EP0453395B1 - Pressure sensitive recording material - Google Patents

Pressure sensitive recording material Download PDF

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Publication number
EP0453395B1
EP0453395B1 EP91810189A EP91810189A EP0453395B1 EP 0453395 B1 EP0453395 B1 EP 0453395B1 EP 91810189 A EP91810189 A EP 91810189A EP 91810189 A EP91810189 A EP 91810189A EP 0453395 B1 EP0453395 B1 EP 0453395B1
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EP
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Prior art keywords
recording material
material according
compound
component
c6alkyl
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EP91810189A
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German (de)
French (fr)
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EP0453395A1 (en
Inventor
Rudolf Zink
Peter Dr. Möckli
Peter Rohringer
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Novartis AG
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Ciba Geigy AG
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    • 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
    • B41M5/26—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

Definitions

  • US-A-3,174,038 describes a heat-sensitive recording material which comprises (A) a romantic aldehyde compound, (B) an organic condensation component having a primary nitrogen atom and (C) an electron-attracting and color-developing component.
  • Components (A), (B) and (C) come into contact with one another by pressure, 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 such as, for example, yellow, orange, red, violet, blue, green, gray, black or mixed colors, can thus be produced by a corresponding combination of the individual components.
  • components (A) and (B) together with one or more conventional color formers for example 3,3- (bis-aminophenyl -) - phthalides such as CVL, 3-indolyl-3-aminophenylaza- or -diazaphthalides , (3,3-bis-indolyl -) - phthalides, 3-aminofluoranes, 6-dialhylamino-2-dibenzylaminofluoranes, 6-dialkylamino-3-methyl-2-arylaminofluoranes, 3,6-bisalkoxyfluoranes, 3,6-bisdiarylaminofluoranes, Leucoauramines, spiropyrans, spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes
  • substituents R1 and R2 represent alkyl groups, they can be straight-chain or branched.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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 and R2 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 R1 and R2 are cyclopentyl or preferably cyclohexyl.
  • 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.
  • 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 and the phenyl group of R1 and R2 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.
  • the substituents R1 and R2 are preferably cyclohexyl, benzyl, tolyl, phenethyl, C1-C6-alkoxy-C1-C6-alkyl, cyano-C1-C6-alkyl e.g. ⁇ -cyanoethyl or primarily C1-C6 alkyl, e.g. Methyl, ethyl or n-butyl.
  • -NR1R2 is also preferably pyrrolidinyl.
  • R1 and R2 are each C1-C6-alkyl, chloro-C1-C6-alkyl, cyano-C1-C6-alkyl, benzyl, phenyl or R1 and R2 together represent with the common nitrogen atom pyrrolidino, piperidino or morpholino, ar naphthylene or phenylene, which is optionally substituted by hydroxy, halogen, trifluoromethyl, C1-C6-alkyl or C1-C6-alkoxy and n is 1 or 2.
  • the mono- or polynuclear heterocyclic radical Z in formula (3) can be ring-substituted one or more times.
  • the C substituents are e.g. Halogen, hydroxy, cyano, nitro, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkoxycarbonyl, acyl with 1 to 8 carbon atoms, preferably C1-C6-alkylcarbonyl, C1-C6- Alkylamino, C1-C6-alkylcarbonylamino or di-C1-C6-alkylamino, C5-C6-cycloalkyl, benzyl or phenyl in question, while N-substituents for example C1-C12-alkyl, C2-C12-alkenyl, C5-C10-cycloalkyl , C1-C8 acyl, phenyl,
  • the alkyl and alkenyl radicals can be straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylbutyl, t-butyl, sec-butyl, amyl, isopentyl, n-hexyl, 2-ethylhexyl, isooctyl, n-octyl, 1,1 , 3,3-tetramethylbutyl, nonyl, isononyl, 3-ethylheptyl, decyl or n-dodecyl or vinyl, allyl, 2-methylallyl, 2-ethylallyl, 2-butenyl or octenyl.
  • Preferred heterocyclic radicals Z are unsubstituted or substituted 2- or 3-pyrrolyl radicals, 3-indolyl radicals or indolinyl radicals such as e.g. 2-pyrrolyl, N-C1-C8-alkylpyrrol-2-yl-, N-phenylpyrrol-3-yl-, 3-indolyl-, N-C1-C8-alkyl-2-methylindol-3-yl-, N -C2-C4-Alkanoyl-2-methylindol-3-yl, 2-phenylindol-3-yl-, N-C1-C8-alkyl-2-phenylindol-3-yl-, N-C1-C8-alkylcarbazol-3 -yl- or 1,3,3-trimethyl-2-methenyl-indolinyl residues.
  • 2-pyrrolyl N-C1-C8-alkylpyrrol-2-yl-, N-phen
  • Acyl is especially formyl, C1-C6 alkylcarbonyl, such as acetyl or propionyl, or benzoyl.
  • Other acyl radicals can be C1-C6 alkylsulfonyl, such as methylsulfonyl or Ethylsulfonyl and phenylsulfonyl.
  • Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
  • C1-C6-alkyl, C1-C6-alkoxy and C1-C6-alkylthio are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, isoamyl or hexyl or methoxy, ethoxy, isopropoxy , Isobutoxy, tert-butoxy or amyloxy or methylthio, ethylthio, propylthio or butylthio.
  • Halogen means for example fluorine, bromine or preferably chlorine.
  • aldehyde compounds of the formulas (1) and (3) which are suitable as component (A) include 4-dimethylaminobenzaldehyde, 4-N-methyl-N- ⁇ -cyanoethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4- (di- ⁇ -cyanoethylamino) benzaldehyde, 4-di-n-propylaminobenzaldehyde, 4-dibenzylaminobenzaldehyde, 4- (di- ⁇ -hydroxyethylamino) benzaldehyde, 4-N-ethyl-N-benzylaminobenzaldehyde, 4-dimethylamino-2-methylsulfonylbenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 4-morpholinobenzaldehyde, 4- (N- ⁇ -chloroethyl-N-ethy
  • components (B) used according to the invention which form chromogenic compounds with component (A), originate. from the series of anilines, naphthylamines, aminoanilines, anilinesulfonic acid anilides, aminophenylethylene compounds, aminophenylstyrene compounds, acylacetarylamides, 3-aminophenol ethers, aminopyrazoles, aminothiazoles, pyrazolones, barbituric acids, phyrolidines, cyanometholeolines, cyanometholeolines, morpholines, piperomines, cyanometholines, morpholines, piperomines, piperomines have an unsubstituted amino group.
  • Preferred condensation components (B) are anilines, such as cresidines or phenetidines, and also amino-diphenylamines and toluidine sulfonic acid anilides.
  • a V is preferably in the ortho position to the amino group.
  • condensation components (B) are aniline, 2-amino-4-methoxytoluene, 2-amino-4-hydroxy-toluene, 3-amino-4-methoxytoluene, 4-methoxyaniline, 4-ethoxyaniline, 2,5-dimethoxyaniline, 4-methylaniline, 4-ethylaniline, 4-n-butylaniline, 2-methylaniline, 3-methylaniline, 4-isopropylaniline, 2-phenoxy-3-chloroaniline, 4- (4'-chlorophenoxy) aniline, 4-acetylaminoaniline, 4 -Benzoylaminoaniline, 3-acetylamino-4-methylaniline, 4-aminotoluene-2-sulfonic acid anilide, 4-aminotoluene-2-sulfonic acid-N-ethylanilide, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-5-methyl -3-pyrazolone, 4-a
  • Preferred components (B) are also phthalide and especially fluoran compounds which have at least one primary amino group. 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-6-diethylaminofluoran, 2-amino-6-dimethylaminofluoran, 2-amino-6-di-n-butylaminofluoran, 2-amino-3-chloro-6-diethylaminofluoran, 3-chloro-6-aminofluorane, 2-amino-3-methyl-6-diethylaminofluoran, 3,3-bis (4'-dimethylaminophenyl) -6-aminophthalide, 3,3-bis- (4'-aminophenyl) -6-dimethylamino-phthalide, 3,3-bis (4'-diethylaminophenyl) -6-aminophthalide.
  • Both components (A) and the condensation components (B) can be used alone or as mixtures in the form of a combination of two or more of them in the recording material.
  • component (C) inorganic or organic color developers known for recording materials and capable of attracting electrons (electron acceptors) can be used.
  • 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 and 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 and 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 carboxylic acids advantageously 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.
  • 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 substituted 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.
