkali acid-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copoly
  • water-insoluble resins e.g. the following water-insoluble resins are used: polyvinyl acetate, polyurethanes, styrene / butadiene copolymers, polyacrylic acid, polyacrylic acid esters, vinyl chloride / vinyl acetate copolymers, polybutyl methacrylate, ethylene / vinyl acetate copolymers and styrene / butadiene / acrylic derivative copolymers.
  • thermoreactive layers and the resin layers can contain further additives.
  • these layers for example antioxidants, UV absorbers, solvents, talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (eg chalk), magnesium carbonate, Contain clays or organic pigments, such as urea-formaldehyde polymers.
  • substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid, benzate, methyl ester, benzate metal, eg, benzate, benzate, for example, benzate, benzylate, for example, benzate, zalatesilate, eg , Dibenzyl isophthalate, dibenzyl terephthalate, benzyldiphenyl or others corresponding, meltable products which induce the simultaneous melting of the color former components and the developer are added.
  • Thermographic recording materials preferably contain waxes, e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
  • waxes e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
  • components (A), (B) and (C) can be enclosed in microcapsules. Any of the methods known per se for enclosing color formers or other active substances in microcapsules can be used for this purpose.
  • Solutions A and B prepared according to Example 1 are mixed in a weight ratio of 1: 1 and coated on the front of the sheet of paper coated with acid-modified bentonite, a black color immediately developing.
  • Example 1 If, instead of solution B, a solution C of 2 g of 1-methyl-2-phenylindole is used in Example 1 and the procedure is otherwise as described in Example 1, a violet color is obtained on the front of the paper coated with acid-modified bentonite.

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Description

Die vorliegende Erfindung betrifft ein druckempfindliches oder wärmeempfindliches Aufzeichnungsmaterial, in dem das Farbreaktantensystem als wesentliche Bestandteile

  • (A) eine elektronenabgebende Verbindung der Formel
    Figure imgb0001
     worin
    Y₁ und Y₂ als Anion abspaltbare Substituenten sind, die gleich, verschieden oder miteinander verbunden sein können,
    Q₁ -O-, -S-, 〉N-R oder 〉N-NH-R,
    Q₂ -CH₂-, -CO-, -CS- oder -SO₂- und
    R Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₀-Cycloalkyl, Aryl wie Phenyl oder Aralkyl wie Benzyl bedeuten und der Ring A einen aromatischen Rest mit 6 Ringatomen darstellt, der einen aromatischen, annellierten Ring aufweisen kann, wobei sowohl der Ring A als auch der annellierte Ring substituiert sein können,
  • (B) zwei gleiche oder voneinander verschiedene, organische Kondensationskomponenten, die zusammen fähig sind mit Komponente (A) eine chromogene Verbindung zu bilden und
  • (C) eine elektronenanziehende und farbentwickelnde Komponente aufweist.
The present invention relates to a pressure-sensitive or heat-sensitive recording material in which the color reactant system is an essential component
  • (A) an electron donating compound of the formula
    Figure imgb0001
     wherein
    Y₁ and Y₂ are substituents which can be split off as anions and which can be identical, different or linked to one another,
    Q₁ -O-, -S-,〉 NR or〉 N-NH-R,
    Q₂ -CH₂-, -CO-, -CS- or -SO₂- and
    R is hydrogen, C₁-C₁₂-alkyl, C₅-C₁₀-cycloalkyl, aryl such as phenyl or aralkyl such as benzyl and the ring A represents an aromatic radical with 6 ring atoms, which may have an aromatic, fused ring, both the ring A and the fused ring can also be substituted,
  • (B) two identical or different organic condensation components which, together with component (A), are capable of forming a chromogenic compound and
  • (C) has an electron attracting and color developing component.

Die Verbindungen der Formel (1) (Komponente (A)) enthalten als Teil ihrer Struktur das Grundgerüst beispielsweise eines Laktons, Laktams, Sultons, Sultams oder Phthalans und diese Grundgerüste unterliegen - vor, während oder nach der Umsetzung der Komponente (A) mit Komponenten (B) - beim Kontakt mit dem Farbentwickler (Komponente (C)) vermutlich einer Ringöffnung oder Bindungsspaltung.The compounds of the formula (1) (component (A)) contain, as part of their structure, the backbone of, for example, a lactone, lactam, sulton, sultam or phthalan and these backbones are subject to - before, during or after the reaction of component (A) with components (B) - upon contact with the color developer (component (C)) presumably a ring opening or bond cleavage.

Komponenten (A), (B) und (C) kommen je nach Aufzeichnungsmaterial durch Druck oder Erhitzen miteinander in Berührung und hinterlassen Aufzeichnungen auf dem Trägermaterial. Die Farbe wird dabei nach Massgabe der Art der Komponenten (A) und (B), die den Elektronendonator darstellen und den chromogenen Teil bilden, erzeugt. Die Farbbildung wird durch die Komponente (C) verursacht. Durch eine entsprechende Kombination der einzelnen Komponenten können somit die gewünschten Farben, wie z.B. gelb, orange, rot, violett, blau, grün, grau, schwarz oder Mischfarben erzeugt werden. Eine weitere Kombinationsmöglichkeit besteht darin, dass man Komponenten (A) und (B) zusammen mit einem oder mehreren konventionellen Farbbildnern z.B. 3,3-(Bis-aminophenyl-)-phthaliden wie CVL, 3-Indolyl-3-aminophenylaza- oder -diazaphthaliden, (3,3-Bis-indolyl-)-phthaliden, 3-Aminofluoranen, 6-Dialkylamino-2-dibenzylaminofluoranen, 6-Dialkylamino-3-methyl-2-arylaminofluoranen, 3,6-Bisalkoxyfluoranen, 3,6-Bisdiarylaminofluoranen, Leukoauraminen, Spiropyranen, Spirodipyranen, Benzoxazine, Chromenopyrazolen, Chromenoindolen, Phenoxazinen, Phenothiazinen, Chinazolinen, Rhodaminlaktamen, Carbazolylmethanen oder Triarylmethane einsetzt.Components (A), (B) and (C) come into contact with one another by pressure or heating, depending on the recording material, and leave records on the carrier material. The color is produced in accordance with the type of components (A) and (B), which represent the electron donor and form the chromogenic part. The color formation is caused by component (C). By a suitable combination of the individual components, the desired colors, e.g. yellow, orange, red, violet, blue, green, gray, black or mixed colors can be generated. Another possible combination is that components (A) and (B) together with one or more conventional color formers, e.g. 3,3- (bis-aminophenyl -) - phthalides such as CVL, 3-indolyl-3-aminophenylaza- or -diazaphthalides, (3,3-bis-indolyl -) - phthalides, 3-aminofluoranes, 6-dialkylamino-2- dibenzylaminofluoranen, 6-dialkylamino-3-methyl-2-arylaminofluoranen, 3,6-Bisalkoxyfluoranen, 3,6-Bisdiarylaminofluoranen, Leukoauraminen, spiropyrans, spirodipyrans, benzoxazines, Chromenopyrazolen, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes used .

Substituenten im Sinne von Y₁ und Y₂ sind am zentralen (meso) Kohlenstoffatom der Verbindung der Formel (1) leicht abspaltbare Substituenten, die dadurch in ein Anion übergehen. Derartige Substituenten können Halogenatome, aliphatische, cycloaliphatische, araliphatische, aromatische oder heterocyclische Ethergruppen, wie z.B. Alkoxy, Cycloalkoxy, Aralkoxy, Aryloxy oder Heteroaryloxy, sowie auch Acyloxygruppen, die z.B. der Formel

Figure imgb0002

entsprechen, worin R' einen organischen Rest, vorzugsweise unsubstituiertes oder z.B. durch Halogen oder Cyano substituiertes Alkyl, Cycloalkyl, Aralkyl, Aryl oder Heteroaryl, Q' -CO- oder -SO₂- und n 1 oder 2, vorzugsweise 1 bedeuten, darstellen.Substituents in the sense of Y₁ and Y₂ are easily removable substituents on the central (meso) carbon atom of the compound of formula (1), which thereby change into an anion. Such substituents can be halogen atoms, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether groups, such as, for example, alkoxy, cycloalkoxy, aralkoxy, aryloxy or heteroaryloxy, and also acyloxy groups, for example of the formula
Figure imgb0002
correspond in which R 'is an organic radical, preferably unsubstituted or, for example, halogen or cyano substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl, Q' is -CO- or -SO₂- and n is 1 or 2, preferably 1.

Als Acyloxy sind Y₁ und Y₂ vorzugsweise eine Gruppe der Formel R''-CO-O-, worin R'' Niederalkyl oder Phenyl bedeutet. Als abspaltbare Substituenten besonders geeignet sind Halogene, wie z.B. Fluor, Brom, Jod und vor allem Chlor.As acyloxy, Y₁ and Y₂ are preferably a group of the formula R ″ -CO-O-, where R ″ is lower alkyl or phenyl. Halogens, such as e.g. Fluorine, bromine, iodine and especially chlorine.

Falls Y₁ und Y₂ miteinander verbunden sind, so bilden sie mit dem gemeinsamen Bindungskohlenstoffatom als abspaltbaren Substituenten zweckmässigerweise einen 5- oder vorzugsweise 6-gliedrigen heterocyclischen Ring, insbesondere cyclische Ether-, Thioether-, Etherester- oder Thioetherestergruppierungen, die vorzugsweise ankondensierte, gegebenenfalls z.B. durch Halogenatome substituierte Benzolringe aufweisen.If Y₁ and Y₂ are bonded to one another, they advantageously form a 5- or preferably 6-membered heterocyclic ring, in particular cyclic ether, thioether, etherester or thioetherester groups, which preferably are fused, optionally e.g. have benzene rings substituted by halogen atoms.

Q₁ steht vorzugsweise für ein Sauerstoffatom, während Q₂ bevorzugt -SO₂-oder vorallem -CO- darstellt. Falls Q₁ 〉NR oder 〉N-NH-R darstellt, so ist R vorzugsweise Wasserstoff, Methyl oder Phenyl.Q₁ preferably represents an oxygen atom, while Q₂ preferably represents -SO₂ or, above all, -CO-. If Q₁ represents〉 NR or〉 N-NH-R, R is preferably hydrogen, methyl or phenyl.

Als 6-gliedriger aromatischer Ring stellt A vorzugsweise einen Benzolring dar, der unsubstituiert oder durch Halogen, Cyano, Nitro, Niederalkyl, Niederalkoxy, Niederalkylthio, Niederalkylcarbonyl, Niederalkoxycarbonyl, Amino, Niederalkylamino, Diniederalkylamino oder Niederalkylcarbonylamino substituiert ist. Der Ring A kann auch einen annellierten aromatischen Ring, vorzugsweise einen Benzolring enthalten und stellt somit z.B. einen Naphthalin- oder Phenanthrenring dar.As a 6-membered aromatic ring, A is preferably a benzene ring which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl, amino, lower alkylamino, di-lower alkylamino or lower alkylcarbonylamino. Ring A may also contain a fused aromatic ring, preferably a benzene ring, and thus represents e.g. represents a naphthalene or phenanthrene ring.

