Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—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

• Components (A), (B) and (C) come into contact with one another by pressure or heating, depending on the recording material, and leave records on the carrier material.
• the color is generated in accordance with the type of components (A) and (B) which constitute the electron donor and form the chromogenic part.
• the color formation is caused by component (C).
• the desired colors such as yellow, orange, red, violet, blue, green, gray, black or mixed colors, can thus be generated 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-dialkylamino-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 triary
• aromatic aldehyde compounds which can be used as component (A) advantageously correspond to the formula wherein R1 and R2, independently of one another, each unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or unsubstituted or by halogen, cyano, lower alkyl, lower alkoxy, Lower 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, preferably saturated, heterocyclic radical, Ar naphthylene or phenylene, which can be substituted by hydroxy, halogen, cyano, nitro, trihalomethyl, lower alkyl, methylsulfonyl, lower alkoxy,
• 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, lower alkoxy lower alkyl, cyano lower alkyl e.g. ⁇ -cyanoethyl or primarily lower alkyl, e.g. Methyl, ethyl or n-butyl.
• -NR1R2 is also preferably pyrrolidinyl.
• R1 and R2 each represent lower alkyl, chloro-lower alkyl, cyano-lower alkyl, benzyl, phenyl or R1 and R2 together with the common nitrogen atom represent pyrrolidino, piperidino or morpholino, ar naphthylene or phenylene, which is optionally substituted by hydroxy, halogen, trifluoromethyl, lower alkyl or lower alkoxy and n is 1 or 2.
• Aromatic compounds are also expediently used as aromatic aldehyde compounds correspond in which A represents a mononuclear or polynuclear aryl radical which is substituted by hydroxyl, halogen, cyano, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl can be substituted in question.
• the aryl radical is derived, for example, from benzene, diphenyl, naphthalene, anthracene, acenaphthene, acenaphthylene or pyrene.
• the nitrogen-containing heterocyclic aldehyde compounds required for component (A) advantageously correspond to the formula Z-CHO wherein Z represents an optionally substituted pyrrolyl, antipyrinyl, triazinyl, indolyl, carbazolyl, julolidinyl, kairolinyl, indolinyl, iminodibenzyl, dihydroquinolinyl or tetrahydroquinolinyl radical.
• the mono- or polynuclear heterocyclic radical Z can be ring-substituted one or more times.
• the C substituents are e.g. Halogen, hydroxy, cyano, nitro, lower alkyl, lower alkoxy, lower alkylthio, lower alkoxycarbonyl, acyl with 1 to 8 carbon atoms, preferably lower alkylcarbonyl, lower alkylamino, lower alkylcarbonylamino or diniederalkylamino, 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
• the alkyl and akenyl 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-Akanoyl-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 is especially formyl, lower alkylcarbonyl, such as acetyl or propionyl, or benzoyl.
• Other acyl radicals can be lower alkylsulfonyl, such as methylsulfonyl or Ethylsulfonyl and phenylsulfonyl.
• Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
• Lower alkyl, lower alkoxy and lower alkylthio are groups or group components which have 1 to 6, in particular 1 to 3, carbon atoms.
• Examples of such groups 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), (2) 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-
• Preferred specific components (A) are 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylaminocinnamaldehyde and indole-3-aldehyde.
• components (B) used according to the invention which form chromogenic compounds with component (A), are preferably mono- or polycyclic aromatic or heterocyclic compounds which supplement a system of conjugated double bonds and, if necessary, auxochromic substituents in addition to the condensable methylene group or primary or secondary amino group, such as e.g. have disubstituted amino groups such as di-lower alkylamino, hydroxyl groups, ether groups such as alkoxy, thiol groups or mercapto groups such as alkylthio.
• Such compounds suitably originate from aromatic amines or from nitrogen heterocycles such as e.g. from the series of anilines, naphthylamines, anilinesulfonic acid anilides, aminophenylethylene compounds, aminophenylstyrene compounds, acylacetarylamides, 3-aminophenol ethers, aminothiazoles, pyrazolones, barbituric acids, pyrrolidines, piperidines, piperomine benzene, morphobenzene
• 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, malononitrile, 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-pyra
• 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-amino-phthalide.
• 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.
• Inorganic or organic color developers known for recording materials and capable of attracting electrons can be used as component (C).
• Typical examples of inorganic developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
• active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite
• activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
• Preferred inorganic color developers are Lewis acids, e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.
• Lewis acids e.g. Aluminum chloride, aluminum bromide, zinc chloride, iron (III) chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride bismuth trichloride, tellurium dichloride or antimony pentachloride.
• Solid organic acids 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 can be used.
• Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be 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 are 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 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. 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 achieved if the 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)), comprises at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.
• component (C) comprises at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.
• the ternary color image system comprising components (A), (B) and (C) used according to the invention is also suitable for producing a heat-sensitive recording material for thermography, components (A), (B) and (C) being heated together to form a color in Come into contact and leave records on the carrier material.
