Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/337—Additives; Binders
  • B41M5/3375—Non-macromolecular compounds
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring

Definitions

• the present invention relates to a heat-sensitive recording material which (A) is a polycyclic compound of the formula wherein X is a monocyclic or polycyclic aromatic or heteroaromatic radical, Y is a substituent which can be split off as an anion, Q2 -CH2-, -CO-, -CS- or -SO2- and R is hydrogen, C1-C12-alkyl, C5-C10-cycloalkyl, aryl, such as phenyl or aralkyl, such as benzyl and the ring A is an aromatic or heterocyclic radical with 6 ring atoms, which may have an aromatic fused ring, both the ring A and the fused ring can be substituted, (B) an organic condensation component, (C) an electron attracting and color developing component and (D) contains an activator.
• A is a polycyclic compound of the formula wherein X is a monocyclic or polycyclic aromatic or heteroaromatic radical, Y is a substituent
• Components (A), (B) and (C) come into contact with each other when exposed to heat 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 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-dibenzylamiofluoranes, 6-dialkylamino-3-methyl-2-arylaminofluoranes, 3,6-bisalkoxyfluoranes, 3,6-bisdiarylaminofluoranes, leucoauramines, spiropyranes, Spirodipyrans, benzoxazines, chromenopyrazoles, chromenoindoles, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or other tri
• 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) the condensation component (B) - upon contact with the color developer (component (C)) a ring opening or bond cleavage, as they are also suspected by the previously common recording materials.
• component (A) 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) the condensation component (B) - upon contact with the color developer (component (C)) a ring opening or bond cleavage, as they are also suspected by the previously common recording materials.
• 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 tetrahydroquinolinyl 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 of this are 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, tert-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 radicals are substituted 2- or 3-pyrrolyl or especially 3-indolyl radicals, such as 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 radicals such as 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-
• 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 by halogen, Trifluoromethyl, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX′X ⁇ or 4-NX′X ⁇ -phenylamino ring-substituted phenalkyl or phenyl, in which X ′ and X ⁇ , independently of one another, 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-methylpiperazio, 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, e.g. Methyl, benzyloxy, C1-C8 alkoxy, primarily lower alkoxy, e.g. Methoxy, ethoxy, isopropoxy or tert-butoxy, or the group -NT1T2, where one of the radicals T1 and T2 is preferably C1-C8 acyl or lower alkyl and the other is hydrogen or lower alkyl.
• the acyl radical in this case is especially lower alkylcarbonyl, e.g. Acetyl or propionyl.
• V is preferably acetylamino, dimethylamino, 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 are 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, then 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, nidieralkylcarbonyl, 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 e.g. represents a pyridine or pyrazine ring.
• Ring A can also contain a fused aromatic ring, preferably a benzene ring and thus represents e.g. represents 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 which is optionally substituted as defined above, the unsubstituted or by halogen, 1,2-benzo radical substituted by 4 chlorine atoms is particularly preferred.
• halogen such as chlorine or bromine
• Particularly important components (A) for the color reactant system according to the invention correspond to the formula in which A 1 is a benzene or pyridine ring optionally substituted by halogen, cyano, lower alkyl, lower alkoxy or di-lower alkylamino, Y1 halogen, acyloxy and especially Nidieralkylcarbonyloxy or benzoyloxy and X1 is a 3-indolyl radical of the formula or a substituted phenyl radical of the formula (2c) mean, where W1 is hydrogen, unsubstituted or substituted by cyano or lower alkoxy, C1-C8alkyl, 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-C
• 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 benzoyloxy or especially acetyloxy 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, especially ethyl and n-butyl.
• 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 changing the hydroxyl group of the carbinol compound of formula (i) through a halogen atom with a halogenating agent e.g. replaced by thionyl chloride, phosgene, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride in dimethylformamide, dichlorobenzene, benzene, toluene or ethylene dichloride.
• a halogenating agent e.g. replaced by thionyl chloride, phosgene, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride in dimethylformamide, dichlorobenzene, benzene, toluene or ethylene dichloride.
• 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, such as methyl or ethyl iodide, ethyl chloride or dialkyl sulfates, such as dimethyl sulfate or diethyl sulfate.
