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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/136—Organic colour formers, e.g. leuco dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/136—Organic colour formers, e.g. leuco dyes
  • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring

Definitions

• Heat-sensitive recording materials are generally prepared by applying a coating composition to the surface of a support such as paper, which is obtained by finely grinding and dispersing a colorless chromogenic substance (color former) and a color developer as an electron acceptor, mixing the dispersions obtained with one another and adding a binder, filler and other aids, such as Lubricants and / or sensitizers have been obtained.
• a coating composition obtained by finely grinding and dispersing a colorless chromogenic substance (color former) and a color developer as an electron acceptor, mixing the dispersions obtained with one another and adding a binder, filler and other aids, such as Lubricants and / or sensitizers have been obtained.
• a chemical reaction of the chromogenic compound with the color developer takes place in the coating, with color formation.
• the color images are generally produced by exerting pressure on the microcapsules applied to the paper, which enclose the chromogenic substance, the color reaction between the chromogen and the acceptor taking place in the presence of solvents.
• Components (A), (B) and (C) come into contact with one another by pressure or heating, depending on the recording material, and leave records on the carrier material.
• the color is produced in accordance with the type of components (A) and (B), which represent the electron donor and form the chromogenic part.
• the color formation is caused by component (C).
• the desired colors e.g. yellow, orange, red, violet, blue, green, gray, black or mixed colors can be generated.
• components (A) and (B) together with one or more conventional color formers e.g.
• 3,3- (bis-aminophenyl -) phthalides such as CVL, 3-indolyl-3-aminophenylaza- or -diazaphthalides, (3,3-bis-indolyl -) - phthalides, 3-aminofluoranes, 6-dialkylamino-2- dibenzylaminofluoranes-, 6-dialkylamino-3-methyl-2-arylaminofluoranes, 3,6-bisalkoxyfluoranes, 3,6-bisdiarylaminofluoranes, leucoauramines, spiropyrans, spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazinesazolines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phen
• the compounds of formula (1) contain, as part of their structure, the basic structure of, for example, a lactone, lactam, sulton, sultam or phthalan, and these basic structures are subject to - before, during or after the reaction of component (A) with the condensation component (B) - upon contact with the color developer (component (C)) a ring opening or bond cleavage, as is also assumed from the recording materials customary hitherto.
• the heteroaromatic radical X is expediently bonded to the central (meso) carbon atom of the polycyclic compound via a carbon atom of the hetero ring.
• X means e.g. a thienyl, acridinyl, benzofuranyl, benzothienyl, naphthothienyl or phenothiazinyl radical, but advantageously a pyrrolyl, indolyl, carbazolyl, julolidinyl, kairolinyl, indolinyl, dihydroquinolinyl or tetrahydroquinolyl radical.
• the mono- or polynuclear heteroaromatic radical 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, amino, lower alkylamino, lower alkylcarbonylamino or di-lower 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,
• 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.
• acyl is especially formyl, lower alkyl carbonyl, e.g. Acetyl or propionyl, or benzoyl. Further acyl residues can be lower alkylsulfonyl, e.g. Be methylsulfonyl or ethylsulfonyl and phenylsulfonyl. Benzoyl and phenylsulfonyl can be substituted by halogen, methyl, methoxy or ethoxy.
• 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.
• Preferred heteroaromatic residues are substituted 2- or 3-pyrrolyl or especially 3-indolyl residues, e.g. N-C1-C8-alkyl-pyrrol-2-yl-, N-phenylpyrrol-3-yl-, N-C1-C8-alkyl-2-methylindol-3-yl-, N-C2-C4-alkanoyl-2 -methylindol-3-yl, 2-phenylindol-3-yl or N-C1-C8-alkyl-2-phenylindol-3-yl radicals.
• 3-indolyl residues e.g. N-C1-C8-alkyl-pyrrol-2-yl-, N-phenylpyrrol-3-yl-, N-C1-C8-alkyl-2-methylindol-3-yl-, N-C2-C4-alkanoyl-2 -methylindol-3-yl, 2-phenylindo
• X can be an aromatic radical which is unsubstituted or substituted by halogen, cyano, lower alkyl, C5-C6-cycloalkyl, C1-C8-acyl, -NR1R2, -OR3 or -SR3 or phenyl or naphthyl.