  • 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- (
  • Organic complexes of zinc thiocyanate and in particular an antipyrine complex of zinc thiocyanate, a pyridine complex of zinc thiocyanate or a cresidine complex of zinc thiocyanate, as described in EP-A-97620, are also very suitable as component (C).
  • Particularly preferred components (C) are active clay, zinc salicylates, metal-free phenols, phenolic resins (novolak resins) or zinc-modified phenolic resins.
  • the developers can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, e.g. 2- (2'-Hydroxyphenyl-) benzotriazoles, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used.
  • pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, e.g. 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 the three components, the type of color change, the color reaction temperature and of course also on the desired color concentration. Satisfactory results are obtained when the color-developing component (C) is used in amounts of 0.1 to 100 parts by weight, preferably 1 to 20 parts by weight, per part of components (A) and (B).
  • both component (A) and component (B) are preferably used together or separately in an organic Solvents are dissolved and the solutions obtained are expediently encapsulated by processes such as, for example, in US Pat. Nos. 2,712,507, 2,800,457, 4,100,103, 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 which are formed by interfacial polymerization, such as capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially of polyamide, polyurea or polyurethane.
  • component (A) is encapsulated.
  • the encapsulation is usually necessary to separate components (A) and (B) from component (C) and thus prevent premature color formation.
  • 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 e.g. halogenated benzene, diphenyls or paraffin, e.g. Chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters, e.g.
  • 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 from each other 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.
  • the arrangement can also be reversed.
  • Another arrangement of the Components consist in 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 the developer is incorporated in the carrier material.
  • the capsule mass which contains components (A) and (B) can be mixed with other 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 primarily paper coating agents such as e.g. 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)), contains at least one inorganic metal salt, especially halides or nitrates, such as zinc chloride, for example. Contains tin chloride, zinc nitrate or mixtures thereof.
  • Example 1 2.2 g of 4-dimethylaminobenzaldehyde are dissolved in 100 g of diisopropylnaphthalene and mixed with a solution of 2 g of 3-amino-4-methoxytoluene in 100 g of diisopropylnaphthalene. The mixture is spread with a doctor blade (10 ⁇ m) on a sheet of paper, the surface of which is coated with acid-modified bentonite (CF sheet). An intense, lightfast yellow color develops.
  • CF sheet acid-modified bentonite
  • Example 2 If the mixture obtained in Example 1 is applied to a sheet of paper which is coated with zinc salicylate according to EP-A-181 283, Example 1, an intense, lightfast, yellow color is also obtained.
  • Example 3 If the mixture obtained in Example 1 is applied to a paper which has been coated with a phenolic resin as coreactant, a lightfast yellow color is obtained with a ⁇ maximum of 460 nm.
  • Example 4 1.2 g of 4-dimethylanlinozimtaldehyde are dissolved in 100 g of diisopropylnaphthalene and mixed with a solution of 0.94 g of 3-amino-4-methoxytoluene in 100 g of diisopropylnaphthalene. The mixture is applied using a 15 ⁇ m gravure plate CF sheet printed, which contains acid-modified bentonite. An intense, lightfast, violet color develops.
  • Example 5 If the mixture obtained in Example 4 is applied to a sheet of paper which contains a zinc salicylate as coreactant, a light-fast violet color is also obtained ( ⁇ max 560 nm).
  • Comparative Example 6 To prepare a dispersion A, 0.97 g of indole-3-aldehyde, 3.5 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 2 g of water with glass balls up to a particle size of 2- 4 ⁇ m ground.
  • Example 2 To prepare a dispersion C, 6 g of the zinc salicylate according to EP-A-181283, Example 1, 21 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 12 g of water with glass balls up to a grain size of 2-4 ⁇ m milled.
  • the dispersions A, B and C are then mixed and applied to a paper using a 15 ⁇ m gravure printing plate in such a way that the applied material corresponds to 4 g / m2 dry weight.
  • a lightfast, yellow color develops.
  • Example 7 1.4 g of 3,3-bis (4'-dimethylaminophenyl) -6-dimethylaminophthalide, 1.0 g of N-butylcarbazol-3-yl-bis- (4'-N-methyl-N-phenylaminophenyl) -methane, 0.5 g 3,3-bis- (Nn-octyl-2'-methylindol-3'-yl) phthalide, 0.66 g 4-dimethylamino-benzaldehyde and 0.6 g 3-amino-4 -methoxytoluene are dissolved in 96 g diisopropylnaphthalene and applied with pressure using a 15 ⁇ m gravure plate to a CF sheet, the surface of which is coated with acid-modified bentonite. An intense, lightfast, black color develops.
  • Example 8 0.51 g of 4-dimethylaminocinnamaldehyde is dissolved in 50 g of diisopropylnaphthalene and mixed with a solution of 0.54 g of 4-aminodiphenylamine in 50 g of diisopropylnaphthalene. With the help of a 15 ⁇ m rotogravure plate, the mixture is spread on a CF sheet which is coated with active clay. An intense, lightfast blue-violet color with ⁇ max 560 nm.
  • Example 9 If 4-dimethylaminocinnamaldehyde is replaced by the same amount of 4-diethylaminobenzaldehyde in Example 8 and the procedure is otherwise as described in the example, an intense light-fast, orange-brown color with ⁇ max 490 nm is obtained.
  • Example 10 0.56 g of 4-dimethylaminobenzaldehyde and 0.51 g of 4-isopropylaniline are dissolved together in diisopropylnaphthalene so that a 1% strength solution is obtained.
  • the solution is microencapsulated in a known manner with gelatin and carboxymethyl cellulose and glutaraldehyde by coacervation.
  • the capsule dispersion obtained is mixed with 5 g of a 20% strength aqueous polyvinyl alcohol solution and starch solution and 11 g of starch granules, coated on 50 g / m 2 raw paper and dried at 30 ° C. for 10 minutes.
  • the application weight atro is 8 g / m2.
  • the CB sheet obtained is placed on a CF sheet which contains active clay. If pressure is exerted on the recording material, a yellow color is immediately produced, which has an optical density of 0.56 and ⁇ max 460 nm.
  • Example 11 0.6 g of 4-dimethylaminocinnamaldehyde and 0.46 g of 4-isopropylaniline are dissolved together in diisopropylnaphthalene in such a way that a 1% strength solution is obtained.
  • the solution is microencapsulated in a known manner with gelatin and carboxymethyl cellulose and glutaraldehyde by coacervation.
  • the capsule dispersion obtained is mixed with 5 g of a 20% strength aqueous polyvinyl alcohol solution and starch solution and 11 g of starch granules, coated on base paper of 50 g / m 2 and dried at 30 ° C. for 10 minutes.
  • the application weight atro is 8 g / m2.
  • the CB sheet obtained is placed on a CF sheet which contains active clay. If pressure is exerted on the recording material, a magenta coloration immediately arises, which has an optical density of 0.76 and ⁇ max 540 nm
  • Example 12 0.51 g of 4-dimethylaminocinnamaldehyde and 0.54 g of 4-aminodiphenylamine are dissolved together in diisopropyinaphthalene so that a 1% solution is formed.
  • the solution is microencapsulated in a known manner with gelatin and carboxymethyl cellulose and glutaraldehyde by coacervation.
  • the capsule dispersion obtained is mixed with 5 g of a 20% strength aqueous polyvinyl alcohol solution and starch solution and 11 g of starch granules, coated on coating base paper of 50 g / m 2 and dried at 30 ° C. for 10 minutes.
  • the application weight atro is 8 g / m2.
  • the CB sheet obtained is placed on a CF sheet which contains active clay. Will print on the recording material exercised, then immediately a blue-violet coloration arises, which has an optical density of 0.78 and ⁇ max 560 nm.