Die durch A wiedergegebenen bevorzugten 6-gliedrigen aromatischen Reste sind der 2,3-Naphthalino-, 1,2-Naphthalino- oder 1,2-Benzorest, der unsubstituiert oder durch Halogen, wie Chlor oder Brom, Nitro, Niederalkyl, Niederalkoxy, Niederalkylthio oder eine wie vorstehend definiert gegebenenfalls substituierte Aminogruppe substituiert ist, wobei der unsubstituierte oder durch 4 Chloratome substituierte 1,2-Benzorest besonders bevorzugt ist.The preferred 6-membered aromatic radicals represented by A are the 2,3-naphthalino, 1,2-naphthalino or 1,2-benzo radical, which is unsubstituted or by halogen, such as chlorine or bromine, nitro, lower alkyl, lower alkoxy, lower alkylthio or one as defined above optionally substituted amino group is substituted, the unsubstituted or substituted by 4 chlorine atoms 1,2-benzo radical is particularly preferred.

Besonders wichtige Komponenten (A) für das erfindungsgemässe Farbreaktantensystem entsprechen der Formel

Figure imgb0003

worin A₁ einen gegebenenfalls durch Halogen, Cyano, Niederalkyl, Niederalkylthio, Niederalkoxy oder Diniederalkylamino substituierten Benzolring und
Y₃ und Y₄ unabhängig voneinander, Halogen oder Acyloxy, wie Niederalkylcarbonyloxy oder Benzoyloxy und besonders Chlor oder Brom bedeuten.Particularly important components (A) for the color reactant system according to the invention correspond to the formula
Figure imgb0003
wherein A₁ is an optionally substituted by halogen, cyano, lower alkyl, lower alkylthio, lower alkoxy or di-lower alkylamino and
Y₃ and Y₄ independently of one another, halogen or acyloxy, such as lower alkylcarbonyloxy or benzoyloxy and especially chlorine or bromine.

Unter den Verbindungen der Formel (2) sind die Laktonverbindungen, in denen Y₃ und Y₄ Halogenatome wie Brom oder besonders Chlor bedeuten und der Ring A₁ einen unsubstituierten oder durch Halogen, Niederalkyl, Niederalkoxy oder Diniederalkylamino substituierten Benzolring darstellt, bevorzugt.Among the compounds of formula (2), the lactone compounds in which Y₃ and Y₄ are halogen atoms such as bromine or especially chlorine and the ring A₁ is an unsubstituted or substituted by halogen, lower alkyl, lower alkoxy or di-lower alkylamino, are preferred.

Von besonderem Interesse sind Laktonverbindungen der Formel

Figure imgb0004

worin der Ring B unsubstituiert oder durch Niederalkyl, Diniederalkylamino oder 1 bis 4 Chloratome substituiert ist und Y₅ und Y₆ Brom oder besonders Chlor bedeuten.Lactone compounds of the formula are of particular interest
Figure imgb0004
wherein the ring B is unsubstituted or substituted by lower alkyl, di-lower alkylamino or 1 to 4 chlorine atoms and Y₅ and Y₆ are bromine or especially chlorine.

Verbindungen der Formel (1), in der Y₁ und Y₂ als abspaltbare Substituenten Halogen bedeuten, werden gemäss Org. Synth. Coll. Vol. II, 528 hergestellt, indem man z.B. das entsprechende Phthalsäureanhydrid zum o-Phthalyldichlorid umsetzt z.B. mit Phosphorpentachlorid, Thionylchlorid oder Benzotrichlorid gegebenenfalls unter Zusatz von Zinkchlorid und dann das symmetrische Phthalyldichlorid mit Aluminiumchlorid oder auch Zinntetrachlorid in das unsymmetrische Phthalyldichlorid umwandelt.Compounds of formula (1) in which Y₁ and Y₂ are halogen as removable substituents are, according to Org. Synth. Coll. Vol. II, 528 prepared by, for example, the corresponding phthalic anhydride for Reacts o-phthalyl dichloride, for example with phosphorus pentachloride, thionyl chloride or benzotrichloride, optionally with the addition of zinc chloride, and then converts the symmetrical phthalyl dichloride with aluminum chloride or tin tetrachloride into the asymmetrical phthalyl dichloride.

Verbindungen der Formel (1), in der Y₁ und Y₂ miteinander verbunden sind, werden z.B. hergestellt, indem man Alkalimetallsalze der Salicylsäure, deren Ester oder Kernsubstitutionsprodukte mit Halogeniden von o-Phthalsäure oder deren Kernsubstitutionsprodukten (gemäss DE-PS 400790) umsetzt.Compounds of formula (1) in which Y₁ and Y₂ are linked are e.g. prepared by reacting alkali metal salts of salicylic acid, its esters or core substitution products with halides of o-phthalic acid or their core substitution products (according to DE-PS 400790).

Zu spezifischen Beispielen für die Verbindungen der Formeln (1) bis (3) gehören
3,3-Dichlorphthalid, 3,3-Dibromphthalid, 3,3,5-Trichlorphthalid,
3,3,5,6-Tetrachlorphthalid, 3,3-Difluor-4,5,6,7-tetrachlorophthalid,
3,3,4,5,6,7-Hexachlorphthalid, 3,3-Dibrom-4,5,6,7-tetra-chlorphthalid,
3,3,4,7-Tetrachlorphthalid, 3,3,6,7-Tetrachlorphthalid,
3,3,4,5,7-Pentabrom-6-acetyloxy-phthalid, 3,3-Diethoxy-phthalid,
3,3-Diethoxy-4,5,6,7-tetrachlor-phthalid,
3,3-Diethoxy-6,7-dichlorphthalid, 3,3-Dimethoxy-4,7-dichlorphthalid,
3,3-Dimethoxyphthalid, 3,3-Dimethoxy-4,5,6,7-tetrachlorphthalid,
3-Ethoxy-3,4,5,6,7-pentachlorphthalid, 3-Ethoxy-4,5-dimethoxyphthalid,
3-Ethoxy-3,6,7-trichlorphthalid, 3,3-Diphenylthio-phthalid,
3,3-(Di-4'-nitrophenylthio)-phthalid,
3,3-(Di-4'-chlorphenylthio)-phthalid,
3,3-(Di-4'-methylphenylthio)-phthalid, 3-Methoxy-3-phenoxy-phthalid,
3,3-Di-4'-tolyloxi-phthalid, 3,3-Dichlor-6-dimethylaminophthalid,
3,3-Dichlor-6-acetylaminophthalid, 3,3-Dichlor-6-methylphthalid,
3,3-Dichlor-6-tert.Butylphthalid, ferner
2-Oxybuttersäurephthalidenetherester, Salicylsäure-phthalidylidenetherester, 5-Bromsalicylsäure-phthalidylidenetherester, 3,5-Dibromsalicylsäure-phthalidylidenetherester, Salicylsäure-tetrachlorphthalidylidenetherester, Thiosalicylsäurephthalidylidenetherester.Specific examples of the compounds of the formulas (1) to (3) include
3,3-dichlorophthalide, 3,3-dibromophthalide, 3,3,5-trichlorophthalide,
3,3,5,6-tetrachlorophthalide, 3,3-difluoro-4,5,6,7-tetrachlorophthalide,
3,3,4,5,6,7-hexachlorophthalide, 3,3-dibromo-4,5,6,7-tetrachlorophthalide,
3,3,4,7-tetrachlorophthalide, 3,3,6,7-tetrachlorophthalide,
3,3,4,5,7-pentabromo-6-acetyloxy-phthalide, 3,3-diethoxy-phthalide,
3,3-diethoxy-4,5,6,7-tetrachlorophthalide,
3,3-diethoxy-6,7-dichlorophthalide, 3,3-dimethoxy-4,7-dichlorophthalide,
3,3-dimethoxyphthalide, 3,3-dimethoxy-4,5,6,7-tetrachlorophthalide,
3-ethoxy-3,4,5,6,7-pentachlorophthalide, 3-ethoxy-4,5-dimethoxyphthalide,
3-ethoxy-3,6,7-trichlorophthalide, 3,3-diphenylthio-phthalide,
3,3- (di-4'-nitrophenylthio) phthalide,
3,3- (di-4'-chlorophenylthio) phthalide,
3,3- (di-4'-methylphenylthio) phthalide, 3-methoxy-3-phenoxy phthalide,
3,3-di-4'-tolyloxiphthalide, 3,3-dichloro-6-dimethylaminophthalide,
3,3-dichloro-6-acetylaminophthalide, 3,3-dichloro-6-methylphthalide,
3,3-dichloro-6-tert-butylphthalide, further
2-oxybutyric acid phthalidene ether esters, salicylic acid phthalidylidene ether esters, 5-bromosalicylic acid phthalidylidene ether esters, 3,5-dibromosalicylic acid phthalidylidene ether esters, salicylic acid tetrachlorophthalidylidene ether esters, thiosalicylic acid phthalidylidene ether esters.

Es ist zu bemerken, daß in der EP-A- 0 373 110 ein ähnliches druck- oder wärmeempfindliches Aufzeichnungsmaterial, wie in der vorliegenden Erfindung, offenbart wird, wobei jedoch der Komponent (A) an der 3-Stelle einen als Anion abspaltbaren Substituenten und einen monocyclischen oder polycyclishen aromatischen oder heteroaromatischen Rest aufweist.
EP-A- 0 373 110 gehört zum Stand der Technik nach Artikel 54(3)(4) EPÜ.It should be noted that EP-A-0 373 110 discloses a pressure- or heat-sensitive recording material similar to that in the present invention, however component (A) at the 3-position has a substituent and which can be removed as an anion has a monocyclic or polycyclic aromatic or heteroaromatic radical.
EP-A-0 373 110 belongs to the prior art under Article 54 (3) (4) EPC.

Die erfindungsgemäss verwendeten Komponenten (B), die mit Komponente (A) chromogene Verbindungen bilden, sind vorzugsweise mono- oder polycyclische aromatische oder heteroaromatische Verbindungen, die ein System konjugierter Doppelbindungen ergänzen und nötigenfalls auxochrome Substituenten, wie z.B. Aminogruppen, substituierte Aminogruppen, wie Diniederalkylamino, Hydroxylgruppen, Ethergruppen wie Alkoxy, Thiogruppen oder Mercaptogruppen, wie Alkylthio aufweisen.The components (B) used according to the invention, which form chromogenic compounds with component (A), are preferably mono- or polycyclic aromatic or heteroaromatic compounds which supplement a system of conjugated double bonds and, if necessary, auxochromic substituents, such as e.g. Amino groups, substituted amino groups such as di-lower alkylamino, hydroxyl groups, ether groups such as alkoxy, thio groups or mercapto groups such as alkylthio.

Derartige Verbindungen entstammen zweckmässigerweise aus der Reihe der unsubstituierten, C- und/oder N-substituierten Aniline, Diarylamine, Naphthylamine, N-substituierten Aminophenylethylenverbindungen, N-substituierten Aminophenylstyrolverbindungen, Acylacetarylamide, einwertigen oder mehrwertigen Phenole, Phenolether, Naphthole, Naphtholcarbonsäureanilide, 3-Aminophenolether, Aminopyrazole, Aminothiazole, Pyrazolone, Pyridone, Pyrrole, Thiophene, Chinolone, Pyrimidone, Barbitursäuren, Indole, Carbazole, Acridine, Benzofurane, Benzothiophene (Thionaphthene), Naphthothiophene, Phenothiazine, Pyrrolidine, Piperidine, Piperazine, Morpholine, Benzomorpholine, Indoline, Kairoline, Dihydrochinoline, Tetrahydrochinoline, Julolidine.Such compounds expediently come from the series of unsubstituted, C- and / or N-substituted anilines, diarylamines, naphthylamines, N-substituted aminophenylethylene compounds, N-substituted aminophenylstyrene compounds, acylacetarylamides, monohydric or polyhydric phenols, phenol ethers, 3-naphthenoic acid aminophenol acid, naphthyl enoltholethene acid, naphthyl enoltholethene acid, naphthyl enoltholetholeic acid, naphthyl enoltholetholeic acid, naphthyl acid, naphthyl enoltholene, naphthyl acid, naphthyl enoltholetholeic acid, , Aminopyrazoles, aminothiazoles, pyrazolones, pyridones, pyrroles, thiophenes, quinolones, pyrimidones, barbituric acids, indoles, carbazoles, acridines, benzofurans, benzothiophenes (thionaphthenes), naphthothiophenes, phenothiazines, pyrrolidines, piperidines, piperidines, piperomines, piperomines, piperomines Dihydroquinolines, tetrahydroquinolines, julolidines.