• X preferably represents a substituted phenyl radical of the formula represents.
• R1, R2 and R3, independently of one another, are each hydrogen, unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, acyl having 1 to 8 Carbon atoms, cycloalkyl having 5 to 10 carbon atoms or unsubstituted or ring-substituted phenalkyl or phenyl, wherein X 'and X ⁇ , independently, by halogen, trifluoromethyl, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X ⁇ or 4-NX'X ⁇ -phenylamino represent hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R1 and R2 together with the nitrogen atom connecting them form a five- or six-membered, preferably saturated, heterocyclic radical.
• V denotes hydrogen, halogen, lower alkyl, C1-C12-alkoxy, C1-C12-acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, benzyl or benzyloxy substituted by halogen, cyano, lower alkyl or lower alkoxy, or the group -NT1T2.
• T1 and T2 independently of one another, each represent hydrogen, lower alkyl, C5-C10 cycloalkyl, unsubstituted or substituted by halogen, cyano, lower alkyl or lower alkoxy, or acyl having 1 to 8 carbon atoms and T1 also unsubstituted or by halogen, cyano, lower alkyl or lower alkoxy substituted phenyl.
• m is 1 or 2.
• -NR1R2 and -OR3 are preferably in the para position to the junction.
• a V is preferably in the ortho position to the connection point.
• R, R1, R2 and R3 represent, for example, the substituents listed above for alkyl radicals.
• alkyl radicals in R1, R2 and R3 are substituted, it is primarily cyanoalkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl each preferably with a total of 2 to 8 carbon atoms, such as e.g. 2-cyanoethyl, 2-chloroethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2,3-dihydroxypropyl, 2-hydroxy-3-chloropropyl, 3-methoxypropyl, 4-methoxybutyl or 4-propoxybutyl.
• cycloalkyl in the meaning of R, R1, R2, R3, T1 and T2 are cyclopentyl, cycloheptyl or preferably cyclohexyl.
• the cycloalkyl radicals can contain one or more C1-C4 alkyl radicals, preferably methyl groups, and have a total of 5 to 10 carbon atoms.
• R, R1, R2 and R3 can be phenethyl, phenylisopropyl or especially benzyl.
• Preferred substituents in the phenalkyl and phenyl group of the R radicals are e.g. Halogen, cyano, methyl, trifluoromethyl, methoxy or carbomethoxy.
• araliphatic or aromatic radicals are methylbenzyl, 2,4- or 2,5-dimethylbenzyl, chlorobenzyl, dichlorobenzyl, cyanobenzyl, tolyl, xylyl, chlorophenyl, methoxyphenyl, 2,6-dimethylphenyl, trifluoromethylphenyl or carbomethoxyphenyl.
• the acyloxy radical in V is, for example, formyloxy, lower alkylcarbonyloxy, e.g. Acetyloxy or propionyloxy, or benzoyloxy.
• V can be a straight-chain or branched group, e.g. Methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, amyloxy, 1,1,3,3-tetramethylbutoxy, n-hexyloxy, n-octyloxy or dodecyloxy.
• the pair of substituents (R1 and R2) together with the common nitrogen atom represent a heterocyclic radical
• this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino, piperazino, N-alkylpiperazino, such as e.g. N-methylpiperazino, N-phenylpiperazino or N-alkylimidazolino.
• Preferred saturated heterocyclic radicals for -NR1R2 are pyrrolidino, piperidino or morpholino.
• R1 and R2 are preferably cyclohexyl, benzyl, phenethyl, cyano-lower alkyl e.g. ⁇ -cyanoethyl or primarily lower alkyl, e.g. Methyl, ethyl or n-butyl.
• -NR1R2 is also preferably pyrrolidinyl.
• R3 is preferably lower alkyl or benzyl.
