EP0453395B1 - Matériau d'enregistrement sensible à la pression - Google Patents

Matériau d'enregistrement sensible à la pression 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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Prior art keywords
recording material
material according
compound
component
c6alkyl
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EP91810189A
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German (de)
English (en)
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EP0453395A1 (fr
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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
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  • Heat Sensitive Colour Forming Recording (AREA)
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Claims (14)

  1. Matériau d'enregistrement sensible à la pression, dans lequel le système de réactifs formant une couleur contient, en tant que constituants principaux :
    (A) un aldéhyde aromatique de formule
    Figure imgb0007
     dans laquelle
    R₁ et R₂ représentent chacun, indépendamment l'un de l'autre, un groupe alkyle comportant au plus 12 atomes de carbone, portant ou non des substituants halogéno, hydroxy, cyano ou alcoxy en C₁-C₆, un groupe acyle comportant de 1 à 8 atomes de carbone, un groupe cycloalkyle comportant de 5 à 10 atomes de carbone ou un groupe phényle ou phényl-(alkyle en C₁-C₃) dont le cycle porte ou non des substituants halogéno, cyano, alkyle en C₁-C₆, alcoxy en C₁-C₆ ou (alcoxy en C₁-C₆)-carbonyle, R₂ pouvant également représenter un atome d'hydrogène, ou bien R₁ et R₂ représentent ensemble, conjointement avec l'atome d'azote auquel ils sont liés, un groupe hétérocyclique à cinq ou six chaînons,
    Ar représente un groupe naphtylène ou phènylène, qui peut porter des substituants hydroxy, halogéno, cyano, nitro, trihalogénométhyle, alkyle en C₁-C₆, méthylsulfonyle, alcoxy en C₁-C₆, acyloxy ou acylamino comportant de 1 à 8 atomes de carbone, (alkyl en C₁-C₆)-amino, di-(alkyl en C₁-C₆)-amino, benzyloxy ou phénoxy, et
    n vaut 1 ou 2, ou bien
    un aldéhyde hétérocyclique azoté, de formule



            Z-CHO   (3)