• Aralkylating agents are particularly suitable for benzyl chloride or the corresponding substitution products, such as 4-chlorobenzyl chloride, which are preferably used in a non-polar, organic solvent, such as benzene, toluene or xylene.
• 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.
• Known coupling components in question provided they do not contain acidic, water-solubilizing groups, e.g. Contain carboxyl and sulfonic acid groups.
• 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, aminoanilines, anilinsulfoniaryoleoleilaminilanesilonilaminilanesilaneilineilonilethaneilineililaminolethaneilineilaneilineilineilanilethililethanilethanilethaneilaneilineilineilanilethaneilineilineilanilethilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanile
• Particularly preferred condensation components are anilines, such as cresidines, phenetidines or N, N-di-lower alkylanilines, 2-lower alkyls, 3-lower alkyls or 2-phenyl indoles, which can each be N-substituted by C1-C8-alkyl and 5-pyrazolones, such as e.g. 1-phenyl-3-methyl-5-pyrazolone.
• Further preferred coupling components are 3-lower alkyl-6-lower alkoxy- or -6-di-lower alkylamioindoles, which can also each be N-substituted by C1-C8-alkyl.
• condensation components are 2-amino-4-methoxytoluene, 3-amino-4-methoxytoluene, 3-amino-4-methoxy-1-ethylbenzene, 4-isopropylaniline, 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, 4-aminodiphenylamine, 4-aminotoluene-2-sulfonic acid anilide, 4-
• 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-diethylamiofluoran, 2-n-butylamino-6-diethylaminofluoran, 2-n-octylamino-6-diethylaminofluoran, 2-sec butylamino-6-diethylaminofluoran, 2-benzylamio-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.
• component (C) Inorganic or organic color developers known for recording materials and capable of attracting electrons (electron acceptors) can be used as component (C).
• Component (C) which reacts thermally with components (A) and (B) to develop a color, can also be used alone or as mixtures in the heat-sensitive recording materials.
• 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 'Cyclohexylidenediphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropy
• 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 zinc salicylates, metal-free phenols, phenolic resins (novolak resins), zinc-modified phenolic resins or the above-mentioned zinc rhodanide complexes.
• Both components (A) and (B) and in particular components (C) and (D) can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, such as e.g. 2- (2'-Hydroxyphenyl) benzotriazoles, 2-hydroxyphenyltriazines, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used.
• pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, magnesium carbonate, 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 these 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) in Amounts of 0.1 to 100 parts by weight, preferably 1 to 20 parts per part of components (A) and (B) are used together.
• Component (D) acts as an activator in the color image system and is preferably present in combination with the color developer (component (C)). It exhibits heat response and sensitivity and ensures that the maximum color strength of the temperature-sensitive color layer is achieved at lower temperatures than without an activator. Component (D) is preferably used in an amount of 5 to 90% by weight, based on the color developer (component C).
• Suitable activators for component (D) are expediently fusible substances which preferably melt at a temperature in the range from 50 to 200 ° C.
• the activators used as component (D) preferably correspond to the formula where m is 1 or 2 R1, R2 and R3, independently of one another, each unsubstituted or substituted by halogen, cyano or lower alkoxy alkyl having at most 6 carbon atoms, C5-C6-cycloalkyl, benzyl, phenethyl, phenyl, naphthyl or phenyl substituted by halogen, cyano, lower alkyl or lower alkoxy or R1 and R2 together with the nitrogen atom connecting them mean pyrrolidino, piperidino or morpholino.
• N N-dimethyl-N'-phenylsulfamide
• N N-dimethyl-N'-naphthyl- (1) -sulfamide or especially N-phenylbenzenesulfonamide.
• Preferred components (D) are also benzoic acid esters or phthalic diesters such as o-phthalic acid diesters, isophthalic acid diesters and especially terephthalic acid diesters, in which the ester groups are C1-C9 alkyl ester, cyclohexyl ester, phenyl ester or benzyl ester groups. Dimethyl terephthalate and dibenzyl terephthalate are particularly preferred.
• unsubstituted or alkyl-substituted benzyldiphenyls or hydrogenated benzyldiphenyls or terphenyls can be used as activators.
• These hydrocarbons are characterized in that they melt at a temperature in the range of 50 to 200 ° C.