• V can advantageously be hydrogen, halogen, lower alkyl, such as methyl, benzyloxy, C1-C8-alkoxy, primarily lower alkoxy, such as methoxy, ethoxy, isopropoxy or tert-butoxy, or the group -NT1T2, with the radicals being T1 and T2 is preferably C1-C8 acyl or lower alkyl and the other is hydrogen or lower alkyl.
• the acyl radical in this case is especially lower alkylcarbonyl, such as acetyl or Propionyl.
• V is preferably acetylamino, dimethylamino, diethylamino, benzyloxy or especially lower alkoxy and especially ethoxy or hydrogen.
• Substituents in the sense of Y are easily removable substituents on the central (meso) carbon atom, which thereby turn into an anion.
• substituents can be halogen atoms, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether groups, such as alkoxy, heteroaryloxy, aryloxy, cycloalkoxy and aralkoxy, or in particular acyloxy groups, for example of the formula (1c) R '- (NH-) n-1 -Q'-O- correspond in which R 'is an organic radical, preferably unsubstituted or substituted C1-C22-alkyl, aryl, cycloalkyl, aralkyl or heteroaryl, Q' -CO- or -SO2- and n is 1 or 2, preferably 1.
• acyloxy groups include acetyloxy, propionyloxy, chloroacetyloxy, benzoyloxy, methylsulfonyloxy, ethylsulfonyloxy, chloroethylsulfonyloxy, trifluoromethylsulfonyloxy, 2-chloroethylsulfonylacetyloxy, phenylsulfonyloxy, tolylsulfonyloxy or phenylaminocarbonyl.
• Y is preferably an acyloxy group of the formula R ⁇ -CO-O-, where R ⁇ is lower alkyl or phenyl.
• Q1 preferably represents an oxygen atom, while Q2 preferably represents -SO2-or especially -CO-. If Q1 represents ⁇ NR or ⁇ N-NH-R, R is preferably hydrogen, methyl or phenyl.
• A is preferably a benzene ring which is unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, lower alkylthio, lower alkylcarbonyl, lower alkoxycarbonyl, amino, lower alkylamino, di-lower alkylamino or lower alkylcarbonylamino.
• A is in particular a nitrogen-containing heterocycle with an aromatic character, such as a pyridine or pyrazine ring.
• Ring A can also contain a fused aromatic ring, preferably a benzene ring and thus represents for example a naphthalene, quinoline or quinoxaline ring.
• the preferred 6-membered aromatic or heterocyclic radicals represented by A are the 2,3-pyridino-, 3,4-pyridino-, 2,3-pyrazino-, 2,3-quinoxalino-, 1,2-naphthalino-, 2 , 3-Naphthalino- or 1,2-benzo radical which is unsubstituted or substituted by halogen, such as chlorine or bromine, nitro, lower alkyl, lower alkoxy, lower alkylthio or an amino group optionally substituted as defined above, the unsubstituted or by halogen, especially 1,2-benzo radical substituted by 4 chlorine atoms is particularly preferred.
• halogen such as chlorine or bromine, nitro, lower alkyl, lower alkoxy, lower alkylthio or an amino group optionally substituted as defined above
• Particularly important components (A) for the color reactant system according to the invention correspond to the formula wherein A1 an optionally substituted by halogen, cyano, lower alkyl, lower alkoxy or di-lower alkylamino benzene or pyridine ring, Y1 halogen, acyloxy and especially lower alkylcarbonyloxy or benzoyloxy and X1 is a 3-indolyl radical of the formula or a substituted phenyl radical of the formula mean, where W1 is hydrogen, unsubstituted or substituted by cyano or lower alkoxy C1-C8-alkyl, acetyl, propionyl or benzyl, W2 is hydrogen, lower alkyl, especially methyl, or phenyl, R4, R5 and R6 independently of one another, each unsubstituted or substituted by hydroxy, cyano or lower alkoxy alkyl having at most 12 carbon atoms, C5-C6-cycloalky
• the lactone compounds in which X1 is a 3-indolyl radical of the formula (2a) in which W1 is C1-C8-alkyl, W2 is methyl or phenyl and Y1 are lower alkylcarbonyloxy, in particular acetyloxy, are preferred.