Description

Die US-A-3,174,038 beschreibt ein wärmeempfindliches Aufzeichnungsmaterial, das (A) eine romatische Aldehydverbindung, (B) eine organische Kondensationskomponente mit einem primären Stickstoffatom und (C) eine elektronenanziehende und farbentwickwlnde Komponente aufweist.US-A-3,174,038 describes a heat-sensitive recording material which comprises (A) a romantic aldehyde compound, (B) an organic condensation component having a primary nitrogen atom and (C) an electron-attracting and color-developing component.

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

  • (A) eine aromatische Aldehydverbindung der Formel
    Figure imgb0001
     worin
    R₁ und R₂, unabhängig voneinander, je unsubstituiertes oder durch Halogen, Hydroxy, Cyano oder C₁-C₆-Alkoxy substituiertes Alkyl mit höchstens 12 Kohlenstoffatomen, Acyl mit 1 bis 8 Kohlenstoffatomen, Cycloalkyl mit 5 bis 10 Kohlenstoffatomen oder unsubstituiertes oder durch Halogen, Cyano, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkoxycarbonyl ringsubstituiertes Phen-C₁-C₃-alkyl oder Phenyl und R₂ auch Wasserstoff oder R₁ und R₂ zusammen mit dem sie verbindenden Stickstoffatom einen fünf- oder sechsgliedrigen heterocyclischen Rest darstellen,
    Ar Naphthylen oder Phenylen, welches durch Hydroxy, Halogen, Cyano, Nitro, Trihalogenmethyl, C₁-C₆-Alkyl, Methylsulfonyl, C₁-C₆-Alkoxy, Acyloxy oder Acylamino mit 1 bis 8 Kohlenstoffatomen, C₁-C₆-Alkylamino, Di-C₁-C₆-Alkylamino, Benzyloxy oder Phenoxy substituiert sein kann und
    n 1 oder 2 bedeuten, oder
    eine stickstoffhaltige heterocyclische Aldehydverbindung der Formel



            (3)   Z-CHO



    worin Z einen gegebenenfalls substituierten Pyrrolyl-, Antipyrinyl-, Triazinyl-, Indolyl-, Carbazolyl-, Julolidinyl-, Kairolinyl-, Indolinyl-, Iminodibenzyl-, Dihydrochinolinyl- oder Tetrahydrochinolinylrest bedeutet,
  • (B) eine Anilin-, Naphthylamin-, Aminoanilin-, Anilinsulfonsäureanilid-, Aminophenylethylen-, Aminophenylstyrol-, Acylacetarylamid-, 3-Aminophenolether-, Aminopyrazol-, Aminothiazol-, Pyrazolon-, Barbitursäure-, Pyrrolidin-, Piperidin-, Piperazin-, Morpholin-, Benzomorpholin-, Indolinverbindung, Cyanomethylbenzoimidazol-, Cyanomethylbenzoxazol- oder Cyanomethylbenzothiazolverbindung oder Fluoran- oder Phthalidverbindung ist, welche eine unsubstituierte Aminogruppe aufweist, und
  • (C) eine elektronenanziehende und farbentwickelnde Komponente
aufweist.The present invention relates to a pressure-sensitive recording material in which the color reactant system is an essential component
  • (A) an aromatic aldehyde compound of the formula
    Figure imgb0001
     wherein
    R₁ and R₂, independently of one another, each unsubstituted or substituted by halogen, hydroxy, cyano or C₁-C₆alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or unsubstituted or by halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkoxycarbonyl ring-substituted phen-C₁-C₃-alkyl or phenyl and R₂ also hydrogen or R₁ and R₂ together with the nitrogen atom connecting them represent a five- or six-membered heterocyclic radical,
    Ar naphthylene or phenylene, which is substituted by hydroxy, halogen, cyano, nitro, trihalomethyl, C₁-C₆-alkyl, methylsulfonyl, C₁-C₆-alkoxy, acyloxy or acylamino having 1 to 8 carbon atoms, C₁-C₆-alkylamino, di-C₁- C₆-alkylamino, benzyloxy or phenoxy may be substituted and
    n is 1 or 2, or
    a nitrogen-containing heterocyclic aldehyde compound of the formula



    (3) Z-CHO



    in which Z represents an optionally substituted pyrrolyl, antipyrinyl, triazinyl, indolyl, carbazolyl, julolidinyl, kairolinyl, indolinyl, iminodibenzyl, dihydroquinolinyl or tetrahydroquinolinyl radical,
  • (B) aniline, naphthylamine, aminoaniline, aniline sulfonic acid anilide, aminophenylethylene, aminophenylstyrene, acylacetarylamide, 3-aminophenol ether, aminopyrazole, aminothiazole, pyrazolone, barbituric acid, pyrrolidine, piperidine , Morpholine, benzomorpholine, indoline compound, cyanomethylbenzoimidazole, cyanomethylbenzoxazole or cyanomethylbenzothiazole compound or fluoran or phthalide compound which has an unsubstituted amino group, and
  • (C) an electron attracting and color developing component
having.

Komponenten (A), (B) und (C) kommen je nach Aufzeichnungsmaterial durch Druck 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-Dialhylamino-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 Triarylmethanen einsetzt.Components (A), (B) and (C) come into contact with one another by pressure, 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, such as, for example, yellow, orange, red, violet, blue, green, gray, black or mixed colors, can thus be produced by a corresponding combination of the individual components. Another possible combination is that components (A) and (B) together with one or more conventional color formers, for example 3,3- (bis-aminophenyl -) - phthalides such as CVL, 3-indolyl-3-aminophenylaza- or -diazaphthalides , (3,3-bis-indolyl -) - phthalides, 3-aminofluoranes, 6-dialhylamino-2-dibenzylaminofluoranes, 6-dialkylamino-3-methyl-2-arylaminofluoranes, 3,6-bisalkoxyfluoranes, 3,6-bisdiarylaminofluoranes, Leucoauramines, spiropyrans, spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes.

Stellen die Substituenten R₁ und R₂ Alkylgruppen dar, so können sie geradkettig oder verzweigt sein. Beispiele solcher Alkylreste sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, 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 R₁ and R₂ represent alkyl groups, they can be straight-chain or branched. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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 und R₂ 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-chlorpropyl, 3-Methoxypropyl, 4-Methoxybutyl oder 4-Propoxybutyl.If the alkyl radicals in R₁ and R₂ 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 R₁ und R₂ sind Cyclopentyl oder vorzugsweise Cyclohexyl.Examples of cycloalkyl in the meaning of R₁ and R₂ are cyclopentyl or preferably cyclohexyl.

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.

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 und der Phenylgruppe von R₁ und R₂ 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 and the phenyl group of R₁ and R₂ 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, C₁-C₆-Alkoxy-C₁-C₆-Alkyl, Cyano-C₁-C₆-Alkyl z.B. β-Cyanoethyl oder in erster Linie C₁-C₆-Alkyl, wie z.B. Methyl, Ethyl oder n-Butyl. -NR₁R₂ ist bevorzugt auch Pyrrolidinyl.The substituents R₁ and R₂ are preferably cyclohexyl, benzyl, tolyl, phenethyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, cyano-C₁-C₆-alkyl e.g. β-cyanoethyl or primarily C₁-C₆ alkyl, e.g. Methyl, ethyl or n-butyl. -NR₁R₂ is also preferably pyrrolidinyl.

Unter den Verbindungen der Formel (1) sind vor allem diejenigen bevorzugt, bei denen R₁ und R₂ je C₁-C₆-Alkyl, Chlor-C₁-C₆-Alkyl, Cyano-C₁-C₆-Alkyl, Benzyl, Phenyl oder R₁ und R₂ zusammen mit dem gemeinsamen Stickstoffatom Pyrrolidino, Piperidino oder Morpholino darstellen, Ar Naphthylen oder Phenylen, welches gegebenenfalls durch Hydroxy, Halogen, Trifluormethyl, C₁-C₆-Alkyl oder C₁-C₆-Alkoxy substituiert ist und n 1 oder 2 bedeuten.Among the compounds of formula (1), especially preferred are those in which R₁ and R₂ are each C₁-C₆-alkyl, chloro-C₁-C₆-alkyl, cyano-C₁-C₆-alkyl, benzyl, phenyl or R₁ and R₂ together represent with the common nitrogen atom pyrrolidino, piperidino or morpholino, ar naphthylene or phenylene, which is optionally substituted by hydroxy, halogen, trifluoromethyl, C₁-C₆-alkyl or C₁-C₆-alkoxy and n is 1 or 2.