Am bevorzugtesten sind Anilinverbindungen der Formel

Figure imgb0005

oder
Indolverbindungen der Formel
Figure imgb0006
worin R₁ und R₂, unabhängig voneinander, je Wasserstoff, unsubstituiertes oder durch Halogen, Hydroxy, Cyano oder Niederalkoxy substituiertes Alkyl mit höchstens 12 Kohlenstoffatomen, Acyl mit 1 bis 8 Kohlenstoffatomen, Cycloalkyl mit 5 bis 10 Kohlenstoffatomen oder unsubstituiertes oder durch Halogen, Cyano, Niederalkyl, Niederalkoxy, Niederalkoxycarbonyl, -NX'X'' oder 4-NX'X''-Phenylamino ringsubstituiertes Phenalkyl oder Phenyl, worin X' und X'', unabhängig voneinander, Wasserstoff, Niederalkyl, Cyclohexyl, Benzyl oder Phenyl darstellen, oder R₁ und R₂ zusammen mit dem sie verbindenden Stickstoffatom einen fünf- oder sechsgliedrigen, vorzugsweise gesättigten, heterocyclischen Rest darstellen. V bedeutet Wasserstoff, Halogen, Niederalkyl, C₁-C₁₂-Alkoxy, C₁-C₁₂-Acyloxy, Benzyl, Phenyl, Benzyloxy, Phenyloxy, durch Halogen, Cyano, Niederalkyl oder Niederalkoxy substituiertes Benzyl oder Benzyloxy, oder die Gruppe -NT₁T₂. T₁ und T₂, unabhängig voneinander, bedeuten je Wasserstoff, Niederalkyl, C₅-C₁₀-Cycloalkyl, unsubstituiertes oder durch Halogen, Cyano, Niederalkyl oder Niederalkoxy substituiertes Benzyl, oder Acyl mit 1 bis 8 Kohlenstoffatomen und T₁ auch unsubstituiertes oder durch Halogen, Cyano, Niederalkyl oder Niederalkoxy substituiertes Phenyl. m ist 1 oder 2. Z₁ bedeutet Wasserstoff, unsubstituiertes oder durch Halogen, Hydroxyl, Cyano oder Niederalkoxy substituiertes Alkyl mit höchstens 12 Kohlenstoffatomen, Acyl mit 1 bis 12 Kohlenstoffatomen oder unsubstituiertes oder durch Halogen, Cyano, Niederalkyl oder Niederalkoxy substituiertes Benzyl. Z₂ bedeutet Wasserstoff, Niederalkyl oder Phenyl und Z₂' bedeutet Niederalkyl, Cyclohexyl, Benzyl oder Phenyl. Der Benzolkern D ist unsubstituiert oder durch Halogen, Cyano, Niederalkyl, Niederalkoxy, Niederalkoxycarbonyl, Amino, Mononiederalkylamino oder Diniederalkylamino substituiert. Ein V ist vorzugsweise in Ortho-Stellung zur Verknüpfungsstelle. -NR₁R₂ befindet sich vorzugsweise in Para-Stellung zur Verknüpfungsstelle.Most preferred are aniline compounds of the formula
Figure imgb0005
or
Indole compounds of the formula
Figure imgb0006
wherein R₁ and R₂, independently of one another, are each hydrogen, unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or unsubstituted or phenalkyl or phenyl ring-substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X '' or 4-NX'X '' - phenylamino, where X 'and X'', independently of one another, are hydrogen, lower alkyl, cyclohexyl, benzyl or represent phenyl, or R₁ and R₂ together with the nitrogen atom connecting them represent a five- or six-membered, preferably saturated, heterocyclic radical. V represents hydrogen, halogen, lower alkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, benzyl or benzyloxy substituted by halogen, cyano, lower alkyl or lower alkoxy, or the group -NT₁T₂. T₁ and T₂, independently of one another, each represent hydrogen, lower alkyl, C₅-C₁₀ cycloalkyl, unsubstituted or substituted by halogen, cyano, lower alkyl or lower alkoxy, or acyl having 1 to 8 carbon atoms and T₁ also unsubstituted or by halogen, cyano, lower alkyl or lower alkoxy substituted phenyl. m is 1 or 2. Z₁ means hydrogen, unsubstituted or substituted by halogen, hydroxyl, cyano or lower alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 12 carbon atoms or unsubstituted or substituted by halogen, cyano, lower alkyl or lower alkoxy benzyl. Z₂ means hydrogen, lower alkyl or phenyl and Z₂ 'means lower alkyl, cyclohexyl, benzyl or phenyl. The benzene nucleus D is unsubstituted or substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, amino, mono-lower alkylamino or di-lower alkylamino. A V is preferably in the ortho position to the connection point. -NR₁R₂ is preferably in the para position to the junction.

Niederalkyl, Niederalkoxy und Niederalkylthio stellen bei der Definition der Komponenten (A) und (B) solche Gruppen oder Gruppenbestandteile dar, die 1 bis 6, insbesondere 1 bis 4 Kohlenstoffatome aufweisen. Beispiele für derartige Gruppen sind Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, tert.Butyl, Amyl, Isoamyl oder Hexyl bzw. Methoxy, Ethoxy, Isopropoxy, Isobutoxy oder tert.Butoxy bzw. Methylthio, Ethylthio, Propylthio oder Butylthio.Lower alkyl, lower alkoxy and lower alkylthio are in the definition of components (A) and (B) those groups or group components which have 1 to 6, in particular 1 to 4, carbon atoms. Examples of such groups are ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or hexyl or methoxy, ethoxy, isopropoxy, isobutoxy or tert-butoxy or methylthio, ethylthio, propylthio or butylthio.

Halogen bedeutet beispielsweise Fluor, Brom oder vorzugsweise Chlor.Halogen means for example fluorine, bromine or preferably chlorine.

Acyl ist besonders Formyl, Niederalkylcarbonyl, wie z.B. Acetyl oder Propionyl, oder Benzoyl. Weitere Acylreste können Niederalkylsulfonyl, wie z.B. Methylsulfonyl oder Ethylsulfonyl sowie Phenylsulfonyl sein. Benzoyl und Phenylsulfonyl können durch Halogen, Methyl, Methoxy oder Ethoxy substituiert sein.Acyl is especially formyl, lower alkylcarbonyl, e.g. Acetyl or propionyl, or benzoyl. Further acyl residues can be lower alkylsulfonyl, e.g. Be methylsulfonyl or ethylsulfonyl and phenylsulfonyl. Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.

Stellen die Substituenten R, R₁, R₂ und Z₁ Alkylgruppen dar, so können sie geradkettig oder verzweigt sein. Beispiele solcher Alkylreste sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, tert.-Butyl, Amyl, Isoamyl, n-Hexyl, 2-Ethyl-hexyl, n-Heptyl, n-Octyl, 1,1,3,3-Tetramethylbutyl, Isooctyl, n-Nonyl, Isononyl oder n-Dodecyl.If the substituents R, R₁, R₂ and Z₁ represent alkyl groups, they can be straight-chain or branched. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, isooctyl, n-nonyl, isononyl or n-dodecyl.

Sind die Alkylreste in R₁, R₂ und Z₁ substituiert, so handelt es sich vor allem um Cyanoalkyl, Halogenalkyl, Hydroxyalkyl, Alkoxyalkyl jeweils vorzugsweise mit insgesamt 2 bis 8 Kohlenstoffatomen, wie z.B. 2-Cyanoethyl, 2-Chlorethyl, 2-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2,3-Dihydroxypropyl, 2-Hydroxy-3-chlor-propyl, 3-Methoxypropyl, 4-Methoxybutyl oder 4-Propoxybutyl.If the alkyl radicals in R₁, R₂ and Z₁ are substituted, it is primarily cyanoalkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl each preferably with a total of 2 to 8 carbon atoms, such as e.g. 2-cyanoethyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2,3-dihydroxypropyl, 2-hydroxy-3-chloropropyl, 3-methoxypropyl, 4-methoxybutyl or 4-propoxybutyl.

Beispiele für Cycloalkyl in der Bedeutung von R, R₁, R₂, T₁ und T₂ sind Cyclopentyl, Cycloheptyl oder vorzugsweise Cyclohexyl. Die Cycloalkylreste können einen oder mehrere C₁-C₄-Alkylreste, vorzugsweise Methylgruppen, enthalten und weisen insgesamt 5 bis 10 Kohlenstoffatome auf.Examples of cycloalkyl in the meaning of R, R₁, R₂, T₁ and T₂ are cyclopentyl, cycloheptyl or preferably cyclohexyl. The cycloalkyl radicals can contain one or more C₁-C₄ alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.

Der Acyloxyrest in V ist beispielsweise Formyloxy, Niederalkylcarbonyloxy, wie z.B. Acetyloxy oder Propionyloxy, oder Benzoyloxy. Als C₁-C₁₂-Alkoxyrest kann V eine geradkettige oder verzweigte Gruppe sein, wie z.B. Methoxy, Ethoxy, Isopropoxy, n-Butoxy, tert-Butoxy, Amyloxy, 1,1,3,3-Tetramethylbutoxy, n-Hexyloxy, n-Octyloxy oder Dodecyloxy.The acyloxy radical in V is, for example, formyloxy, lower alkylcarbonyloxy, e.g. Acetyloxy or propionyloxy, or benzoyloxy. As a C₁-C₁₂ alkoxy radical, V can be a straight-chain or branched group, e.g. Methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, amyloxy, 1,1,3,3-tetramethylbutoxy, n-hexyloxy, n-octyloxy or dodecyloxy.

Wenn das Substituentenpaar (R₁ und R₂) zusammen mit dem gemeinsamen Stickstoffatom einen heterocyclischen Rest darstellt, so ist dieser beispielsweise Pyrrolidino, Piperidino, Pipecolino, Morpholino,Thiomorpholino, Piperazino, N-Alkylpiperazino, wie z.B. N-Methylpiperazino, N-Phenylpiperazino oder N-Alkylimidazolino. Bevorzugte gesättigte heterocyclische Reste für -NR₁R₂ sind Pyrrolidino, Piperidino oder Morpholino.If the pair of substituents (R₁ and R₂) together with the common nitrogen atom represents a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino, piperazino, N-alkylpiperazino, such as N-methylpiperazino, N-phenylpiperazino or N-alkylimidazolino. Preferred saturated heterocyclic radicals for -NR₁R₂ are pyrrolidino, piperidino or morpholino.