    dans laquelle Z représente un reste pyrrolyle, antipyrinyle, triazinyle, indolyle, carbazolyle, julolidinyle, kairolinyle, indolinyle, iminodibenzyle, dihydroquinolinyle ou tétrahydroquinolinyle, éventuellement substitué,
    (B) un dérivé d'aniline, de naphtylamine, d'aminoaniline, d'anilide d'acide sulfanilique, d'aminophényléthylène, d'aminophénylstyrène, d'acylacétarylamide, d'éther de 3-aminophénol, d'aminopyrazole, d'aminothiazole, de pyrazolone, d'acide barbiturique, de pyrrolidine, de pipéridine, de pipérazine, de morpholine, de benzomorpholine, d'indoline, de cyanométhylbenzoimidazole, de cyanométhylbenzoxazole ou de cyanométhylbenzothiazole, ou encore de fluoranne ou de phtalide, qui comporte un groupe amino nonsubstitué, et
    (C) un composant électro-attracteur servant à faire apparaître une couleur.
  2. Matériau d'enregistrement conforme à la revendication 1, caractérisé en ce que, dans la formule (1), R₁ et R₂ représentent chacun un groupe alkyle en C₁-C₆, chloroalkyle en C₁-C₆, cyano-alkyle en C₁-C₆, benzyle ou phényle, ou R₁ et R₂ représentent, conjointement avec l'atome d'azote qui les relie, un groupe pyrrolidino, pipéridino ou morpholino, Ar représente un groupe naphtylène ou phénylène portant éventuellement des substituants hydroxy, halogéno, trifluorométhyle, alkyle en C₁-C₆ ou alcoxy en C₁-C₆, et n vaut 1 ou 2.
  3. Matériau d'enregistrement conforme à la revendication 1, caractérisé en ce que, dans la formule (3), Z représente un groupe 2-pyrrolyle, N-(alkyl en C₁-C₈)-pyrrole-2-yle, N-phényl-pyrrole-3-yle, 3-indolyle, N-(alkyl en C₁-C₈)-2-méthyl-indole-3-yle, N-(alcanoyl en C₂-C₄)-2-méthyl-indole-3-yle, 2-phényl-indole-3-yle, N-(alkyl en C₁-C₈)-2-phényl-indole-3-yle, N-(alkyl en C₁-C₈)-carbazole-3-yle ou 1,3,3-triméthyl-2-méthényl-indolinyle.
  4. Matériau d'enregistrement conforme à la revendication 1, caractérisé en ce que le composant (B) est un dérivé de l'aniline, de la crésidine, de la phénétidine, d'une aminodiphénylamine ou d'un toluidinesulfanilide.
  5. Matériau d'enregistrement conforme à la revendication 1, caractérisé en ce que le composant (B) est un dérivé d'aniline de formule :
    Figure imgb0008
     dans laquelle V représente un atome d'hydrogène ou d'halogène ou un groupe hydroxy, trifluorométhyle, alkyle en C₁-C₆, alcoxy en C₁-C₆, (alcoxy en C₁-C₆)-carbonyle, alcanoyloxy en C₁-C₆, benzyloxy ou phénoxy, et m vaut 1 ou 2.
  6. Matériau d'enregistrement conforme à la revendication 5, caractérisé en ce que le composant de condensation (B) est un dérivé d'une aminodiphénylamine.
  7. Matériau d'enregistrement conforme à l'une des revendications 1 à 6, caractérisé en ce que le composant (C) de développement de couleur est un acide de Lewis, une argile active, un acide carboxylique solide ou un composé comportant un groupe hydroxy phénolique.
  8. Matériau d'enregistrement conforme à l'une des revendications 1 à 7, caractérisé en ce que le composant (C) de développement de couleur est une argile active, un salicylate de zinc, un composé phénolique non-métallé, une résine phénol-formaldéhyde, une résine phénolformaldéhyde modifiée par du zinc, ou un complexe de thiocyanate de zinc.
  9. Matériau d'enregistrement conforme à l'une des revendications 1 à 8, caractérisé en ce que les composants (A) et (B) sont dissous dans un solvant organique.
  10. Matériau d'enregistrement conforme à l'une des revendications 1 à 8, caractérisé en ce que les composants (A) et (B) sont enfermés dans des microcapsules.
  11. Matériau d'enregistrement conforme à l'une des revendications 1 à 10, caractérisé en ce que les composants (A) et (B) se trouvent dans une ou deux couches déposées au verso d'une feuille de transfert, et le composant (C) se trouve dans une couche déposée au recto d'une feuille réceptrice.
  12. Matériau sensible à la pression, conforme à l'une des revendications 1 à 11, caractérisé en ce que le composant (C) est une argile active ou un salicylate de zinc.
  13. Matériau d'enregistrement conforme à l'une des revendications 1 à 12, caractérisé en ce que les composants (A) et (B) sont présents conjointement avec un ou plusieurs agents chromogènes classiques, appartenant à l'ensemble constitué par les 3,3-bis(aminophényl)-phtalides comme le CVL, les 3-indolyl-3-aminophénylazaou -diaza-phtalides, les 3,3-bis-indolylphtalides, les 3-aminofluorannes, les 6-dialkylamino-2-dibenzylaminofluorannes, les 6-dialkylamino-3-méthyl-2-arylaminofluorannes, les 3,6-bis(alcoxy)fluorannes, les 3,6-bis-(diarylamino)fluorannes, les leuco-auramines, les spiropyrannes, les spirodipyrannes, les benzoxazines, les chroménopyrazoles, les chroménoindoles, les phénoxazines, les phénothiazines, les quinazolines, les lactames de rhodamine, les carbazolylméthanes et les triarylméthanes.
  14. Matériau conforme à la revendication 13, caractérisé en ce que l'on y trouve, comme agents chromogènes classiques, des 3,3-bis(aminophényl)phtalides, des 3-indolyl-3-aminophénylaza- ou diazaphtalides, des 3,3-bis-indolylphtalides, des 3-aminofluorannes, des 6-dialkylamino-2-dibenzylamino-fluorannes, des 6-dialkylamino-3-méthyl-2-arylamino-fluorannes, des 3,6-bis(alcoxy)fluorannes, des leuco-auramines, des spilopyrannes, des spirodipyrannes, des benzoxazines, des chroménopyrazoles, des chroménoindoles, des phénoxazines, des phénothiazines, des quinazolines, des lactames de rhodamine, des carbazolyl-méthanes ou des triarylméthanes.
EP91810189A 1990-03-29 1991-03-21 Matériau d'enregistrement sensible à la pression Expired - Lifetime EP0453395B1 (fr)

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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
US11970467B1 (en) 2023-10-13 2024-04-30 King Faisal University N′-(2-naphthoyloxy)-2-(benzo[d]oxazol-2-yl)acetimidamide as an antimicrobial compound
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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EP0453395A1 (fr) 1991-10-23
US5254522A (en) 1993-10-19
AU636968B2 (en) 1993-05-13
DE59106793D1 (de) 1995-12-07
JPH04221675A (ja) 1992-08-12

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