Der ein- oder mehrkernige heterocyclische Rest Z in Formel (3) kann einfach oder mehrfach ringsubstituiert sein. Als C-Substituenten kommen dabei z.B. Halogen, Hydroxy, Cyano, Nitro, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Akylthio, C₁-C₆-Alkoxycarbonyl, Acyl mit 1 bis 8 Kohlenstoffatomen, vorzugsweise C₁-C₆-Alkylcarbonyl, C₁-C₆-Alkylamino, C₁-C₆-Alkylcarbonylamino oder Di-C₁-C₆-Alkylamino, C₅-C₆-Cycloalkyl, Benzyl oder Phenyl in Frage, während N-Substituenten beispielsweise C₁-C₁₂-Alkyl, C₂-C₁₂-Alkenyl, C₅-C₁₀-Cycloalkyl, C₁-C₈-Acyl, Phenyl, Benzyl, Phenethyl oder Phenisopropyl sind, die jeweils z.B. durch Cyano, Halogen, Nitro, Hydroxy, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkylamino oder C₁-C₆-Alkoxycarbonyl substituiert sein können.The mono- or polynuclear heterocyclic radical Z in formula (3) can be ring-substituted one or more times. The C substituents are e.g. Halogen, hydroxy, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkoxycarbonyl, acyl with 1 to 8 carbon atoms, preferably C₁-C₆-alkylcarbonyl, C₁-C₆- Alkylamino, C₁-C₆-alkylcarbonylamino or di-C₁-C₆-alkylamino, C₅-C₆-cycloalkyl, benzyl or phenyl in question, while N-substituents for example C₁-C₁₂-alkyl, C₂-C₁₂-alkenyl, C₅-C₁₀-cycloalkyl , C₁-C₈ acyl, phenyl, benzyl, phenethyl or phenisopropyl, each of which, for example can be substituted by cyano, halogen, nitro, hydroxy, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino or C₁-C₆-alkoxycarbonyl.

Die Alkyl- und Alkenylreste können geradkettig oder verzweigt sein. Beispiele hierfür sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, 1-Methylbutyl, t-Butyl, sek.Butyl, Amyl, Isopentyl, n-Hexyl, 2-Ethylhexyl, Isooctyl, n-Octyl, 1,1,3,3-Tetramethylbutyl, Nonyl, Isononyl, 3-Ethylheptyl, Decyl oder n-Dodecyl bzw. Vinyl, Allyl, 2-Methylallyl, 2-Ethylallyl, 2-Butenyl oder Octenyl.The alkyl and alkenyl radicals can be straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylbutyl, t-butyl, sec-butyl, amyl, isopentyl, n-hexyl, 2-ethylhexyl, isooctyl, n-octyl, 1,1 , 3,3-tetramethylbutyl, nonyl, isononyl, 3-ethylheptyl, decyl or n-dodecyl or vinyl, allyl, 2-methylallyl, 2-ethylallyl, 2-butenyl or octenyl.

Bevorzugte heterocyclische Reste Z sind unsubstituierte oder substituierte 2- oder 3-Pyrrolylreste, 3-Indolylreste oder Indolinylreste wie z.B. 2-Pyrrolyl-, N-C₁-C₈-Alkylpyrrol-2-yl-, N-Phenylpyrrol-3-yl-, 3-Indolyl-, N-C₁-C₈-Alkyl-2-methylindol-3-yl-, N-C₂-C₄-Alkanoyl-2-methylindol-3-yl, 2-Phenylindol-3-yl-, N-C₁-C₈-Alkyl-2-phenylindol-3-yl-, N-C₁-C₈-Alkylcarbazol-3-yl- oder 1,3,3-Trimethyl-2-methenyl-indolinylreste.Preferred heterocyclic radicals Z are unsubstituted or substituted 2- or 3-pyrrolyl radicals, 3-indolyl radicals or indolinyl radicals such as e.g. 2-pyrrolyl, N-C₁-C₈-alkylpyrrol-2-yl-, N-phenylpyrrol-3-yl-, 3-indolyl-, N-C₁-C₈-alkyl-2-methylindol-3-yl-, N -C₂-C₄-Alkanoyl-2-methylindol-3-yl, 2-phenylindol-3-yl-, N-C₁-C₈-alkyl-2-phenylindol-3-yl-, N-C₁-C₈-alkylcarbazol-3 -yl- or 1,3,3-trimethyl-2-methenyl-indolinyl residues.

"Acyl" ist besonders Formyl, C₁-C₆-Alkylcarbonyl, wie z.B. Acetyl oder Propionyl, oder Benzoyl. Weitere Acylreste können C₁-C₆-Alkylsulfonyl, 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, C₁-C₆ alkylcarbonyl, such as acetyl or propionyl, or benzoyl. Other acyl radicals can be C₁-C₆ alkylsulfonyl, such as methylsulfonyl or Ethylsulfonyl and phenylsulfonyl. Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.

Beispiele für C₁-C₆-Alkyl, C₁-C₆-Alkoxy und C₁-C₆-Alkylthio sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, Amyl, Isoamyl oder Hexyl bzw. Methoxy, Ethoxy, Isopropoxy, Isobutoxy, tert.Butoxy oder Amyloxy bzw. Methylthio, Ethylthio, Propylthio oder Butylthio.Examples of C₁-C₆-alkyl, C₁-C₆-alkoxy and C₁-C₆-alkylthio are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, isoamyl or hexyl or methoxy, ethoxy, isopropoxy , Isobutoxy, tert-butoxy or amyloxy or methylthio, ethylthio, propylthio or butylthio.

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

Zu spezifischen Beispielen für die als Komponente (A) in Betracht kommenden Aldehydverbindungen der Formeln (1) und (3) gehören
4-Dimethylaminobenzaldehyd, 4-N-Methyl-N-β-cyanoethylaminobenzaldehyd, 4-Diethylaminobenzäldehyd, 4-(Di-β-cyanoethylamino)-benzaldehyd, 4-Di-n-propylaminobenzaldehyd, 4-Dibenzylaminobenzaldehyd, 4-(Di-β-hydroxyethylamino)-benzaldehyd, 4-N-Ethyl-N-benzylaminobenzaldehyd, 4-Dimethylamino-2-methylsulfonylbenzaldehyd, 4-Pyrrolidinobenzaldehyd, 4-Morpholinobenzaldehyd, 4-(N-β-Chlorethyl-N-ethylamino)benzaldehyd, 4-Diallylaminobenzaldehyd, 4-(N-Phenyl-N-methylamino)-benzaldehyd, 4-(N-β-Hydroxyethyl-N-ethylamino)-2-methylbenzaldehyd, 4-Dimethylaminosalicylaldehyd, 4-Di-n-propylaminosalicylaldehyd, 4-Dimethylamino-2-cyanobenzaldehyd, 4-Dimethylamino-2-carbomethoxy-benzaldehyd, 4-Dimethylamino-2-methoxybenzaldehyd, 4-Diethylamino-2-methoxybenzaldehyd, 4-Diethylamino-2-hydroxybenzaldehyd, 4-Dimethylamino-3-chlorbenzaldehyd, 4-Dimethylamino-2,6-dimethylbenzaldehyd, 4-Diethylamino-2-methylbenzaldehyd, 4-Dimethylamino-2-nitrobenzaldehyd, 4-Dimethylaminozimtaldehyd, 4-Diethylaminozimtaldehyd, Indol-3-aldehyd, N-Ethylcarbazol-3-aldehyd, 2-Methylindol-3-aldehyd, 4-Phenylaminobenzaldehyd, 2-Diethylamino-thiazol-5-aldehyd, Pyrrol-2-aldehyd, N-Methyl-pyrrol-2-aldehyd, 1-Methylindol-3-aldehyd, 1-Methyl-2-phenylindol-3-aldehyd, 1-Ethyl-2-methylindol-3-aldehyd, 1-n-Octyl-2-methylindol-3-aldehyd, 1-β-Cyanoethyl-2-phenylindol-3-aldehyd, Julolidinaldehyd, 3,3-Dimethyl-2-methylenindolin-ω-aldehyd, 1,3,3-Trimethyl-2-methylenindolin-ω-aldehyd, 1,3,3-Trimethyl-5-cyano-2-methylenindolin-ω-aldehyd, 1,3,3-Trimethyl-5-acetylamino-2-methylenindolin-ω-aldehyd, 1,3,3-Trimethyl-5-carbomethoxy-2-methylenindolin-ω-aldehyd, 1,3,3-Trimethyl-5-chlor-2-methylenindolin-ω-aldehyd, Antipyrinaldehyd, Iminodibenzylaldehyd,
Bevorzugte spezifische Komponenten (A) sind 4-Dimethylaminobenzaldehyd, 4-Diethylaminobenzaldehyd, 4-Dimethylaminozimtaldehyd und Indol-3-aldehyd.Specific examples of the aldehyde compounds of the formulas (1) and (3) which are suitable as component (A) include
4-dimethylaminobenzaldehyde, 4-N-methyl-N-β-cyanoethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4- (di-β-cyanoethylamino) benzaldehyde, 4-di-n-propylaminobenzaldehyde, 4-dibenzylaminobenzaldehyde, 4- (di-β -hydroxyethylamino) benzaldehyde, 4-N-ethyl-N-benzylaminobenzaldehyde, 4-dimethylamino-2-methylsulfonylbenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 4- (N-β-chloroethyl-N-ethylamino) benzaldehyde, 4-diallylaminobenzene , 4- (N-phenyl-N-methylamino) benzaldehyde, 4- (N-β-hydroxyethyl-N-ethylamino) -2-methylbenzaldehyde, 4-dimethylaminosalicylaldehyde, 4-di-n-propylaminosalicylaldehyde, 4-dimethylamino-2 -cyanobenzaldehyde, 4-dimethylamino-2-carbomethoxy-benzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4-diethylamino-2-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-3-chlorobenzaldehyde, 4-dimethylamino-2 , 6-dimethylbenzaldehyde, 4-diethylamino-2-methylbenzaldehyde, 4-dimethylamino-2-nitrobenzaldehyde, 4-dimethylaminocinnamaldehyde, 4-diethylaminocinnamaldehyde, Indole-3-aldehyde, N-ethylcarbazole-3-aldehyde, 2-methylindole-3-aldehyde, 4-phenylaminobenzaldehyde, 2-diethylamino-thiazole-5-aldehyde, pyrrole-2-aldehyde, N-methylpyrrole-2- aldehyde, 1-methylindole-3-aldehyde, 1-methyl-2-phenylindole-3-aldehyde, 1-ethyl-2-methylindole-3-aldehyde, 1-n-octyl-2-methylindole-3-aldehyde, 1- β-cyanoethyl-2-phenylindole-3-aldehyde, julolidinaldehyde, 3,3-dimethyl-2-methyleneindoline-ω-aldehyde, 1,3,3-trimethyl-2-methyleneindoline-ω-aldehyde, 1,3,3- Trimethyl-5-cyano-2-methyleneindoline-ω-aldehyde, 1,3,3-trimethyl-5-acetylamino-2-methyleneindoline-ω-aldehyde, 1,3,3-trimethyl-5-carbomethoxy-2-methyleneindoline- ω-aldehyde, 1,3,3-trimethyl-5-chloro-2-methyleneindoline-ω-aldehyde, antipyrinaldehyde, iminodibenzylaldehyde,
Preferred specific components (A) are 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylaminocinnamaldehyde and indole-3-aldehyde.