V kann vorteilhafterweise Wasserstoff, Halogen, Niederalkyl, wie z.B. Methyl, Benzyloxy, C₁-C₈-Alkoxy, in erster Linie Niederalkoxy, wie z.B. Methoxy, Ethoxy, n-Propoxy, Isopropoxy, n-Butoxy oder tert.Butoxy, oder die Gruppe -NT₁T₂ sein, wobei von den Resten T₁ und T₂ eines vorzugsweise C₁-C₈-Acyl oder Niederalkyl und das andere Wasserstoff oder Niederalkyl ist. Der Acylrest ist in diesem Falle besonders Niederalkylcarbonyl, wie z.B. Acetyl oder Propionyl. Vorzugsweise ist V Acetylamino, Dimethylamino, Benzyloxy oder besonders Niederalkoxy und vor allem Ethoxy oder Wasserstoff.V can advantageously be hydrogen, halogen, lower alkyl, e.g. Methyl, benzyloxy, C₁-C₈ alkoxy, primarily lower alkoxy, e.g. Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy, or the group -NT₁T₂, where one of the radicals T₁ and T₂ is preferably C₁-C₈ acyl or lower alkyl and the other is hydrogen or lower alkyl. The acyl radical in this case is especially lower alkylcarbonyl, e.g. Acetyl or propionyl. V is preferably acetylamino, dimethylamino, benzyloxy or especially lower alkoxy and especially ethoxy or hydrogen.

R₁ und R₂ in der Bedeutung von Phenalkyl weisen vorteilhafterweise insgesamt 7 bis 9 Kohlenstoffatome auf und stehen in der Regel für α-Methylbenzyl, Phenethyl, Phenisopropyl oder in erster Linie für Benzyl, das bevorzugterweise auch ringsubstituiert sein kann.R₁ and R₂ in the meaning of phenalkyl advantageously have a total of 7 to 9 carbon atoms and are generally α-methylbenzyl, phenethyl, phenisopropyl or primarily benzyl, which can preferably also be ring-substituted.

Bevorzugte Substituenten in der Benzylgruppe der R-, T- und Z-Reste, in der Phenylgruppe von R₁, R₂ und T₁ und in der Benzyloxygruppe von V sind z.B. Halogen, Methyl oder Methoxy. Beispiele für derartige araliphatische bzw. aromatische Reste sind p-Methylbenzyl, o- oder p-Chlorbenzyl, 2,5-Dimethylbenzyl, o- oder p-Tolyl, Xylyl, 2,6-Dimethylphenyl, o-, m-oder p-Chlorphenyl, o- oder p-Methoxyphenyl, o- oder p-Chlorbenzyloxy oder o- oder p-Methylbenzyloxy.Preferred substituents in the benzyl group of the R, T and Z radicals, in the phenyl group of R₁, R₂ and T₁ and in the benzyloxy group of V are e.g. Halogen, methyl or methoxy. Examples of such araliphatic or aromatic radicals are p-methylbenzyl, o- or p-chlorobenzyl, 2,5-dimethylbenzyl, o- or p-tolyl, xylyl, 2,6-dimethylphenyl, o-, m- or p-chlorophenyl , o- or p-methoxyphenyl, o- or p-chlorobenzyloxy or o- or p-methylbenzyloxy.

Die Substituenten R₁ und R₂ sind vorzugsweise Cyclohexyl, Benzyl, Tolyl, Phenethyl, Cyano-Niederalkyl z.B. β-Cyanoethyl oder in erster Linie Niederalkyl, wie z.B. Methyl, Ethyl oder n-Butyl. -NR₁R₂ ist bevorzugt auch Pyrrolidinyl.The substituents R₁ and R₂ are preferably cyclohexyl, benzyl, tolyl, phenethyl, cyano-lower alkyl e.g. β-cyanoethyl or primarily lower alkyl, e.g. Methyl, ethyl or n-butyl. -NR₁R₂ is also preferably pyrrolidinyl.

Der Indolsubstituent Z₁ ist vorzugsweise Wasserstoff, Benzyl, Acetyl, Propionyl oder besonders C₁-C₈-Alkyl, wie z.B. Methyl, Ethyl, n-Butyl oder n-Octyl.The indole substituent Z₁ is preferably hydrogen, benzyl, acetyl, propionyl or especially C₁-C₈-alkyl, such as methyl, ethyl, n-butyl or n-octyl.

Z₂ ist vorzugsweise Phenyl oder vor allem Methyl. Z₂' ist vorzugsweise Niederalkyl.Z₂ is preferably phenyl or especially methyl. Z₂ 'is preferably lower alkyl.

Der Benzolring D ist vorzugsweise nicht weiter substituiert. Wenn D Substituenten enthält, so sind diese besonders Halogen, Niederalkyl, z.B. Methyl, tert.Butyl, Niederalkoxy oder Diniederalkylamino wie Dimethylamino.The benzene ring D is preferably not further substituted. If D contains substituents, these are especially halogen, lower alkyl, e.g. Methyl, tert-butyl, lower alkoxy or di-lower alkylamino such as dimethylamino.

Spezifische Beispiele für Komponenten (B) sind
2-Amino-4-methoxytoluol, N,N-Dimethylanilin, N,N-Diethylanilin,
N-Phenylpyrrolidin, N-3-Ethoxyphenylpyrrolidin, N-Phenylmorpholin, m-Phenetidin,
3-Ethoxy-N,N-dimethylanilin, 3-Ethoxy-N,N-diethylanilin (N,N-Diethyl-m-phenetidin),
3-Ethoxy-N,N-dibutylanilin, 3-n-Butoxy-N,N-di-n-butylanilin,
1,3-Bisdimethylaminobenzol, 3-Acetylamino-N,N-dimethylanilin, N-Methyl-N-4-methylphenylanilin,
4-Ethoxy-diphenylamin, N-Methyl-diphenylamin, N,N-Dibenzylanilin,
N-Phenyl-toluidin, N-Phenyl-xylidin,
3-N,N-(Di-2-cyclohexylethyl)aminophenol, 3-Diethylaminophenol,
1,1-Bis(4-diethylaminophenyl-)ethylen, 1-(4-Diethylaminophenyl)-1-(4-methoxyphenyl-)ethylen, N-Cyclohexyl-N-methylanilin, Thiophen,
N-Methylpyrrol, Kairolin, Julolidin, N-Ethylcarbazol, 2-Methylindol,
2-Phenylindol, 1,2-Dimethylindol, 1-n-Butyl-2-methylindol,
1-Ethyl-2-methylindol, 1-n-Octyl-2-methylindol, 1-Methyl-2-phenylindol,
1-Ethyl-2-phenylindol, 3-Methyl-6-dimethylaminoindol, 1-Phenyl-3-methyl-5-pyrazolon, Benzthiazol-2-yl-acetonitril,
1-Phenyl-5-methyl-3-pyrazolon, 1-(2'-chlorphenyl)-5-methyl-3-pyrazolon, Thionaphthen, α-Naphthol, β-Naphthol, α-Naphthylamin, β-Naphthylamin,
1-Methyl-1,2,3,4-tetrahydrochinolin, N-Ethyl-N-2-chlorethylanilin,
1-Benzyl-2-methylindolin, N-Ethyl-N-benzylanilin, Phenothiazin, 10-Methyl-phenothiazin, 10-Acetylphenothiazin, 2,3,3-Trimethylindolenin,
1,3,3-Trimethyl-2-methylen-indolin.Specific examples of components (B) are
2-amino-4-methoxytoluene, N, N-dimethylaniline, N, N-diethylaniline,
N-phenylpyrrolidine, N-3-ethoxyphenylpyrrolidine, N-phenylmorpholine, m-phenetidine,
3-ethoxy-N, N-dimethylaniline, 3-ethoxy-N, N-diethylaniline (N, N-diethyl-m-phenetidine),
3-ethoxy-N, N-dibutylaniline, 3-n-butoxy-N, N-di-n-butylaniline,
1,3-bisdimethylaminobenzene, 3-acetylamino-N, N-dimethylaniline, N-methyl-N-4-methylphenylaniline,
4-ethoxy-diphenylamine, N-methyl-diphenylamine, N, N-dibenzylaniline,
N-phenyl-toluidine, N-phenyl-xylidine,
3-N, N- (di-2-cyclohexylethyl) aminophenol, 3-diethylaminophenol,
1,1-bis (4-diethylaminophenyl) ethylene, 1- (4-diethylaminophenyl) -1- (4-methoxyphenyl) ethylene, N-cyclohexyl-N-methylaniline, thiophene,
N-methylpyrrole, kairolin, julolidine, N-ethylcarbazole, 2-methylindole,
2-phenylindole, 1,2-dimethylindole, 1-n-butyl-2-methylindole,
1-ethyl-2-methylindole, 1-n-octyl-2-methylindole, 1-methyl-2-phenylindole,
1-ethyl-2-phenylindole, 3-methyl-6-dimethylaminoindole, 1-phenyl-3-methyl-5-pyrazolone, benzothiazol-2-yl-acetonitrile,
1-phenyl-5-methyl-3-pyrazolone, 1- (2'-chlorophenyl) -5-methyl-3-pyrazolone, thionaphthene, α-naphthol, β-naphthol, α-naphthylamine, β-naphthylamine,
1-methyl-1,2,3,4-tetrahydroquinoline, N-ethyl-N-2-chloroethylaniline,
1-benzyl-2-methylindoline, N-ethyl-N-benzylaniline, phenothiazine, 10-methylphenothiazine, 10-acetylphenothiazine, 2,3,3-trimethylindolenine,
1,3,3-trimethyl-2-methylene indoline.

Bevorzugte Komponenten (B) sind auch Phthalid- und vor allem Fluoranverbindungen, welche mindestens eine primäre Aminogruppe oder eine durch Niederalkyl, Cyclohexyl oder Benzyl monosubstituierte Aminogruppe aufweisen. Diese Phthalid- und Fluoranverbindungen sind beispielsweise in FR-A-1 553 291, GB-A-1 211 393, DE-A-2 138 179, DE-A-2 422 899 und EP-A-138 177 beschrieben.Preferred components (B) are also phthalide and especially fluoran compounds which have at least one primary amino group or an amino group monosubstituted by lower alkyl, cyclohexyl or benzyl. These phthalide and fluoran compounds are described for example in FR-A-1 553 291, GB-A-1 211 393, DE-A-2 138 179, DE-A-2 422 899 and EP-A-138 177.