• Lactone compounds of the formula are of particular interest in which the ring D is unsubstituted or substituted by 4 chlorine atoms, Y2 acetyloxy or benzoyloxy and W3 C1-C8-alkyl, such as ethyl, n-butyl or n-octyl mean.
• Lactone compounds of the formula are also particularly preferred wherein D and Y2 have the meaning given in formula (3) and R7, R8 and R9 each represent lower alkyl.
• Compounds of formula (1) which have an acyloxy group as removable substituents Y can be prepared by using a keto acid or carbinol compound (lactol) of the formula wherein A, Q1, Q2 and X have the meaning given, reacted with an acylating agent.
• Suitable acylating agents are reactive functional derivatives of aliphatic, cycloaliphatic or aromatic carboxylic acids or sulfonic acids, especially carboxylic acid halides or anhydrides such as e.g. Acetyl bromide, acetyl chloride, benzoyl chloride and especially acetic anhydride.
• carboxylic acid halides or anhydrides such as e.g. Acetyl bromide, acetyl chloride, benzoyl chloride and especially acetic anhydride.
• Mixed anhydrides i.e. Anhydrides of two different acids can be used.
• Compounds of formula (1) which contain halogen as removable substituents Y are prepared by passing the hydroxyl group of the carbinol compound of formula (i) through a halogen atom with a halogenating agent, for example by means of thionyl chloride, phosgene, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride in dimethylformamide, dichlorobenzene , Benzene, toluene or ethylene dichloride replaced.
• a halogenating agent for example by means of thionyl chloride, phosgene, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride in dimethylformamide, dichlorobenzene , Benzene, toluene or ethylene dichloride replaced.
• the halogenating agent can also be used in excess without a solvent.
• ether groups By reacting compounds of the formula (1) in which Y is halogen or acyloxy with aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic hydroxy compounds, ether groups can be introduced as further removable substituents Y.
• Suitable alkylating agents are alkyl halides, e.g. Methyl or ethyl iodide, ethyl chloride or dialkyl sulfates, such as dimethyl sulfate or diethyl sulfate.
• Particularly suitable aralkylating agents are benzyl chloride or the corresponding substitution products, e.g. 4-chlorobenzyl chloride, preferably in a non-polar organic solvent such as e.g. Benzene, toluene or xylene can be used.
• condensation components are all those customary in azochemistry and from the relevant literature, such as MR. Swiss, artificial org. Dyes and their intermediates, Springer-Verlag 1964, p. 420 ff.
• condensation components of the benzene series the naphthalene series, the open-chain methylene-active compounds and the heterocyclic series.
• condensation components are N-substituted aminophenylethylene compounds, N-substituted aminophenylstyrene compounds, acylacetarylamides, monovalent or polyvalent phenols, phenol ethers (phenetols), 3-aminophenol ethers, anilines, naphthylamines, thionaphthenes, diarylamines, naphthols, naphtholololidine piperoline, pyridoline pidylidene pidoxides, Aminopyrazoles, pyrazolones, thiophenes, acridines, aminothiazoles, phenothiazines, pyridones, indoles, indolizines, quinolones, pyrimidones, barbituric acids, carbazoles, benzomorpholines, 2-methylene-benzopyrans, dihydroquinolines, tetrahydroquinolines, indolines, acy
• Particularly preferred condensation components are anilines, such as cresidines, phenetidines or N, N-di-lower alkylanilines, 2-lower alkyls, 3-lower alkylindoles or 2-phenylindoles, each of which may be N-substituted by C1-C8-alkyl and 5-pyrazolones.
• Further preferred coupling components are 3-lower alkyl-6-lower alkoxy- or -6-di-lower alkylaminoindoles, which can also each be N-substituted by C1-C8-alkyl.