Die erfindungsgemäss verwendeten Komponenten (B), die mit Komponente (A) chromogene Verbindungen bilden, entstammen. aus der Reihe der Aniline, Naphthylamine, Aminoaniline, Anilinsulfonsäureanilide, Aminophenylethylenverbindungen, Aminophenylstyrolverbindungen, Acylacetarylamide, 3-Aminophenolether, Aminopyrazole, Aminothiazole, Pyrazolone, Barbitursäuren, Pyrrolidine, Piperidine, Piperazine, Morpholine, Benzomorphline, Indoline, Cyanmethylbenzimidazole oder Fluoran- oder Phthalidverbindungen, welche eine unsubstitutierte Aminogruppe aufweisen.The components (B) used according to the invention, which form chromogenic compounds with component (A), originate. from the series of anilines, naphthylamines, aminoanilines, anilinesulfonic acid anilides, aminophenylethylene compounds, aminophenylstyrene compounds, acylacetarylamides, 3-aminophenol ethers, aminopyrazoles, aminothiazoles, pyrazolones, barbituric acids, phyrolidines, cyanometholeolines, cyanometholeolines, morpholines, piperomines, cyanometholines, morpholines, piperomines, piperomines have an unsubstituted amino group.

Bevorzugte Kondensationskomponenten (B) sind Aniline, wie Kresidine oder Phenetidine sowie Amino-Diphenylamine und Toluidinsulfonsäureanilide.Preferred condensation components (B) are anilines, such as cresidines or phenetidines, and also amino-diphenylamines and toluidine sulfonic acid anilides.

Am bevorzugtesten sind Anilinverbindungen der Formel

Figure imgb0002

worin
V Wasserstoff, Hydroxy, Halogen, Trifluormethyl, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkoxycarbonyl, C₁-C₆-Alkanoyloxy, Benzyloxy oder Phenoxy und
m 1 oder 2 bedeuten.
Ein V befindet sich vorzugsweise in Ortho-Stellung zur Aminogruppe.Most preferred are aniline compounds of the formula
Figure imgb0002
wherein
V is hydrogen, hydroxy, halogen, trifluoromethyl, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy, benzyloxy or phenoxy and
m is 1 or 2.
A V is preferably in the ortho position to the amino group.

Spezifische Beispiele für Kondensationskomponenten (B) sind Anilin, 2-Amino-4-methoxytoluol, 2-Amino-4-hydroxy-toluol, 3-Amino-4-methoxytoluol, 4-Methoxyanilin, 4-Ethoxyanilin, 2,5-Dimethoxyanilin, 4-Methylanilin, 4-Ethylanilin, 4-n-Butylanilin, 2-Methylanilin, 3-Methylanilin, 4-Isopropylanilin, 2-Phenoxy-3-chloranilin, 4-(4'-Chlorphenoxy)-anilin, 4-Acetylaminoanilin, 4-Benzoylaminoanilin, 3-Acetylamino-4-methylanilin, 4-Aminotoluol-2-sulfonsäureanilid, 4-Aminotoluol-2-sulfonsäure-N-ethylanilid, 1-Phenyl-3-methyl-5 -pyrazolon, 1-Phenyl-5-methyl-3-pyrazolon, 4-Aminodiphenylamin, 1-(2'-Chlorphenyl)-5-methyl-3-pyrazolon, Naphthylamin, 1-Amino-7-naphthol, 3-Methyl-5-amino-pyrazol, 1-(4'-Tolyl)-3-methyl-5-aminopyrazol, 2-(4'-Aminophenyl)-6-methylbenzothiazol, 2-Cyanomethylbenzothiazol, 3-Phenyl-4-methylindolizin, 2,3-Diphenylindolizin.Specific examples of condensation components (B) are aniline, 2-amino-4-methoxytoluene, 2-amino-4-hydroxy-toluene, 3-amino-4-methoxytoluene, 4-methoxyaniline, 4-ethoxyaniline, 2,5-dimethoxyaniline, 4-methylaniline, 4-ethylaniline, 4-n-butylaniline, 2-methylaniline, 3-methylaniline, 4-isopropylaniline, 2-phenoxy-3-chloroaniline, 4- (4'-chlorophenoxy) aniline, 4-acetylaminoaniline, 4 -Benzoylaminoaniline, 3-acetylamino-4-methylaniline, 4-aminotoluene-2-sulfonic acid anilide, 4-aminotoluene-2-sulfonic acid-N-ethylanilide, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-5-methyl -3-pyrazolone, 4-aminodiphenylamine, 1- (2'-chlorophenyl) -5-methyl-3-pyrazolone, naphthylamine, 1-amino-7-naphthol, 3-methyl-5-aminopyrazole, 1- (4th '-Tolyl) -3-methyl-5-aminopyrazole, 2- (4'-aminophenyl) -6-methylbenzothiazole, 2-cyanomethylbenzothiazole, 3-phenyl-4-methylindolizine, 2,3-diphenylindolizine.

Bevorzugte Komponenten (B) sind auch Phthalid- und vor allem Fluoranverbindungen, welche mindestens eine primäre 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. 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-6-diethylaminofluoran,
2-Amino-6-dimethylaminofluoran,
2-Amino-6-di-n-butylaminofluoran,
2-Amino-3-chlor-6-diethylaminofluoran,
3-Chlor-6-aminofluoran,
2-Amino-3-methyl-6-diethylaminofluoran,
3,3-Bis-(4'-dimethylaminophenyl)-6-aminophthalid,
3,3-Bis-(4'-aminophenyl)-6-dimethylamino-phthalid,
3,3-Bis-(4'-diethylaminophenyl)-6-amino-phthalid.Specific examples of such components (B) are:
2-amino-6-diethylaminofluoran,
2-amino-6-dimethylaminofluoran,
2-amino-6-di-n-butylaminofluoran,
2-amino-3-chloro-6-diethylaminofluoran,
3-chloro-6-aminofluorane,
2-amino-3-methyl-6-diethylaminofluoran,
3,3-bis (4'-dimethylaminophenyl) -6-aminophthalide,
3,3-bis- (4'-aminophenyl) -6-dimethylamino-phthalide,
3,3-bis (4'-diethylaminophenyl) -6-aminophthalide.