Spezifische Beispiele für solche Komponenten (B) sind:
2-Amino-3-chlor-6-diethylaminofluoran
2-Amino-6-dibutylaminofluoran
6-Amino-3-chlorfluoran
2-Amino-6-diethylaminofluoran
2-Methylamino-6-dimethylaminofluoran
2-Ethylamino-6-diethylaminofluoran
2-Methylamino-6-diethylaminofluoran
2-n-Butylamino-6-diethylaminofluoran
2-n-Octylamino-6-diethylaminofluoran
2-sek.Butylamino-6-diethylaminofluoran
2-Benzylamino-6-diethylaminofluoran
2,3-Dimethyl-6-ethylaminofluoran
2,3,7-Trimethyl-6-ethylaminofluoran
2,3,7-Trimethyl-6-ethylamino-5'(6')-tert.butylfluoran
2-Chlor-3,7-dimethyl-6-ethylamino-5'(6')-tert.butylfluoran
2-tert.Butyl-6-ethylamino-7-methyl-5'(6')-tert.butylfluoran
3-Chlor-6-cyclohexylaminofluoran,
2,7-Dimethyl-3,6-bis-ethylaminofluoran,
2-(2'-Chloranilino-6-ethylamino-7-methylfluoran,
3,3-Bis-(4'-dimethylaminophenyl)-6-aminophthalid,
3,3-Bis-(4'-ethylaminophenyl)-6-dimethylaminophthalid.Specific examples of such components (B) are:
2-amino-3-chloro-6-diethylaminofluoran
2-amino-6-dibutylaminofluoran
6-amino-3-chlorofluorane
2-amino-6-diethylaminofluoran
2-methylamino-6-dimethylaminofluoran
2-ethylamino-6-diethylaminofluoran
2-methylamino-6-diethylaminofluoran
2-n-butylamino-6-diethylaminofluoran
2-n-octylamino-6-diethylaminofluoran
2 sec butylamino-6-diethylaminofluoran
2-benzylamino-6-diethylaminofluoran
2,3-dimethyl-6-ethylaminofluoran
2,3,7-trimethyl-6-ethylaminofluoran
2,3,7-trimethyl-6-ethylamino-5 '(6') - tert.butylfluorane
2-chloro-3,7-dimethyl-6-ethylamino-5 '(6') - tert.butylfluorane
2-tert-butyl-6-ethylamino-7-methyl-5 '(6') - tert.butylfluorane
3-chloro-6-cyclohexylaminofluoran,
2,7-dimethyl-3,6-bis-ethylaminofluoran,
2- (2'-chloroanilino-6-ethylamino-7-methylfluorane,
3,3-bis (4'-dimethylaminophenyl) -6-aminophthalide,
3,3-bis (4'-ethylaminophenyl) -6-dimethylaminophthalide.

Die Mengenverhältnisse, in denen Komponenten (A) und (B) verwendet werden, sind nicht kritisch, jedoch verwendet man sie vorzugsweise in stöchiometrischen Mengen.The proportions in which components (A) and (B) are used are not critical, but are preferably used in stoichiometric amounts.

Sowohl Komponente (A) als auch Komponenten (B) können entweder einzeln oder in Form einer Kombination von zwei oder mehrerer derselben verwendet werden.Both component (A) and component (B) can be used either individually or in the form of a combination of two or more of them.

Sind die zwei verwendeten Komponenten (B) identisch, so entstehen in der Regel symmetrisch substituierte polycyclische chromogene Verbindungen. Werden hingegen zwei voneinander verschiedene Komponenten (B) verwendet, so liefern sie eher unsymmetrisch substituierte chromogene Verbindungen.If the two components (B) used are identical, symmetrically substituted polycyclic chromogenic compounds are generally formed. If, on the other hand, two different components (B) are used, they provide asymmetrically substituted chromogenic compounds.

Als Komponente (C) können anorganische oder organische, für Aufzeichnungsmaterialien bekannte Farbentwickler, die fähig sind Elektronen anzuziehen (Elektronenakzeptoren), verwendet werden.Inorganic or organic color developers known for recording materials and capable of attracting electrons (electron acceptors) can be used as component (C).

Typische Beispiele für anorganische Entwickler sind Aktivton-Substanzen, wie Attapulgus-Ton, Säureton, Bentonit, Montmorillonit; aktivierter Ton z.B. säureaktiviertes Bentonit oder Montmorillonit sowie Halloysit, Kaolin, Zeolith, Siliciumdioxid, Zirkondioxid, Aluminiumoxid, Aluminiumsulfat, Aluminiumphosphat oder Zinknitrat.Typical examples of inorganic developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.

Bevorzugte anorganische Farbentwickler sind Lewis-Säuren, wie z.B. Aluminiumchlorid, Aluminiumbromid, Zinkchlorid, Eisen(III)chlorid, Zinntetrachlorid, Zinndichlorid, Zinntetrabromid, Titantetrachlorid Wismuttrichlorid, Tellurdichlorid oder Antimonpentachlorid.Preferred inorganic color developers are Lewis acids, e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.

Als organische Farbentwickler können feste Carbonsäuren, zweckmässigerweise aliphatische Dicarbonsäuren, wie z.B. Weinsäure, Oxalsäure, Maleinsäure, Zitronensäure, Citraconsäure oder Bernsteinsäure sowie Alkylphenolacetylenharz, Maleinsäure-Kolophonium-Harz, Carboxypolymethylen oder ein teilweise oder vollständig hydrolisiertes Polymerisat von Maleinsäureanhydrid mit Styrol, Ethylen oder Vinylmethylether verwendet werden.Solid organic acids, suitably aliphatic dicarboxylic acids, such as e.g. Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid as well as alkylphenol acetylene resin, maleic acid rosin resin, carboxypolymethylene or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether can be used.

Als organische Farbentwickler eignen sich insbesondere Verbindungen mit einer phenolischen Hydroxylgruppe. Diese können sowohl einwertige als auch mehrwertige Phenole sein. Diese Phenole können durch Halogenatome, Carboxylgruppen, Alkylreste, Aralkylreste, wie α-Methylbenzyl, α,α-Dimethylbenzyl, Arylreste, Acylreste, wie Arylsulfonyl oder Alkoxycarbonylreste oder Aralkoxycarbonylreste, wie Benzyloxycarbonyl substituiert sein.Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be replaced by halogen atoms, carboxyl groups, alkyl radicals, aralkyl radicals, such as α-methylbenzyl, α, α-dimethylbenzyl, Aryl radicals, acyl radicals, such as arylsulfonyl or alkoxycarbonyl radicals, or aralkoxycarbonyl radicals, such as benzyloxycarbonyl, can be substituted.

Spezielle Beispiele für als Komponente (C) geeignete Phenole sind 4-tert.-Butylphenol, 4-Phenylphenol, Methylen-bis-(p-phenylphenol), 4-Hydroxydiphenylether, α-Naphthol, β-Naphthol, 4-Hydroxybenzoesäuremethylester oder -benzylester, 2,4-Dihydroxybenzoesäuremethylester, 4-Hydroxydiphenylsulfon, 4'-Hydroxy-4-methyldiphenylsulfon, 4'-Hydroxy-4-isopropoxydiphenylsulfon, 4-Hydroxy-acetophenon, 2,4-Dihydroxybenzophenon, 2,2'-Dihydroxydiphenyl, 2,4-Dihydroxydiphenylsulfon, 4,4'-Cyclohexylidendiphenol, 4,4'-Isopropylidendiphenol, 4,4'-Isopropyliden-bis-(2-methylphenol), 4,4-Bis-(4-hydroxyphenyl)valeriansäure, Resorcin, Hydrochinon, Pyrogallol, Phloroglucin, p-, m-, o-Hydroxybenzoesäure, Hydroxyphthalsäure, 3,5-Di-(α-methylbenzyl)-salicylsäure, 3,5-Di-(α,α-dimethylbenzyl)salicylsäure, Salicylosalicylsäure, Gallussäurealkylester, Gallussäure, 1-Hydroxy-2-naphthoesäure oder Phenol-Formaldehyd-Vorpolymerisate (Novolaks), die auch mit Zink modifiziert sein können. Von den aufgezählten Carbonsäuren sind die Salicylsäurederivate bevorzugt, die vorzugsweise als Zinksalze eingesetzt werden. Besonders bevorzugte Zinksalicylate sind in EP-A-181283 oder DE-A-2242250 beschrieben.Specific examples of phenols suitable as component (C) are 4-tert-butylphenol, 4-phenylphenol, methylene-bis (p-phenylphenol), 4-hydroxydiphenyl ether, α-naphthol, β-naphthol, 4-hydroxybenzoic acid methyl ester or benzyl ester , 2,4-dihydroxybenzoic acid methyl ester, 4-hydroxydiphenyl sulfone, 4'-hydroxy-4-methyldiphenyl sulfone, 4'-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-acetophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxydiphenyl, 2, 4-dihydroxydiphenyl sulfone, 4,4'-cyclohexylidene diphenol, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4-bis- (4-hydroxyphenyl) valeric acid, resorcinol, hydroquinone, Pyrogallol, phloroglucin, p-, m-, o-hydroxybenzoic acid, hydroxyphthalic acid, 3,5-di- (α-methylbenzyl) -salicylic acid, 3,5-di- (α, α-dimethylbenzyl) salicylic acid, salicylosalicylic acid, gallic acid alkyl ester, gallic acid , 1-hydroxy-2-naphthoic acid or phenol-formaldehyde prepolymers (novolaks), which can also be modified with zinc. Of the carboxylic acids listed, the salicylic acid derivatives are preferred, which are preferably used as zinc salts. Particularly preferred zinc salicylates are described in EP-A-181283 or DE-A-2242250.

Gut geeignet als Komponente (C) sind auch organische Komplexe von Zinkthiocyanat und insbesondere ein Antipyrinkomplex von Zinkthiocyanat oder ein Pyridinkomplex von Zinkthiocyanat, wie sie in EP-A-97620 beschrieben sind.Organic complexes of zinc thiocyanate and in particular an antipyrine complex of zinc thiocyanate or a pyridine complex of zinc thiocyanate as described in EP-A-97620 are also very suitable as component (C).

Bevorzugte Komponenten (C) sind Zinksalicylate, zinkmodifizierte Phenolharze (Novolakharze) oder vor allem Aktivtone.Preferred components (C) are zinc salicylates, zinc-modified phenolic resins (novolak resins) or, above all, active clays.

Die Entwickler können zusätzlich auch im Gemisch mit an sich unreaktiven oder wenig reaktiven Pigmenten oder weiteren Hilfsstoffen wie Kieselgel oder UV-Absorbern, wie z.B. 2-(2'-Hydroxyphenyl-)benztriazolen, Benzophenonen, Cyanoacrylaten, Salicylsäurephenylestern, eingesetzt werden. Beispiele für solche Pigmente sind: Talk, Titandioxid, Aluminiumoxid, Aluminiumhydroxid, Zinkoxid, Kreide, Tone wie Kaolin, sowie organische Pigmente, z.B. Harnstoff-Formaldehydkondensate (BET-Oberfläche 2-75 m²/g) oder Melamin-Formaldehyd-KondensationsprodukteThe developers can also be used in a mixture with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, such as 2- (2'-hydroxyphenyl) benzotriazoles, benzophenones, cyanoacrylates, salicylic acid phenyl esters. Examples of such pigments are: talc, titanium dioxide, aluminum oxide, Aluminum hydroxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, eg urea-formaldehyde condensates (BET surface 2-75 m² / g) or melamine-formaldehyde condensation products

Das Mischungsverhältnis der Komponente (C) zu den Komponenten (A) und (B) hängt von der Art der drei Komponenten, der Art des Farbumschlags, vom Druck bzw. von der Farbreaktionstemperatur und selbstverständlich auch von der gewünschten Farbkonzentration ab. Es werden jedoch zufriedenstellende Ergebnisse erzielt, wenn die farbentwickelnde Komponente (C) in Mengen von 0,1 bis 100 Gew. Teilen pro Teil der Komponenten (A) und (B) zusammen eingesetzt werden.The mixing ratio of component (C) to components (A) and (B) depends on the type of three components, the type of color change, the pressure or the color reaction temperature and of course also on the desired color concentration. However, satisfactory results are obtained when the color developing component (C) is used in an amount of 0.1 to 100 parts by weight per part of the components (A) and (B).