• the heat-sensitive recording material generally contains at least one layer support, components (A), (B) and (C) and optionally also a binder and / or wax. If desired, activators or sensitizers, for example Benzyldiphenyl be present in the recording material.
• Thermoreactive recording systems include, e.g. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. in electronic calculating machines, printers, facsimile or copying machines or in medical and technical recording devices and measuring instruments, e.g. Electrocardiographs or for the production of labels or bar codes.
• the imaging (marking) can also be done manually with a heated spring.
• Another device for generating markings using heat is laser beams.
• thermoreactive recording material can be constructed such that components (A) and (B) are dissolved or dispersed in a binder layer and in a second layer the developer (component (C)) is dissolved or dispersed in the binder. Another possibility is that all three components are dispersed in the same layer.
• the layer or layers are softened in specific areas by means of heat, components (A), (B) and (C) coming into contact with one another on the parts to which heat is applied and the desired color develops immediately.
• thermoreactive recording material can also contain the encapsulated component (A) and / or (B).
• Fusible, film-forming binders are preferably used to produce the heat-sensitive recording material. These binders are normally water soluble, while components (A), (B) and (C) are insoluble in water. The binder should be able to disperse the three components at room temperature and fix them on the substrate.
• Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, alkali metal polyacrylates, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.
• hydrophilic polymers such as polyvinyl alcohol, alkali metal polyacrylates, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.
• water-insoluble binders ie nonpolar or only weakly polar solvents soluble binders, such as natural rubber, synthetic rubber, chlorinated rubber, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
• soluble binders such as natural rubber, synthetic rubber, chlorinated rubber, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole.
• the preferred arrangement is one in which all three components are contained in one layer in a water-soluble binder.
• Protective layers of this type generally consist of water-soluble and / or water-insoluble resins which are conventional polymer materials or aqueous emulsions of these polymer materials.
• water-soluble polymer materials are polyvinyl alcohol, starch, starch derivatives, cellulose derivatives, such as methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose or ethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, polyacrylamide / acrylic acid ester copolymers, acrylamide / acrylic acid ester / methacrylic acid / copolymeric acid-alkali acid-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copoly
• water-insoluble resins e.g. the following water-insoluble resins are used: polyvinyl acetate, polyurethanes, styrene / butadiene copolymers, polyacrylic acid, polyacrylic acid esters, vinyl chloride / vinyl acetate copolymers, polybutyl methacrylate, ethylene / vinyl acetate copolymers and styrene / butadiene / acrylic derivative copolymers.
• thermoreactive layers and the resin layers can contain further additives.
• these layers for example antioxidants, UV absorbers, solution aids, talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (eg chalk), magnesium carbonate, Contain clays or organic pigments, such as urea-formaldehyde polymers.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid benzyl ester, Metal stearates, such as, for example, zinc stearate, phthalonitrile, dimethyl terephthalate, dibenzyl terephthalate, dibenzyl isophthalate, benzyl diphenyl or other corresponding meltable products which induce the simultaneous melting of the color former components and the developer, are added.
• Thermographic recording materials preferably contain waxes, e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, micro wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• waxes e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, micro wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• thermochromatic materials the three components (A), (B) and (C) can be enclosed in microcapsules.
• any of the above-known methods for enclosing color formers or other active substances in microcapsules can be used.
• 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 light-fast, yellow color is obtained with a ⁇ maximum of 460 nm.
• Example 4 1.2 g of 4-dimethylaminocinnamaldehyde 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 ( ⁇ max 560 nm) is also obtained.
• Example 6 To prepare 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 milled.
• 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 material applied 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 of 3,3-bis (Nn-octyl-2'-methylindol-3'-yl) phthalide, 0.66 g of 4-dimethylamino-benzaldehyde and 0.6 g of 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 gravure 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 in example 8 4-dimethylaminocinnamaldehyde is replaced by the same amount of 4-diethylaminobenzaldehyde and the procedure is otherwise as described in the example, an intense lightfast, 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% 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 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 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 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 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. 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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• Optics & Photonics (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Color Printing (AREA)

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• 1991
  • 1991-03-21 DE DE59106793T patent/DE59106793D1/de not_active Expired - Fee Related
  • 1991-03-21 EP EP91810189A patent/EP0453395B1/fr not_active Expired - Lifetime
  • 1991-03-26 US US07/675,213 patent/US5254522A/en not_active Expired - Fee Related
  • 1991-03-28 JP JP3063641A patent/JPH04221675A/ja not_active Withdrawn
  • 1991-03-28 AU AU73966/91A patent/AU636968B2/en not_active Ceased

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