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

Sowohl Komponenten (A) als auch die Kondensationskomponenten (B) können für sich allein oder als Mischungen in Form einer Kombination von zwei oder mehrerer derselben in dem Aufzeichnungsmaterial eingesetzt werden.Both components (A) and the condensation components (B) can be used alone or as mixtures in the form of a combination of two or more of them in the recording material.

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

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 and 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, vorteilhafterweise 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 carboxylic acids, advantageously 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 substituted 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.

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, 3,5-Di-(α-methylbenzyl)-salicylsäure, 3,5-Di-(α,α-dimethylbenzyl)-salicylsäure, Salicylosalicylsäure, Gallussäurealkylester, Gallussäure, Hydroxyphthalsäure, 4-Hydroxyphthalsäuredimethylester, 1-Hydroxy-2-naphthoesäure oder Phenol-Formaldehyde-Vorpolymerisate, 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-181 283 oder DE-A-2 242 250 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, 3,5-di- (α-methylbenzyl) -salicylic acid, 3,5-di- (α, α-dimethylbenzyl ) -salicylic acid, salicylosalicylic acid, gallic acid alkyl ester, gallic acid, hydroxyphthalic acid, 4-hydroxyphthalic acid dimethyl ester, 1-hydroxy-2-naphthoic acid or phenol-formaldehyde prepolymers, 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-181 283 or DE-A-2 242 250.

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

Besonders bevorzugte Komponenten (C) sind Aktivton, Zinksalicylate, metallfreie Phenole, Phenolharze (Novolakharze) oder zinkmodifizierte Phenolharze.Particularly preferred components (C) are active clay, zinc salicylates, metal-free phenols, phenolic resins (novolak resins) or zinc-modified phenolic resins.

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-Kondensationsprodukte.The developers can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, e.g. 2- (2'-Hydroxyphenyl-) benzotriazoles, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used. Examples of such pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, e.g. 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, von der Farbreaktionstemperatur und selbstverständlich auch von der gewünschten Farbkonzentration ab. Es werden zufriedenstellende Ergebnisse erzielt, wenn die farbentwickelnde Komponente (C) in Mengen von 0,1 bis 100 Gew. Teilen, vorzugsweise 1 bis 20 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 the three components, the type of color change, the color reaction temperature and of course also on the desired color concentration. Satisfactory results are obtained when the color-developing component (C) is used in amounts of 0.1 to 100 parts by weight, preferably 1 to 20 parts by weight, per part of components (A) and (B).

Für das druckempfindliche Aufzeichnungsmaterial werden sowohl Komponente (A) als auch Komponente (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, 4 100 103, 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, Polyharnstoff oder Polyurethan. In manchen Fällen genügt, dass lediglich Komponente (A) eingekapselt wird. Die Einkapselung ist in der Regel erforderlich, um Komponenten (A) und (B) von Komponente (C) zu trennen und somit eine frühzeitige Farbbildung 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 used together or separately in an organic Solvents are dissolved and the solutions obtained are expediently encapsulated by processes such as, for example, in US Pat. Nos. 2,712,507, 2,800,457, 4,100,103, 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. Also suitable are microcapsules which are formed by interfacial polymerization, such as capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially of polyamide, polyurea or polyurethane. In some cases it is sufficient that only component (A) is encapsulated. The encapsulation is usually necessary to separate components (A) and (B) from component (C) and thus prevent premature color formation. 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, Triocrylphosphat, 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-älkylierte 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 e.g. halogenated benzene, diphenyls or paraffin, e.g. Chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters, e.g. Dibutyl adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl adipate, trichloroethyl phosphate, triocryl phosphate, tricresyl phosphate, aromatic ethers such as benzylphenyl ether; Hydrocarbon oils such as paraffin oil or kerosene, e.g. with isopropyl, isobutyl, sec-butyl or tert-butyl alkylated derivatives of diphenyl, 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 voneinander durch die Anordnung der Kapseln, der Farbreaktanten und durch das Trägermaterial.Microcapsules containing components (A) and (B) can be used to produce pressure-sensitive copying materials of various known types. The different systems differ essentially from each other 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. Die Anordnung kann aber auch umgekehrt sein. 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 vorliegen oder der Entwickler im Trägermaterial eingebaut ist.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. The arrangement can also be reversed. Another arrangement of the Components consist in 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 the developer is incorporated in the carrier material.

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 einkapselt.To achieve the desired color, the capsule mass which contains components (A) and (B) can be mixed with other 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. Gummiarabicum, 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 backing material, this binder is primarily paper coating agents such as e.g. 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)), contains at least one inorganic metal salt, especially halides or nitrates, such as zinc chloride, for example. Contains tin chloride, zinc nitrate or mixtures thereof.

In den folgenden Herstellungsvorschriften und Beispielen beziehen sich die angegebenen Prozentsätze, wenn nichts anderes angegeben ist, auf das Gewicht. Teile sind Gewichtsteile.In the following manufacturing instructions and examples, the percentages given are by weight unless otherwise specified. Parts are parts by weight.

Beispiel 1: 2,2 g 4-Dimethylaminobenzaldehyd werden in 100 g Diisopropylnaphthalin gelöst und mit einer Lösung aus 2 g 3-Amino-4-methoxytoluol in 100 g Diisopropylnaphthalin vermischt. Die Mischung wird mit einem Rakel (10 µm) auf ein Blatt Papier gestrichen, dessen Oberfläche mit säuremodifiziertem Bentonit beschichtet ist (CF-Blatt). Es entwickelt sich eine intensive, lichtechte gelbe Farbe. Example 1 : 2.2 g of 4-dimethylaminobenzaldehyde are dissolved in 100 g of diisopropylnaphthalene and mixed with a solution of 2 g of 3-amino-4-methoxytoluene in 100 g of diisopropylnaphthalene. The mixture is spread with a doctor blade (10 µm) on a sheet of paper, the surface of which is coated with acid-modified bentonite (CF sheet). An intense, lightfast yellow color develops.

Beispiel 2: Wird die in Beispiel 1 erhaltene Mischung auf ein Blatt Papier appliziert, welches mit Zinksalicylat gemäss EP-A- 181 283, Beispiel 1 beschichtet ist, so erhält man ebenfalls eine intensive, lichtechte, gelbe Farbe. Example 2 : If the mixture obtained in Example 1 is applied to a sheet of paper which is coated with zinc salicylate according to EP-A-181 283, Example 1, an intense, lightfast, yellow color is also obtained.

Beispiel 3: Wird die in Beispiel 1 erhaltene Mischung auf ein Papier applizert, welches mit einem Phenolharz als Koreaktant gestrichen ist, so erhält man eine lichtechte, gelbe Farbe, mit einem λ-Maximum von 460 nm. Example 3 : If the mixture obtained in Example 1 is applied to a paper which has been coated with a phenolic resin as coreactant, a lightfast yellow color is obtained with a λ maximum of 460 nm.

Beispiel 4: 1,2 g 4-Dimethylanlinozimtaldehyd werden in 100 g Diisopropylnaphthalin gelöst und mit einer Lösung von 0,94 g 3-Amino-4-methoxytoluol in 100 g Diisopropylnaphthalin vermischt. Die Mischung wird mit Hilfe einer 15 µm Tiefdruckplatte auf ein CF-Blatt gedruckt, welches säuremodifiziertes Bentonit enthält. Es entwickelt sich eine intensive, lichtechte, violette Farbe. Example 4 : 1.2 g of 4-dimethylanlinozimtaldehyde are dissolved in 100 g of diisopropylnaphthalene and mixed with a solution of 0.94 g of 3-amino-4-methoxytoluene in 100 g of diisopropylnaphthalene. The mixture is applied using a 15 µm gravure plate CF sheet printed, which contains acid-modified bentonite. An intense, lightfast, violet color develops.

Beispiel 5: Wird die in Beispiel 4 erhaltene Mischung auf ein Blatt Papier appliziert, welches ein Zinksalicylat als Koreaktanten enthält, so erhält man ebenfalls eine lichtechte violette Farbe (λmax 560 nm). Example 5 : If the mixture obtained in Example 4 is applied to a sheet of paper which contains a zinc salicylate as coreactant, a light-fast violet color is also obtained (λ max 560 nm).

Vergleichsbeispiel 6: Zur Herstellung einer Dispersion A werden 0,97 g Indol-3-aldehyd, 3,5 g einer 10%igen wässrigen Lösung von Polyvinylalkohol (Polyviol V03/140) und 2 g Wasser mit Glaskugeln bis zu einer Korngrösse von 2-4 µm gemahlen. Comparative Example 6 : To prepare a dispersion A, 0.97 g of indole-3-aldehyde, 3.5 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 2 g of water with glass balls up to a particle size of 2- 4 µm ground.