• Particularly preferred components (D) which can be used according to the invention are N-phenylbenzenesulfonamide, N, N-dimethyl-N'-phenylsulfamide, dimethyl terephthalate, dibenzyl terephthalate, benzyl diphenyl, 2-benzyloxynaphthalene, 4-benzyloxybenzoic acid, benzyl phenyl, benzyl phenylbenzene or their mixtures.
• 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, or used 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.
• Heat-sensitive recording materials expediently contain at least one layer support, such as e.g. Paper, synthetic paper or plastic film, and one or more temperature-sensitive layers formed thereon, which have components (A) and (B) as dye-forming constituents, component (C) as color developer and component (D) as activator.
• Recording materials according to the invention preferably additionally contain a binder and / or wax.
• thermoreactive recording material can be constructed such that components (C) and (D) are dissolved or dispersed in a binder layer and components (A), (B) and (D) are dissolved in the binder in a second layer or is dispersed. Another possibility is that components (B) and (D) are first applied in a binder dispersion, then a second layer with components (C) and (D) and a third layer with components (A) and (D) are formed . All four components are preferably dispersed in the same layer.
• the layer or layers are softened or fused in specific areas by means of heat, components (A), (B), (C) and (D) coming into contact with one another at the points at which heat is applied and immediately develops the desired color.
• thermoreactive recording material can also contain component (A) and / or (B) encapsulated.
• Fusible, film-forming binders are preferably used to produce the heat-sensitive recording material. These binders are normally water soluble, while components (A), (B), (C) and (D) are insoluble in water. The binder should be able to disperse the four 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 four 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, vinyl alcohol-vinyl chloride-vinyl acetate terpolymers, polybutyl methacrylate, ethylene / vinyl acetate copolymers and styrene / butadiene / acrylic derivative .
• thermoreactive layers and the resin layers can contain further additives.
• these layers e.g. Antioxidants, UV absorbers, dissolution aids, talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (e.g. chalk), magnesium carbonate, clays or even organic pigments, e.g. Urea-formaldehyde polymers.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid benzyl ester, metal stearates, e.g. Zinc stearate, phthalonitrile, triphenylmethane, aromatic isocyanates or other corresponding meltable products which induce the simultaneous melting of the color former components and the developer are added.
• urea thiourea, diphenylthiourea, acetamide, acetanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid benzyl ester, metal stearates, e.g. Zinc stearate, phthalonitrile, triphenylmethane, aromatic isocyanates or other corresponding melt
• Thermographic recording materials preferably contain waxes, for example 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 for example 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 four components (A), (B), (C) and (D) can be enclosed in microcapsules, which, however, are preferably meltable. Any known methods for enclosing color formers or other active substances in microcapsules can be used for this purpose.
• the IR spectra shows the acetate-CO band at 1770 cm ⁇ 1, and the lactone-CO band at 1790 cm ⁇ 1.
• Regulation B The procedure is as described in Regulation A, but is used instead of acetic anhydride, 25 ml of propionic anhydride and maintaining the temperature at 110 ° C. for 3 hours, 3.8 g of the lactol ester of the formula are obtained after recrystallization from toluene with a melting point of 197-198 ° C.
• Rule D The procedure is as described in Rule A, but is used instead of the phthalide described there 24.6 g of 3- (1'-methyl-2'phenylindol-3'-yl) -3-hydroxy-4,5,6,7-tetrachlorophthalide, 14.3 is obtained after recrystallization from toluene g of the lactol ester of the formula with a melting point of 220-221 ° C (Z).
• Instructions F 4.8 g of the lactol ester of the formula (11) according to Instructions A are stirred under reflux in 100 ml of methanol for 1 hour. After cooling and filtering off 4 g of a phthalide compound of the formula are obtained After recrystallization from toluene and methanol, the product melts at 184-185 ° C.
• Instructions G If the procedure is as described in Instructions F, but 50 ml of benzyl alcohol are used instead of methanol, a phthalide compound of the formula is obtained Mp 183-184 ° C.