• condensation components are 2-amino-4-methoxytoluene, 3-amino-4-methoxytoluene N, N-dimethylaniline, N, N-diethylaniline, N, N-dibenzylaniline, 3-n-butoxy-N, N-di- n-butylaniline, 2-methyl-5-acetyloxy-N, N-diethylaniline, 4-ethoxydiphenylamine, 3-ethoxy-N, N-dimethylaniline, N, N'-diphenyl-p-phenylenediamine, m-phenetidine, 3-ethoxy -N, N-diethylaniline, 1,3-bis-dimethylaminobenzene, 3-hydroxy-N, N- (di-2'-cyclohexylethyl) aminobenzene, 1,1- (4'-diethylaminophenyl) ethylene, 1-phenyl-3 -methyl-5-pyrazol
• Preferred components (B) are also phthalide and especially fluoran compounds which have at least one primary amino group or an amino group monosubstituted by lower alkyl, cyclohexyl or benzyl. These phthalide and fluoran compounds are described for example in FR-A-1 553 291, GB-A-1 211 393, DE-A-2 138 179, DE-A-2 422 899 and EP-A-138 177.
• components (B) are: 2-amino-6-diethylaminofluoran, 2-amino-6-dibutylaminofluoran, 2-amino-3-chloro-6-diethylaminofluoran, 2-methylamino-6-dimethylaminofluoran, 2-ethylamino-6-diethylaminofluoran, 2-methylamino-6-diethylaminofluoran, 2-n-butylamino-6-diethylaminofluoran, 2-n-octylamino-6-diethylaminofluoran, 2-sec butylamino-6-diethylaminofluoran, 2-benzylamino-6-diethylaminofluoran, 2,3-dimethyl-6-ethylaminofluoran, 2,3,7-trimethyl-6-ethylaminofluoran, 2,3,7-trimethyl-6-ethylamino-5 '(6') -
• Both polycyclic 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- (4-hydroxy
• 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 per part of the components (A) and (B).
• both component (A) and component (B) are preferably dissolved together or separately in an organic solvent and the solutions obtained are expediently encapsulated by processes such as e.g. in the U.S. Patents 2,712,507, 2,800,457, 3,016,308, 3,429,827 and 3,578,605 or in British Patents 989,264, 1,156,725, 1,301,052 or 1,355,124.
• Microcapsules formed by interfacial polymerization such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
• Encapsulation is usually required 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, for example halogenated benzene, diphenyls or paraffin, such as, for example, chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters such as dibutyl adipate, dibutyl phthalate, dioctyl phthalate, butyl benzyl adipate, trichloroethyl phosphate, trioctyl phosphate, tricresyl phosphate; aromatic ethers such as benzylphenyl ether; Hydrocarbon oils, such as paraffin oil or kerosene, for example derivatives of diphenyl, naphthalene or terphenyl, dibenzyltoluene, partially hydrogenated terphenyl, mono- to tetra-C1-C3-alkylated diphenyl
• Mixtures of various solvents in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
• Microcapsules containing components (A) and (B) can be used to produce pressure-sensitive copying materials of various known types.
• the different systems differ essentially in the arrangement of the capsules, the color reactants and the carrier material.
• An arrangement is advantageous in which encapsulated components (A) and (B) are present in the form of a layer on the back of a transfer sheet and the electron acceptor (component (C)) in the form of a layer on the front of a receiver sheet.
• the arrangement can also be reversed.
• Another arrangement of the components is that the microcapsules containing components (A) and (B) and the developer (component (C)) are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
• the capsule mass which contains components A and B
• further capsules which contain conventional color formers. Similar results are obtained if components A and B are encapsulated together with one or more of the conventional color formers.
• the capsules are preferably attached to the carrier by means of a suitable binder.
• this binder is 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 can also 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. Electrocardiograph used.
• 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 in specific districts softened or fused by means of heat, components (A), (B) and (C) coming into contact with one another at the points where 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 i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
• 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, solvents, talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (eg chalk), clays or also contain organic pigments, such as urea-formaldehyde polymers.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid, benzate, methyl ester, benzate metal, eg, benzate, benzate, for example, benzate, benzylate, for example, benzate, zalatesilate, eg , Dibenzyl terephthalate, dibenzyl isophthalate, benzyldiphenyl or other corresponding meltable products which induce the simultaneous melting of the color former components and the developer can be added.