Für das druckempfindliche Aufzeichnungsmaterial werden sowohl Komponente (A) als auch Komponenten (B) vorzugsweise gemeinsam oder auch getrennt in einem organischen Lösungsmittel gelöst und die erhaltenen Lösungen werden zweckmässigerweise eingekapselt nach Verfahren, wie z.B. in den U.S. Patentschriften 2 712 507, 2 800 457, 3 016 308, 3 429 827 und 3 578 605 oder in den britischen Patentschriften 989 264, 1 156 725, 1 301 052 oder 1 355 124 beschrieben werden. Ebenfalls geeignet sind Mikrokapseln, welche durch Grenzflächenpolymerisation gebildet werden, wie z.B. Kapseln aus Polyester, Polycarbonat, Polysulfonamid, Polysulfonat, besonders aber aus Polyamid oder Polyurethan. In manchen Fällen genügt, dass lediglich Komponente (A) eingekapselt wird. Die Einkapselung ist in der Regel erfoderlich um Komponenten (A) und (B) von Komponente (C) zu trennen und somit eine frühzeitige Aktivierung zu verhindern. Letzteres kann auch erzielt werden, indem man Komponenten (A) und (B) in schaum-, schwamm-oder bienenwabenartigen Strukturen einarbeitet.For the pressure-sensitive recording material, both component (A) and component (B) are preferably dissolved together or separately in an organic solvent and the solutions obtained are expediently encapsulated by processes such as e.g. in the U.S. Patents 2,712,507, 2,800,457, 3,016,308, 3,429,827 and 3,578,605 or in British Patents 989,264, 1,156,725, 1,301,052 or 1,355,124. Microcapsules formed by interfacial polymerization, such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane. In some cases it is sufficient that only component (A) is encapsulated. The encapsulation is usually required to separate components (A) and (B) from component (C) and thus prevent early activation. The latter can also be achieved by incorporating components (A) and (B) into foam, sponge or honeycomb structures.

Beispiele für geeignete Lösungsmittel sind vorzugsweise nichtflüchtige Lösungsmittel z.B. halogeniertes Benzol, Diphenyle oder Paraffin, wie z.B. Chlorparaffin, Trichlorbenzol, Monochlordiphenyl, Dichlordiphenyl, oder Trichlordiphenyl; Ester, wie z.B. Dibutyladipat, Dibutylphthalat, Dioctylphthalat, Butylbenzyladipat, Trichlorethylphosphat, Trioctylphosphat, Tricresylphosphat; aromatische Ether wie Benzylphenylether; Kohlenwasserstofföle, wie Parrafinöl oder Kerosin, z.B. mit Isopropyl, Isobutyl, sek.-Butyl oder tert.-Butyl alkylierte Derivate von Diphenyl, Naphthalin oder Terphenyl, Dibenzyltoluol, partiell hydriertes Terphenyl, mono- bis tetra-C₁-C₃-alkylierte Diphenylalkane, Dodecylbenzol, benzylierte Xylole, oder weitere chlorierte oder hydrierte, kondensierte, aromatische Kohlenwasserstoffe. Oft werden Mischungen verschiedener Lösungsmittel, insbesondere Mischungen aus Paraffinölen oder Kerosin und Diisopropylnaphthalin oder partiell hydriertem Terphenyl, eingesetzt, um eine optimale Löslichkeit für die Farbbildung, eine rasche und intensive Färbung und eine für die Mikroverkapselung günstige Viskosität zu erreichen.Examples of suitable solvents are preferably non-volatile solvents, for example halogenated benzene, diphenyls or paraffin, such as, for example, chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters such as dibutyl adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl adipate, trichloroethyl phosphate, trioctyl phosphate, tricresyl phosphate; aromatic ethers such as benzylphenyl ether; Hydrocarbon oils, such as paraffin oil or kerosene, for example derivatives of diphenyl alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl, Naphthalene or terphenyl, dibenzyltoluene, partially hydrogenated terphenyl, mono- to tetra-C₁-C₃-alkylated diphenylalkanes, dodecylbenzene, benzylated xylenes, or other chlorinated or hydrogenated, condensed, aromatic hydrocarbons. Mixtures of various solvents, in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.

Die Komponenten (A) und (B) enthaltenden Mikrokapseln können zur Herstellung von druckempfindlichen Kopiermaterialien der verschiedensten bekannten Arten verwendet werden. Die verschiedenen Systeme unterscheiden sich im wesentlichen durch die Anordnung der Kapseln, der Farbreaktanten und durch das Trägermaterial voneinander.Microcapsules containing components (A) and (B) can be used to produce pressure-sensitive copying materials of various known types. The different systems differ essentially in the arrangement of the capsules, the color reactants and the carrier material.

Vorteilhaft ist eine Anordnung, bei der eingekapselte Komponenten (A) und (B) in Form einer Schicht auf der Rückseite eines Uebertragungsblattes und der Elektronenakzeptor (Komponente (C)) in Form einer Schicht auf der Vorderseite eines Empfangsblattes vorhanden sind. Eine andere Anordnung der Bestandteile besteht darin, dass die Komponenten (A) und (B) enthaltenden Mikrokapseln und der Entwickler (Komponente (C)) in oder auf dem gleichen Blatt in Form einer oder mehrerer Einzelschichten oder in der Papierpulpe vorliegen.An arrangement is advantageous in which encapsulated components (A) and (B) are present in the form of a layer on the back of a transfer sheet and the electron acceptor (component (C)) in the form of a layer on the front of a receiver sheet. Another arrangement of the components is that the microcapsules containing components (A) and (B) and the developer (component (C)) are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.

Zur Erzielung der gewünschten Farbe, kann die Kapselmasse, welche die Komponenten A und B enthält, mit weiteren Kapseln, welche konventionelle Farbbildner enthalten, vermischt werden. Aehnliche Resultate werden erzielt, wenn man die Komponenten A und B gemeinsam mit einem oder mehreren der konventionellen Farbbildner einkapsuliert.To achieve the desired color, the capsule mass, which contains components A and B, can be mixed with further capsules, which contain conventional color formers. Similar results are obtained if components A and B are encapsulated together with one or more of the conventional color formers.

Die Kapseln werden vorzugsweise mittels eines geeigneten Binders auf dem Träger befestigt. Da Papier das bevorzugte Trägermaterial ist, handelt es sich bei diesem Binder hauptsächlich um Papierbeschichtungsmittel, wie z.B. Gummi arabicum, Polyvinylalkohol, Hydroxymethylcellulose, Casein, Methylcellulose, Dextrin, Stärke, Stärkederivate oder Polymerlatices. Letztere sind beispielsweise Butadien-Styrolcopolymerisate oder Acrylhomo- oder -copolymere.The capsules are preferably attached to the carrier by means of a suitable binder. Since paper is the preferred carrier material, this binder is mainly paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, Methyl cellulose, dextrin, starch, starch derivatives or polymer latices. The latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.

Als Papier werden nicht nur normale Papiere aus Cellulosefasern, sondern auch Papiere, in denen die Cellulosefasern (teilweise oder vollständig) durch Fasern aus synthetischen Polymerisaten ersetzt sind, verwendet. Schichtträger kann auch eine Kunststoffolie sein.The paper used is not only normal paper made from cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers. The substrate can also be a plastic film.

Vorzugsweise besteht das Durchschreibematerial auch darin, dass es eine kapselfreie, Komponenten (A) und (B) enthaltende Schicht und eine farbentwickelnde Schicht, die als Farbentwickler (Komponente (C)) mindestens ein anorganisches Metallsalz vor allem Halogenide oder Nitrate, wie z.B. Zinkchlorid, Zinnchlorid, Zinknitrat oder deren Gemische enthält, aufweist.The carbonless material preferably also consists of a capsule-free layer containing components (A) and (B) and a color-developing layer which, as color developer (component (C)), comprises at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.

Das erfindungsgemäss verwendete ternäre Farbbildungssystem aus Komponenten (A), (B) und (C) eignet sich auch zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials für die Thermographie, wobei die Komponenten (A), (B) und (C) beim Erhitzen miteinander unter Farbbildung in Berührung kommen und Aufzeichnungen auf dem Trägermaterial hinterlassen.The ternary color image system comprising components (A), (B) and (C) used according to the invention is also suitable for producing a heat-sensitive recording material for thermography, components (A), (B) and (C) being heated together to form a color in Come into contact and leave records on the carrier material.

Das wärmeempfindliche Aufzeichnungsmaterial enthält in der Regel mindestens einen Schichtträger, Komponenten (A), (B) und (C) und gegebenenfalls auch ein Bindemittel und/oder Wachs. Gewünschtenfalls können auch Aktivatoren oder Sensibilisatoren im Aufzeichnungsmaterial vorhanden sein.The heat-sensitive recording material generally contains at least one layer support, components (A), (B) and (C) and optionally also a binder and / or wax. If desired, activators or sensitizers can also be present in the recording material.

Thermoreaktive Aufzeichnungssysteme umfassen, z.B. wärmeempfindliche Aufzeichnungs- und Kopiermaterialien und -papiere. Diese Systeme werden beispielsweise zum Aufzeichnen von Informationen, z.B. in elektronischen Rechnern, Ferndruckern, Fernschreibern oder in Aufzeichnungsgeräten und Messinstrumenten, wie z.B. Elektrocardiographen, verwendet. Die Bilderzeugung (Markierung) kann auch manuell mit einer erhitzten Feder erfolgen. Eine weitere Einrichtung zur Erzeugung von Markierungen mittels Wärme sind Laserstrahlen.Thermoreactive recording systems include, for example, heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, for example in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, such as, for example, electrocardiographs. The imaging (marking) can also be done manually with a heated spring. Another device for generating markings using heat is laser beams.

Das thermoreaktive Aufzeichnungsmaterial kann so aufgebaut sein, dass Komponenten (A) und (B) in einer Bindemittelschicht gelöst oder dispergiert sind und in einer zweiten Schicht der Entwickler (Komponente (C)) in dem Bindemittel gelöst und dispergiert ist. Eine andere Möglichkeit besteht darin, dass alle Komponenten in derselben Schicht dispergiert sind. Die Schicht bzw. Schichten werden in spezifischen Bezirken mittels Wärme erweicht oder verschmolzen, worauf sich sofort in den erwärmten Teilen die erwünschte Farbe entwickelt.The thermoreactive recording material can be constructed such that components (A) and (B) are dissolved or dispersed in a binder layer and in a second layer the developer (component (C)) is dissolved and dispersed in the binder. Another possibility is that all components are dispersed in the same layer. The layer or layers are softened or fused in specific areas by means of heat, whereupon the desired color develops immediately in the heated parts.

Vorzugsweise werden zur Herstellung des wärmeempfindlichen Aufzeichnungsmaterials schmelzbare, filmbildende Bindemittel verwendet. Diese Bindemittel sind normalerweise wasserlöslich, während Komponenten (A), (B) und (C) in Wasser unlöslich sind. Das Bindemittel sollte in der Lage sein, alle Komponenten bei Raumtemperatur zu dispergieren und auf dem Schichtträger zu fixieren.Fusible, film-forming binders are preferably used to produce the heat-sensitive recording material. These binders are normally water soluble, while components (A), (B) and (C) are insoluble in water. The binder should be able to disperse all components at room temperature and fix them on the substrate.

Wasserlösliche oder mindestens in Wasser quellbare Bindemittel sind z.B. hydrophile Polymerisate, wie Polyvinylalkohol, Polyacrylsäure, Hydroxyethylcellulose, Methylcellulose, Carboxymethylcellulose, Polyacrylamid, Polyvinylpyrrolidon, carboxylierte Butadien-Styrolcopolymerisate, Gelatine, Stärke oder veresterte Maisstärke.Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.