Zur Herstellung einer Dispersion B werden 1,17 g 1-Phenyl-3-methyl-5-pyrazolon, 3,5 g einer 10%igen wässrigen Lösung von Polyvinylalkohol (Polyviol V03/140) und 2 g Wasser mit Glaskugeln bis zu einer Korngrösse von 2-4 µm gemahlen.To prepare a dispersion B, 1.17 g of 1-phenyl-3-methyl-5-pyrazolone, 3.5 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 2 g of water with glass balls up to a particle size ground from 2-4 µm.

Zur Herstellung einer Dispersion C werden 6 g des Zinksalicylates gemäss EP-A-181283, Beispiel 1, 21 g einer 10%igen wässrigen Lösung von Polyvinylalkohol (Polyviol V03/140) und 12 g Wasser mit Glaskugeln bis zu einer Korngrösse von 2-4 µm gemahlen.To prepare a dispersion C, 6 g of the zinc salicylate according to EP-A-181283, Example 1, 21 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 12 g of water with glass balls up to a grain size of 2-4 µm milled.

Anschliessend werden die Dispersionen A, B und C vermischt und mit Hilfe einer 15 µm Tiefdruckplatte so auf ein Papier aufgetragen, dass das aufgebrachte Material 4 g/m² Trockengewicht entspricht. Durch Berührung des Papiers mit einem erhitzten Metallstift entwickelt sich eine lichtechte, gelbe Farbe.The dispersions A, B and C are then mixed and applied to a paper using a 15 μm gravure printing plate in such a way that the applied material corresponds to 4 g / m² dry weight. By touching the paper with a heated metal pen, a lightfast, yellow color develops.

Beispiel 7: 1,4 g 3,3-Bis-(4'-dimethylaminophenyl)-6-dimethylaminophthalid, 1,0 g N-Butylcarbazol-3-yl-bis-(4'-N-methyl-N-phenylaminophenyl)-methan, 0,5 g 3,3-Bis-(N-n-octyl-2'-methylindol-3'-yl)-phthalid, 0,66 g 4-Dimethylamino-benzaldehyd und 0,6 g 3-Amino-4-methoxytoluol werden in 96 g Diisopropylnaphthälin gelöst und mit Druck mit Hilfe einer 15 µm Tiefdruckplatte auf ein CF-Blatt appliziert, dessen Oberfläche mit säuremoddiziertem Bentonit gestrichen ist Es entwickelt sich eine intensive, lichtechte, schwarze Farbe. Example 7 : 1.4 g of 3,3-bis (4'-dimethylaminophenyl) -6-dimethylaminophthalide, 1.0 g of N-butylcarbazol-3-yl-bis- (4'-N-methyl-N-phenylaminophenyl) -methane, 0.5 g 3,3-bis- (Nn-octyl-2'-methylindol-3'-yl) phthalide, 0.66 g 4-dimethylamino-benzaldehyde and 0.6 g 3-amino-4 -methoxytoluene are dissolved in 96 g diisopropylnaphthalene and applied with pressure using a 15 µm gravure plate to a CF sheet, the surface of which is coated with acid-modified bentonite. An intense, lightfast, black color develops.

Beispiel 8: 0,51 g 4-Dimethylaminozimtaldehyd werden in 50 g Diisopropylnaphthalin gelöst und mit einer Lösung von 0,54 g 4-Aminodiphenylamin in 50 g Diisopropylnaphthalin vermischt. Mit Hilfe einer 15 µm Tiefdruckplatte wird die Mischung auf ein CF-Blatt, welches mit Aktivton beschichtet ist, gestrichen. Es entwickelt sich sofort eine intensive, lichtechte blauviolette Farbe mit λmax 560 nm. Example 8 : 0.51 g of 4-dimethylaminocinnamaldehyde is dissolved in 50 g of diisopropylnaphthalene and mixed with a solution of 0.54 g of 4-aminodiphenylamine in 50 g of diisopropylnaphthalene. With the help of a 15 µm rotogravure plate, the mixture is spread on a CF sheet which is coated with active clay. An intense, lightfast blue-violet color with λ max 560 nm.

Beispiel 9: Ersetzt man im Beispiel 8 4-Dimethylaminozimtaldehyd durch gleiche Menge 4-Diethylaminobenzaldehyd und verfährt ansonst wie im Beispiel beschrieben, erhält man eine intensive lichtechte, orangebraune Farbe mit λmax 490 nm. Example 9 : If 4-dimethylaminocinnamaldehyde is replaced by the same amount of 4-diethylaminobenzaldehyde in Example 8 and the procedure is otherwise as described in the example, an intense light-fast, orange-brown color with λ max 490 nm is obtained.

Beispiel 10: 0,56 g 4-Dimethylaminobenzaldehyd und 0,51 g 4-Isopropylanilin werden zusammen in Diisopropylnaphthalin so gelöst, dass eine 1%ige Lösung entsteht. Die Lösung wird auf bekannte Weise mit Gelatine und Carboxymethylcellulose und Glutaraldehyd durch Koazervation mikroverkapselt. Die erhaltene Kapseldispersion wird mit 5 g einer 20%igen wässrigen Polyvinylalkohollösung und Stärkelösung und 11 g Stärkekörner vermischt, auf Rohpapier von 50 g/m² gestrichen und 10 Minuten bei 30°C getrocknet. Das Auftragsgewicht atro betragt 8 g/m². Das erhaltene CB-Blatt wird auf ein CF-Blatt, welches Aktivton enthält, gelegt. Wird Druck auf das Aufzeichnungsmaterial ausgeübt, dann entsteht sofort eine gelbe Färbung, die eine optische Dichte von 0,56 und λmax 460 nm aufweist. Example 10 : 0.56 g of 4-dimethylaminobenzaldehyde and 0.51 g of 4-isopropylaniline are dissolved together in diisopropylnaphthalene so that a 1% strength solution is obtained. The solution is microencapsulated in a known manner with gelatin and carboxymethyl cellulose and glutaraldehyde by coacervation. The capsule dispersion obtained is mixed with 5 g of a 20% strength aqueous polyvinyl alcohol solution and starch solution and 11 g of starch granules, coated on 50 g / m 2 raw paper and dried at 30 ° C. for 10 minutes. The application weight atro is 8 g / m². The CB sheet obtained is placed on a CF sheet which contains active clay. If pressure is exerted on the recording material, a yellow color is immediately produced, which has an optical density of 0.56 and λ max 460 nm.

Beispiel 11: 0,6 g 4-Dimethylaminozimtaldehyd und 0,46 g 4-Isopropylanilin werden zusammen in Diisopropylnaphthalin so gelöst, dass eine 1%ige Lösung entsteht. Die Lösung wird auf bekannte Weise mit Gelatine und Carboxymethylcellulose und Glutaraldehyd durch Koazervation mikroverkapselt. Die erhaltene Kapseldispersion wird mit 5 g einer 20%igen wässrigen Polyvinylalkohollösung und Stärkelösung und 11 g Stärkekörner vermischt, auf Streichrohpapier von 50 g/m² gestrichen und 10 Minuten bei 30°C getrocknet. Das Auftragsgewicht atro beträgt 8 g/m². Das erhaltene CB-Blatt wird auf ein CF-Blatt, welches Aktivton enthält, gelegt. Wird Druck auf das Aufzeichnungsmaterial ausgeübt, dann entsteht sofort eine magenta Färbung, die eine optische Dichte von 0,76 und λmax 540 nm aufweist Example 11 : 0.6 g of 4-dimethylaminocinnamaldehyde and 0.46 g of 4-isopropylaniline are dissolved together in diisopropylnaphthalene in such a way that a 1% strength solution is obtained. The solution is microencapsulated in a known manner with gelatin and carboxymethyl cellulose and glutaraldehyde by coacervation. The capsule dispersion obtained is mixed with 5 g of a 20% strength aqueous polyvinyl alcohol solution and starch solution and 11 g of starch granules, coated on base paper of 50 g / m 2 and dried at 30 ° C. for 10 minutes. The application weight atro is 8 g / m². The CB sheet obtained is placed on a CF sheet which contains active clay. If pressure is exerted on the recording material, a magenta coloration immediately arises, which has an optical density of 0.76 and λ max 540 nm