• Thermographic recording materials preferably contain waxes, e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• waxes e.g. Carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• 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.
• the IR spectrum shows the acetate-CO band at 1770 cm ⁇ 1, and the lactone-CO band at 1790 cm ⁇ 1.
• 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 with a doctor blade to paper with a basis weight of 50 g / m2 in such a way that the material applied corresponds to 4 g / m2 dry weight.
• a facsimile device Infotec 6510
• a lightfast, intense, violet color develops.
• a solution of 1 g of 2-phenylindole in 99 g of diisopropylnaphthalene is also microencapsulated with gelatin and gum arabic by coacervation.
• the two capsule masses A and B are mixed with starch solution and spread on a sheet of paper.
• a second sheet of paper is coated with activated clay as a color developer.
• the two sheets of paper are placed next to each other with the coatings.
• Example 12 If, instead of the capsule mass B, a capsule mass C from an encapsulated solution of 0.84 g of 3-methyl-6-dimethylaminoindole in 99 g of diisopropylnaphthalene is used in Example 12 and the procedure is otherwise as described in Example 12, a blue-gray, lightfast copy.
• Example 12 If, instead of the capsule mass B, a capsule mass D from an encapsulated solution of 0.66 g of 3-amino-4-methoxytoluene in 99 g of diisopropylnaphthalene is used in Example 12 and the procedure is otherwise as described in Example 12, a yellow copy is obtained after writing .
• Example 12 If, instead of the capsule mass B, a capsule mass E from an encapsulated solution of 0.84 g of 1-phenyl-3-methyl-5-pyrazolone in 99 g of diisopropylnaphthalene is used in Example 12 and the procedure otherwise described in Example 12 is obtained according to Write a red copy.
• Example 12 If, in Example 12, a capsule mass F from an encapsulated solution of 1 g of 3-phenyl-4-methylindolizine in 99 g of diisopropylnaphthalene is used instead of the capsule mass B and the procedure is otherwise as described in Example 12, a blue copy is obtained after writing.
• the capsule mass is mixed with starch solution and spread on a sheet of paper.
• a second sheet of paper is coated on the front with acid-modified bentonite as the developer. If pressure is then exerted on the papers lying opposite with the coated sides by hand or with a typewriter, a black copy is formed on the sheet coated with developer.
• this CB sheet is placed on a CF sheet, which contains an activated clay or zinc salicylate as coreactant, and written on by hand or by machine, a gray copy develops on the CF sheet, which absorbs into the near infrared and has good light fastness.
• the pressure exerted creates a lightfast, black copy on the CF sheet.
• Example 12 the capsule compositions prepared with the corresponding components listed in columns 2 and 3 of the table and depending on the developer used (active clay or zinc salicylate according to EP-A-181 283 example) are obtained 1) the colors specified in columns 4 and 5.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Plural Heterocyclic Compounds (AREA)
• Indole Compounds (AREA)
• Color Printing (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Measuring Temperature Or Quantity Of Heat (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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• 1989
  • 1989-11-23 ES ES198989810899T patent/ES2041442T3/es not_active Expired - Lifetime
  • 1989-11-23 EP EP89810899A patent/EP0373110B1/de not_active Expired - Lifetime
  • 1989-11-23 DE DE8989810899T patent/DE58904148D1/de not_active Expired - Fee Related
  • 1989-11-28 US US07/442,087 patent/US5024988A/en not_active Expired - Lifetime
  • 1989-11-29 FI FI895726A patent/FI96402C/fi not_active IP Right Cessation
  • 1989-11-30 CA CA002004229A patent/CA2004229C/en not_active Expired - Fee Related
  • 1989-11-30 KR KR1019890017534A patent/KR0137946B1/ko not_active IP Right Cessation
  • 1989-12-01 AU AU45795/89A patent/AU612291B2/en not_active Ceased
  • 1989-12-02 JP JP1312290A patent/JPH02258388A/ja active Granted

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