Wenn Komponenten (A), (B) und (C) in zwei, drei oder je nach Komponenten (B) auch vier getrennten Schichten vorliegen, können in Wasser unlösliche Bindemittel, d.h. in nichtpolaren oder nur schwach polaren Lösungsmitteln lösliche Bindemittel, wie z.B. Naturkautschuk, synthetischer Kautschuk, chlorierter Kautschuk, Alkydharze, Polystyrol, Styrol/Butadien-Mischpolymerisate, Polymethylacrylate, Ethylcellulose, Nitrocellulose und Polyvinylcarbazol, verwendet werden. Die bevorzugte Anordnung ist jedoch diejenige, bei der alle Komponenten in einer Schicht in einem wasserlöslichen Bindemittel enthalten sind.If components (A), (B) and (C) are present in two, three or, depending on component (B), four separate layers, water-insoluble binders, i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used. However, the preferred arrangement is one in which all of the components are contained in a layer in a water-soluble binder.

Um die Stabilität des wärmeempfindlichen Aufzeichnungsmaterials oder die Bilddichte des entwickelten Bildes zu gewährleisten, kann das Material mit einer zusätzlichen Schutzschicht versehen sein. Derartige Schutz schichten bestehen in der Regel aus wasserlöslichen und/oder wasserunlöslichen Harzen, die herkömmliche Polymermaterialien oder wässrige Emulsionen von diesen Polymermaterialien sind.In order to ensure the stability of the heat-sensitive recording material or the image density of the developed image, the material can be provided with an additional protective layer. Such protection Layers usually consist of water-soluble and / or water-insoluble resins, which are conventional polymer materials or aqueous emulsions of these polymer materials.

Spezielle Beispiele für wasserlösliche Polymermaterialien sind Polyvinylalkohol, Stärke, Stärkederivate, Cellulosederivate, wie Methoxycellulose, Hydroxyethylcellulose, Carboxymethylcellulose, Methylcellulose oder Ethylcellulose, Natriumpolyacrylat, Polyvinylpyrrolidon, Polyacrylamid/Acrylsäureester-Copolymere, Acrylamid/Acrylsäureester/Methacrylsäure-Copolymere, Styrol/Maleinsäureanhydrid-Copolymer-Alkalisalze, Isobuten/Maleinsäureanhydrid-Copolymer-Alkalisalze, Polyacrylamid, Natriumalginat, Gelatine, Casein, wasserlösliche Polyester oder Carboxylmodifizierter Polyvinylalkohol.Specific examples of water-soluble polymer materials are polyvinyl alcohol, starch, starch derivatives, cellulose derivatives, such as methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose or ethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, polyacrylamide / acrylic acid ester copolymers, acrylamide / acrylic acid ester / methacrylic acid / copolymeric acid-alkali acid-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, stearic acid-copolymeric acid, and / or , Isobutene / maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, casein, water-soluble polyester or carboxyl-modified polyvinyl alcohol.

Gegebenenfalls können in der Schutzschicht in Kombination mit den genannten wasserlöslichen Polymerharzen z.B. die folgenden wasserunlöslichen Harze angewandt werden: Polyvinylacetat, Polyurethane, Styrol/Butadien-Copolymere, Polyacrylsäure, Polyacrylsäureester, Vinylchlorid/Vinylacetat-Copolymere, Polybutylmethacrylat, Ethylen/Vinylacetat-Copolymere und Styrol/Butadien/Acrylderivate-Copolymere.If necessary, in the protective layer in combination with the water-soluble polymer resins mentioned, e.g. the following water-insoluble resins are used: polyvinyl acetate, polyurethanes, styrene / butadiene copolymers, polyacrylic acid, polyacrylic acid esters, vinyl chloride / vinyl acetate copolymers, polybutyl methacrylate, ethylene / vinyl acetate copolymers and styrene / butadiene / acrylic derivative copolymers.

Sowohl die thermoreaktiven Schichten als auch die Harzschichten können weitere Zusätze enthalten. Zur Verbesserung des Weissgrades oder der Thermokopfeignung des Aufzeichnungsmaterials und zur Verhinderung des Festklebens der erhitzten Feder oder Platte können diese Schichten, z.B. Antioxidantien, UV-Absorber, Lösungshilfen, Talk, Titandioxyd, Zinkoxyd, Aluminiumoxyd, Aluminiumhydroxyd, Calciumcarbonat (z.B. Kreide), Magnesiumcarbonat, Tone oder auch organische Pigmente, wie z.B. Harnstoff-Formaldehydpolymerisate, enthalten. Um zu bewirken, dass nur innerhalb eines begrenzten Temperaturbereiches die Farbe gebildet wird, können Substanzen, wie Harnstoff, Thioharnstoff, Diphenylthioharnstoff, Acetamid, Acetanilid, Benzolsulfanilid, Bis-stearoylethylendiamid, Stearinsäureamid, Phthalsäureanhydrid, Benzyloxybenzoesäurebenzylester, Metallstearate, wie z.B. Zinkstearat, Phthalsäurenitril, Dimethylterephthalat, Dibenzylisophthalat, Dibenzylterephthalat, Benzyldiphenyl oder andere entsprechende, schmelzbare Produkte, welche das gleichzeitige Schmelzen der Farbbildnerkomponenten und des Entwicklers induzieren, zugesetzt werden.Both the thermoreactive layers and the resin layers can contain further additives. To improve the whiteness or the thermal head suitability of the recording material and to prevent the heated spring or plate from sticking, these layers, for example antioxidants, UV absorbers, solvents, talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (eg chalk), magnesium carbonate, Contain clays or organic pigments, such as urea-formaldehyde polymers. In order to ensure that the color is formed only within a limited temperature range, substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid, benzate, methyl ester, benzate metal, eg, benzate, benzate, for example, benzate, benzylate, for example, benzate, zalatesilate, eg , Dibenzyl isophthalate, dibenzyl terephthalate, benzyldiphenyl or others corresponding, meltable products which induce the simultaneous melting of the color former components and the developer are added.

Bevorzugt enthalten thermographische Aufzeichnungsmaterialien Wachse, z.B. Carnaubawachs, Montanwachs, Paraffinwachs, Polyethylenwachs, Kondensate höherer Fettsäureamide und Formaldehyd oder Kondensate höherer Fettsäuren und Ethylendiamin.Thermographic recording materials preferably contain waxes, e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.

Zur Verbesserung der Verwendbarkeit der thermochromatischen Materialien können Komponenten (A), (B) und (C) in Mikrokapseln eingeschlossen sein. Dazu können beliebige obengenannte an sich bekannte Verfahren zum Einschliessen von Farbbildnern oder anderen Wirkstoffen in Mikrokapseln verwendet werden.To improve the usability of the thermochromatic materials, components (A), (B) and (C) can be enclosed in microcapsules. Any of the methods known per se for enclosing color formers or other active substances in microcapsules can be used for this purpose.

In den folgenden Beispielen sind Teile Gewichtsanteile.In the following examples, parts are parts by weight.

Beispiel 1:Example 1:

Zur Herstellung einer Lösung A werden 1,0 g 3,3-Dichlorphthalid in 50 ml Toluol bei 25°C gelöst.To prepare solution A, 1.0 g of 3,3-dichlorophthalide is dissolved in 50 ml of toluene at 25 ° C.

Zur Herstellung einer Lösung B werden 2 g 2-Phenylindol in 50 ml Toluol bei 50°C gelöst.To prepare solution B, 2 g of 2-phenylindole are dissolved in 50 ml of toluene at 50.degree.

Alsdann streicht man mit einem 10 µm Rakel die Lösung B auf ein Blatt Papier, das auf der Vorderseite mit säuremodifiziertem Bentonit als Farbentwickler beschichtet ist (CF-Blatt). Anschliessend wird auch die Lösung A gestrichen, wobei sich sogleich eine schwarze Farbe entwickelt, die ausgezeichnet lichtecht ist.Then, using a 10 µm doctor blade, spread solution B on a sheet of paper which is coated on the front with acid-modified bentonite as a color developer (CF sheet). Then solution A is also streaked, a black color developing immediately which is outstandingly lightfast.

Beispiel 2:Example 2:

Die gemäss Beispiel 1 hergestellten Lösungen A und B werden in Gewichtsverhältnis 1:1 gemischt und auf der Vorderseite des mit säuremodifizierten Bentonit beschichteten Blatt Papiers gestrichen, wobei sich sogleich eine schwarze Farbe entwickelt.Solutions A and B prepared according to Example 1 are mixed in a weight ratio of 1: 1 and coated on the front of the sheet of paper coated with acid-modified bentonite, a black color immediately developing.

Beispiel 3:Example 3:

Verwendet man in Beispiel 1 anstelle der Lösung B eine Lösung C von 2 g 1-Methyl-2-phenylindol und verfährt ansonsten wie in Beispiel 1 beschrieben, so erhält man auf der Frontseite des mit säuremodifizierten Bentonit beschichteten Papiers eine violette Farbe.If, instead of solution B, a solution C of 2 g of 1-methyl-2-phenylindole is used in Example 1 and the procedure is otherwise as described in Example 1, a violet color is obtained on the front of the paper coated with acid-modified bentonite.

Beispiel 4:Example 4:

2 g 2-Phenylindol werden in 35 g Toluol bei 50°C gelöst. 1 g 3,3-Dichlorphthalid werden in 22 g Toluol bei 25°C gelöst. Man vermischt die beiden Lösungen und gibt unter Rühren 12 g Polyvinylacetat, 8 g Calciumcarbonat und 2 g Titandioxid zu. Die erhaltene Suspension wird mit einem 10 µm Rakel auf ein Blatt Papier gestrichen. Auf dieses Blatt Papier wird ein zweites Blatt Papier gelegt, dessen Unterseite bei einem Auftragsgewicht von 3 g/m² mit einer Mischung bestehend aus 1 Teil eines Amidwachses, 1 Teil eines Stearinwachses und 1 Teil Zinkchlorid beschichtet ist. Durch Schreiben mit der Hand oder mit der Schreibmaschine auf dem oberen Blatt wird Druck ausgeübt. Auf dem mit Lösungen beschichteten Blatt entwickelt sich eine violette Farbe.2 g of 2-phenylindole are dissolved in 35 g of toluene at 50 ° C. 1 g of 3,3-dichlorophthalide is dissolved in 22 g of toluene at 25 ° C. The two solutions are mixed and 12 g of polyvinyl acetate, 8 g of calcium carbonate and 2 g of titanium dioxide are added with stirring. The suspension obtained is spread on a sheet of paper using a 10 μm doctor blade. A second sheet of paper is placed on this sheet of paper, the underside of which is coated with a mixture consisting of 1 part of an amide wax, 1 part of a stearic wax and 1 part of zinc chloride at an application weight of 3 g / m². Pressure is applied by hand or typewriter on the top sheet. A violet color develops on the sheet coated with solutions.

Beispiel 5:Example 5:

100 mg 3,3-Dichlorphthalid und 129 mg 2-Methylindol werden zusammen in 10 ml Diisopropylnaphthalin gelöst und mittels einer Tiefdruckplatte auf ein mit säuremodifiziertem Ton beschichtetes Papier aufgebracht. Es entwickelt sich eine lichtechte, rote Farbe.100 mg of 3,3-dichlorophthalide and 129 mg of 2-methylindole are dissolved together in 10 ml of diisopropylnaphthalene and applied to paper coated with acid-modified clay using a gravure printing plate. A lightfast, red color develops.