Beispiel 12: 0,51 g 4-Dimethylaminozimtaldehyd und 0,54 g 4-Aminodiphenylamin werden zusammen in Diisopropyinaphthalin so gelöst, dass eine 1%ige Lösung entsteht. Die Lösung wird auf bekannte Weise mit Gelatine und Carboxymethylcellulose und Glutaraldehyd durch Koazervation mikroverkapselt. Die erhaltene Kapseldispersion wird mit 5 g einer 20%igen wässrigen Polyvinylälkohollösung und Stärkelösung und 11 g Stärkekörner vermischt, auf Streichrohpapier von 50 g/m² gestrichen und 10 Minuten bei 30°C getrocknet. Das Auftragsgewicht atro beträgt 8 g/m². Das erhaltene CB-Blatt wird auf ein CF-Blatt, welches Aktivton enthält, gelegt. Wird Druck auf das Aufzeichnungsmaterial ausgeübt, dann entsteht sofort eine blauviolette Färbung, die eine optische Dichte von 0,78 und λmax 560 nm aufweist. Example 12 : 0.51 g of 4-dimethylaminocinnamaldehyde and 0.54 g of 4-aminodiphenylamine are dissolved together in diisopropyinaphthalene so that a 1% solution is formed. The solution is microencapsulated in a known manner with gelatin and carboxymethyl cellulose and glutaraldehyde by coacervation. The capsule dispersion obtained is mixed with 5 g of a 20% strength aqueous polyvinyl alcohol solution and starch solution and 11 g of starch granules, coated on coating base paper of 50 g / m 2 and dried at 30 ° C. for 10 minutes. The application weight atro is 8 g / m². The CB sheet obtained is placed on a CF sheet which contains active clay. Will print on the recording material exercised, then immediately a blue-violet coloration arises, which has an optical density of 0.78 and λ max 560 nm.

Claims (14)

  1. A pressure-sensitive recording material in which the colour reactant system comprises as essential components
    (A) an aromatic aldehyde compound of the formula
    Figure imgb0005
     wherein
    R₁ and R₂ are each independently of the other alkyl of not more than 12 carbon atoms which is unsubstituted or substituted by halogen, hydroxy, cyano or C₁-C₆alkoxy, acyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, or phenyl-C₁-C₃alkyl or phenyl, each unsubstituted or ring-substituted by halogen, cyano, C₁-C₆alkyl, C₁-C₆alkoxy or C₁-C₆alkoxycarbonyl, and R₂ is also hydrogen, or R₁ and R₂, together with the nitrogen atom linking them, are a five- or six-membered heterocyclic radical,
    Ar is naphthylene or phenylene which may be substituted by hydroxy, halogen, cyano, nitro, trihalomethyl, C₁-C₆alkyl, methylsulfonyl, C₁-C₆alkoxy, acyloxy or acylamino containing 1 to 8 carbon atoms, C₁-C₆alkylamino, di-C₁-C₆alkylamino, benzyloxy or phenoxy, and n is 1 or 2, or a nitrogen-containing heterocyclic aldehyde compound of the formula



            (3)   Z-CHO



    wherein Z is an unsubstituted or substituted pyrrolyl, antipyrinyl, triazinyl, indolyl, carbazolyl, julolidinyl, kairolinyl, indolinyl, iminodibenzyl, dihydroquinolinyl or tetrahydroquinolinyl radical,
    (B) an aniline, naphthylamine, aminoaniline, anilinesulfoanilide, aminophenylethylene, aminophenylstyrene, acylacetarylamide, 3-aminophenol ether, aminopyrazole, aminothiazole, pyrazolone, barbituric acid, pyrrolidine, piperidine, piperazine, morpholine, benzomorpholine, indoline, cyanomethylbenzimidazole, cyanomethylbenzoxazole or cyanomethylbenzothiazole compound or a fluoran or phthalide compound which has an unsubstituted amino group, and
    (C) an electron-withdrawing and colour-developing component.
  2. A recording material according to claim 1, wherein in formula (1) R₁ and R₂ are each C₁-C₆alkyl, chloro-C₁-C₆alkyl, cyano-C₁-C₆alkyl, benzyl or phenyl, or R₁ and R₂, together with the nitrogen atom they have in common, are pyrrolidino, piperidino or morpholino, Ar is naphthylene or phenylene which may be substituted by halogen, trifluoromethyl, C₁-C₆alkyl or C₁-C₆alkoxy, and n is 1 or 2.
  3. A recording material according to claim 1, wherein in formula (3) Z is a 2-pyrrolyl, N-C₁-C₈alkyl-pyrrol-2-yl, N-phenylpyrrol-3-yl, 3-indolyl, N-C₁-C₈alkyl-2-methylindol-3-yl, N-C₂-C₄alkanoyl-2-methylindol-3-yl, 2-phenylindol-3-yl, N-C₁-C₈alkyl-2-phenylindol-3-yl, N-C₁-C₈alkylcarbazol-3-yl or 1,3,3-trimethyl-2-methenylindolinyl radical.
  4. A recording material according to claim 1, wherein component (B) is an aniline, cresidine, phenetidine, aminodiphenylamine or toluidinesulfoanilide compound.
  5. A recording material according to claim 1, wherein component (B) is an aniline compound of the formula
    Figure imgb0006
     wherein
    V is hydrogen, hydroxyl, halogen, trifluoromethyl, C₁-C₆alkyl,
    C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkanoyloxy, benzyloxy or phenoxy, and
    m is 1 or 2.
  6. A recording material according to claim 5, wherein the condensation component (B) is an aminodiphenylamine compound.
  7. A recording material according to one of claims 1 to 6, wherein the colour-developing component (C) is a Lewis acid, an activated clay, a solid carboxylic acid or a compound containing a phenolic hydroxyl group.
  8. A recording material according to one of claims 1 to 7, wherein the colour-developing component (C) is an activated clay, a zinc salicylate, a metal-free phenol compound, a phenol-formaldehyde, a zinc-modified phenol-formaldehyde phenolic resin or a zinc thiocyanate complex.
  9. A recording material according to one of claims 1 to 8, wherein components (A) and (B) are dissolved in an organic solvent.
  10. A recording material according to one of claims 1 to 8, wherein components (A) and (B) are encapsulated in microcapsules.
  11. A recording material according to one of claims 1 to 10, wherein components (A) and (B) are present in the form of one or two layers on the back of a transfer sheet and component (C) is present in the form of a layer on the front of a receiver sheet.
  12. A pressure-sensitive recording material according to one of claims 1 to 11, wherein component (C) is an activated clay or a zinc salicylate.
  13. A recording material according to one of claims 1 to 12, wherein components (A) and (B) are present together with one or more conventional colour formers from the class of 3,3-(bisaminophenyl)-phthalides such as CVL, 3-indolyl-3-aminophenylaza- or diazaphthalides, (3,3-bisindolyl)-phthalides, 3-aminofluorans, 6-dialkylamino-2-dibenzylaminofluorans, 6-dialkylamino-3-methyl-2-arylaminofluorans, 3,6 bisalkoxyfluorans, 3,6-bisdiarylaminofluorans, leucoauramines, spiropyrans, spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes and triarylmethanes.
  14. A material according to claim 13, wherein the conventional colour formers present are 3,3-(bisaminophenyl)phthalides, 3-indolyl-3-aminophenylaza- or diazaphthalides, (3,3-bisindolyl)-phthalides, 3-aminofluorans, 6-dialkylamino-2-dibenzylaminofluorans, 6-dialkylamino-3-methyl-2-arylaminofluorans, 3,6-bisalkoxyfluorans, 3,6-bisdiarylaminofluorans, leucoauramines, spiropyrans, spirodipyrans, chromenopyrazoles, chromenoindoles, benzoxazines, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes.
EP91810189A 1990-03-29 1991-03-21 Pressure sensitive recording material Expired - Lifetime EP0453395B1 (en)

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CH103590 1990-03-29

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JPH07223371A (en) * 1993-04-30 1995-08-22 Ricoh Co Ltd Thermal recording material
US5709738A (en) * 1996-06-06 1998-01-20 Moore Business Forms Inc Coating composition for ink jet printing
US5814579A (en) * 1996-08-06 1998-09-29 The Standard Register Company Multicolor printing system
US11905260B1 (en) 2023-10-13 2024-02-20 King Faisal University N′-(1-naphthoyloxy)-2-(benzo[d]oxazol-2-yl)acetimidamide as an antimicrobial compound

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US3174038A (en) * 1962-06-18 1965-03-16 Dietzgen Co Eugene Thermographic reproduction paper and method of using
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AU7396691A (en) 1991-10-03
AU636968B2 (en) 1993-05-13

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