Beispiel 6:Example 6:

100 mg 3,3-Dichlorphthalid und 171 mg 3-Methyl-6-dimethylaminoindol werden zusammen in 10 ml Diisopropylnaphthalin gelöst und mittels einer Tiefdruckplatte auf ein mit säuremodifizierten Ton beschichtetes Papier aufgebracht. Es entwickelt sich eine lichtechte dunkelviolette Farbe. Die Färbung zeigt Absorption bis in den NIR-Bereich.100 mg of 3,3-dichlorophthalide and 171 mg of 3-methyl-6-dimethylaminoindole are dissolved together in 10 ml of diisopropylnaphthalene and applied to a paper coated with acid-modified clay by means of a gravure printing plate. A lightfast dark purple color develops. The color shows absorption up to the NIR range.

Beispiel 7:Example 7:

100 mg 3,3-Dichlorphthalid und 249 mg 1-(4-Dimethylaminophenyl)-1-(4-methoxyphenyl)-ethylen werden zusammen in 10 ml Diisopropylnaphthalin gelöst und mittels einer Tiefdruckplatte auf ein mit säuremodifiziertem Ton beschichtetes Papier aufgebracht. Es entwickelt sich eine lichtechte violette Farbe.100 mg of 3,3-dichlorophthalide and 249 mg of 1- (4-dimethylaminophenyl) -1- (4-methoxyphenyl) ethylene are dissolved together in 10 ml of diisopropylnaphthalene and applied to a paper coated with acid-modified clay by means of a gravure printing plate. A lightfast violet color develops.

Beispiel 8:Example 8:

20 mg 3,3-Dichlorphthalid und 100 mg 2-n-Octylamino-6-diethylaminofluoran werden zusammen in 10 ml Diisopropylnaphthalin gelöst und mittels einer Tiefdruckplatte auf ein mit säuremodifizertem Ton beschichtetes Papier aufgebracht. Es entwickelt sich eine rote Farbe.20 mg of 3,3-dichlorophthalide and 100 mg of 2-n-octylamino-6-diethylaminofluoran are dissolved together in 10 ml of diisopropylnaphthalene and applied to a paper coated with acid-modified clay by means of a gravure printing plate. A red color develops.

Claims (26)

  1. A pressure-sensitive or heat-sensitive recording material in which the colour reactant system contains, as essential components,
    (A) an electron-donating compound of the formula
    Figure imgb0013
     in which Y₁ and Y₂ are substituents which are detachable as anions and can be identical, different or bound to one another and Q₁ is -O-, -S-, 〉N-R or 〉N-NH-R, Q₂ is -CH₂-, -CO-, -CS- or SO₂- and R is hydrogen, C₁-C₁₂alkyl, aryl or aralkyl and ring A is an aromatic radical which has 6 ring atoms and can contain an aromatic fused ring, it being possible not only for ring A but also for the fused ring to be substituted,
    (B) two organic condensation components which are identical to or different from one another and together are capable of forming a chromogenic compound with component (A) and
    (C) an electron-withdrawing and colour-developing component.
  2. A recording material according to claim 1, where Y₁ and Y₂ in formula (1), independently of one another, are each halogen, an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether group or an acyloxy group.
  3. A recording material according to any one of claims 1 and 2, wherein Y₁ and Y₂ in formula (1) are halogen.
  4. A recording material according to any one of claims 1 to 3, wherein in formula (1) Q₁ is oxygen and Q₂ is -CO-.
  5. A recording material according to any one of claims 1 to 4, wherein ring A in formula (1) is a substituted or unsubstituted benzene, naphthaline, or phenanthrene ring.
  6. A recording material according to claim 1, wherein component (A) is a lactone compound of the formula
    Figure imgb0014
     in which A₁ is a benzene ring which is unsubstituted or substituted by halogen, cyano, lower alkyl, lower alkylthio, lower alkoxy or lower dialkylamino and Y₃ and Y₄, independently of one another, are acyloxy or halogen and in particular chlorine or bromine.
  7. A recording material according to claim 6, wherein in formula (2) Y₃ and Y₄ are halogen and ring A₁ is a benzene ring which is unsubstituted or substituted by halogen, lower alkyl, lower alkoxy or lower dialkylamino.
  8. A recording material according to claim 1, wherein component (A) is a lactone compound of the formula
    Figure imgb0015
     in which ring B is unsubstituted or substituted by lower alkyl, lower dialkylamino or 1 to 4 chlorine atoms and Y₅ and Y₆ are bromine or chlorine.
  9. A recording material according to claim 1, wherein component (A) is 3,3-dichlorophthalide or 3,3-dibromophthalide.
  10. A recording material according to any one of claims 1 to 9, wherein components (B) are at least two compounds which are identical or different from one another and come from the series of unsubstituted or C-substituted anilines, N-substituted anilines, C- and N-substituted anilines, diarylamines, naphthylamines, N-substituted aminophenylethylene compounds, N-substituted aminophenylstyrene compounds, acylacetarylamides, monohydric or polyhydric phenols, phenol ethers, naphthols, naphtholcarboxanilides, 3-aminophenol ethers, aminopyrazoles, aminothiazoles, pyrazolones, pyridones, pyrroles, thiophenes, quinolones, pyrimidones, barbituric acids, indoles, carbazoles, acridines, benzofurans, benzothiophenes, naphthothiophenes, phenothiazines, pyrrolidines, piperidines, piperazines, morpholines, benzomorpholines, indolines, dihydroquinolines, tetrahydroquinolines, kairolines or julolidines.
  11. A recording material according to any one of claims 1 to 10, wherein components (B) comprise at least two compounds which are identical to or different from one another and have the formula
    Figure imgb0016
     or
    the formula
    Figure imgb0017
     in which R₁ and R₂, independently of one another, are each hydrogen, alkyl which is unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy and has a maximum number of 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or phenalkyl or phenyl which is unsubstituted or ring-substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X'' or 4-NX'X''-phenylamino in which X' and X'', independently of one another, are hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R₁ and R₂ together with the nitrogen atom which links them are a five- or six-membered heterocyclic radical, V is hydrogen, halogen, lower alkyl, C₁-C₁₂alkoxy, C₁-C₁₂acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, halogen-, cyano-, lower alkyl- or lower alkoxy-substituted benzyl or benzyloxy, or the group -NT₁T₂ and T₁ and T₂, independently of one another, are each hydrogen, lower alkyl, C₅-C₁₀cycloalkyl, unsubstituted or halogen-, cyano-, lower alkyl- or lower alkoxy-substituted benzyl, or acyl having 1 to 8 carbon atoms and T₁ is also unsubstituted or halogen-, cyano-, lower alkyl- or lower alkoxy-substituted phenyl, m is 1 or 2, Z₁ is hydrogen, unsubstituted or halogen-, hydroxyl-, cyano- or lower alkoxy-substituted alkyl having a maximum number of 12 carbon atoms, acyl having 1 to 12 carbon atoms or unsubstituted or halogen-, cyano-, lower alkyl- or lower alkoxy-substituted benzyl, Z₂ is hydrogen, lower alkyl or phenyl and Z₂' is lower alkyl, cyclohexyl, benzyl or phenyl and the benzene ring D is unsubstituted or substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, amino, lower monoalkylamino or lower dialkylamino.
  12. A recording material according to claim 11, wherein the group
    Figure imgb0018
     in formula (4) is in the para-position relative to H.
  13. A recording material according to any one of claims 1 to 12, wherein components (B) comprise two identical aniline compounds of the formula (4) or indole compounds of the formula (5a) or (5b).
  14. A recording material according to any one of claims 11 to 13, wherein R₁ and R₂ in formula (4) are each lower alkyl, cyclohexyl, tolyl, benzyl, phenethyl or cyano-lower alkyl.
  15. A recording material according to any one of claims 11 to 14, wherein in formula (4) V is hydrogen, halogen, lower alkyl, C₁-C₈alkoxy, benzyloxy or -NT₁T₂, in which T₁ is lower alkyl or C₁-C₈acyl and T₂ is hydrogen or lower alkyl.
  16. A recording material according to any one of claims 11 and 13, wherein in formula (5a) Z is hydrogen, C₁-C₈alkyl, acetyl, propionyl or benzyl and Z₂ is methyl or phenyl.
  17. A recording material according to any one of claims 1 to 9, wherein at least one component B is a fluoran or phthalide compound which contains at least one amino group which is unsubstituted or monosubstituted by lower alkyl, cyclohexyl or benzyl.
  18. A recording material according to any one of claims 1 to 17, wherein component (C) is an acid clay, a Lewis acid, a solid carboxylic acid or a compound having a phenolic hydroxyl group.
  19. A recording material according to any one of claims 1 to 18, which is pressure-sensitive.
  20. A recording material according to claim 19, wherein components (A) and (B), independently of one another, are dissolved in an organic solvent.
  21. A recording material according to claim 20, wherein components (A) and (B), independently of one another, are microencapsulated.
  22. A recording material according to any one of claims 19 to 21, wherein components (A) and (B) are present in the form of one or two layers on the reverse side of a transfer sheet and component (C) is present in the form of a layer on the front of a receptor sheet.
  23. A recording material according to any one of claims 19 to 22, wherein component (C) is a zinc salicylate, a zinc-modified phenol-formaldehyde resin or an acid clay.
  24. A thermoreactive recording material according to any one of claims 1 to 18, which has 1 to 4 layers on a substrate in which components (A), (B) and (C) and, if necessary, a binder and/or wax are present.
  25. A recording material according to any one of claims 1 to 24, wherein the colour-forming components (A) and (B) are present together with one or several conventional colour formers.
  26. A recording material according to claim 25, wherein the conventional colour formers present are 3,3-bis(aminophenyl)phthalides, 3-indolyl-3-aminophenylaza - or -diazaphthalides, 3,3-bis(indolyl)phthalides, 3-aminofluorans, 6-dialkylamino-2-dibenzylaminofluorans, 6-dialkylamino-3-methyl-2-arylaminofluorans, 3,6-bisalkoxyfluorans, 3,6-bis (diarylamino)fluorans, leukoauramines, spiropyrans, spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes.
EP89810944A 1988-12-21 1989-12-12 Pressure-sensitive or heat-sensitive recording material Expired - Lifetime EP0377406B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH471488 1988-12-21
CH4714/88 1988-12-21

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EP0377406B1 true EP0377406B1 (en) 1993-06-09

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Publication number Priority date Publication date Assignee Title
EP0432091A1 (en) * 1989-11-21 1991-06-12 Ciba-Geigy Ag Heat sensitive recording material
DE59106793D1 (en) * 1990-03-29 1995-12-07 Ciba Geigy Ag Pressure sensitive recording material.
US7727319B2 (en) * 2006-04-19 2010-06-01 Crayola Llc Water-based ink system
US7815723B2 (en) * 2006-04-19 2010-10-19 Crayola Llc Water-based ink system
US9399716B2 (en) 2013-07-02 2016-07-26 Chromatic Technologies Inc. Yellow thermochromic dyes, inks composition and level indicators

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Publication number Priority date Publication date Assignee Title
US4251092A (en) * 1976-12-29 1981-02-17 Sterling Drug Inc. Pressure sensitive carbonless duplicating systems and thermal marking systems
US4535172A (en) * 1982-01-08 1985-08-13 The Hilton-Davis Chemical Co. 3(Ether and thioether) 3-(4-dialkylaminophenyl) phthalides
US4688059A (en) * 1982-01-08 1987-08-18 The Hilton-Davis Chemical Co. Marking systems

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DE58904636D1 (en) 1993-07-15
JPH02215580A (en) 1990-08-28
EP0377406A1 (en) 1990-07-11

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