• Procedure H Procedure as described in Procedure C, but using 30 ml of propionic anhydride instead of acetic anhydride, keeping the reaction temperature at 75-78 ° C for 21/2 hours and diluting with 10 ml of propionic anhydride before filtration, then 18 is obtained after drying , 8 g of the lactol ester of the formula with a melting point of 154-155.5 ° C (Z).
• Instructions L 45.2 g of benzoic anhydride are melted at 50.degree. At this temperature, 8.9 g of 3- (1′-ethyl-2′-methylindol-3′-yl) 3-hydroxy-4,5,6,7-tetrachlorophthalide (or that of the corresponding keto acid tautomeric form) are introduced, warms to 100 ° C and maintains this temperature for 3 hours. The mixture is cooled to 50 ° C., 25 ml of methyl ethyl ketone and 10 ml of petroleum ether are added, and the mixture is left for 2 Crystallize for hours at 20 ° C. After filtration and drying, 2.9 g of the compound of the formula are obtained which precipitates after recrystallization from methyl ethyl ketone in pure form with a melting point of 129-131 ° C.
• Example 1 To prepare a dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 20 g of 3-amino-4-methoxytoluene are suspended in 100 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140).
• Example 1 The 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide used in Example 1 is prepared according to regulation A.
• Example 2 To prepare a dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 20 g of 3-amino-4-methoxytoluene are suspended in 100 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140).
• a dispersion C 50 g of benzyl p-hydroxybenzoate and 45 g of a 5% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground with glass balls up to a particle size of 2-4 ⁇ m.
• Example 3 To prepare dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 50 g of 2-phenylindole and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground to a particle size of 2-4 ⁇ m.
• dispersion A 2 g of dispersion A, 4 g of dispersion B, 4.5 g of dispersion C, 1.85 g of dispersion D and 5.0 g of water are processed into a coating slip and so with a doctor blade on paper with a basis weight of 50 g / m2 applied, that the applied coating mix corresponds to 2.7 g / m2 dry weight.
• Example 4 To prepare dispersion A, 50 g of 3- (1′-ethyl-2′-methylindol-3′-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 50 g of 2-phenylindole and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground to a particle size of 2-4 ⁇ m.
• a dispersion C 50 g of benzyl p-hydroxybenzoate and 45 g of a 5% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground with glass balls up to a particle size of 2-4 ⁇ m.
• Example 5 To prepare a dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 50 g of 2-phenylindole and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground to a particle size of 2-4 ⁇ m.
• a dispersion D 25 g of terephthalic acid dibenzyl ester and 75 g of a 10% strength aqueous solution of starch (Sobex 222) are ground with glass balls to a particle size of 2-4 ⁇ m.
• 2 g of dispersion A, 4 g of dispersion B, 4.5 g of dispersion C, 2 g of dispersion D and 5.0 g of water are processed into a coating slip and so with a doctor knife onto paper with a basis weight of 50 g / m2 applied that the applied spreading mixture corresponds to 2.4 g / m2 dry weight.
• Example 6 To prepare dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength watery Solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 50 g of 2-phenylindole and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground to a particle size of 2-4 ⁇ m.
• a dispersion C 50 g of benzyl p-hydroxybenzoate and 45 g of a 5% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) are ground with glass balls up to a particle size of 2-4 ⁇ m.
• a dispersion D 25 g of terephthalic acid dibenzyl ester and 75 g of a 10% strength aqueous solution of starch (Sobex 222) are ground with glass balls to a particle size of 2-4 ⁇ m.
• Example 7 To prepare a dispersion A, 50 g of 3- (1′-ethyl-2′-methylindol-3′-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 20 g of 3-amino-4-methoxytoluene are suspended in 100 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140).
• 2 g of dispersion A, 6 g of dispersion B, 4.5 g of dispersion C, 2 g of dispersion D and 5.0 g of water are processed into a coating slip and so with a doctor blade onto paper with a basis weight of 50 g / m2 applied that the applied coating mix corresponds to 1.1 g / m2 dry weight.
• Example 8 To prepare a dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 20 g of 3-amino-4-methoxytoluene are suspended in 100 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140).
• a dispersion D 25 g of dimethyl terephthalate and 75 g of a 10% strength aqueous solution of starch (Sobex 222) are ground with glass balls to a particle size of 2-4 ⁇ m.
• Example 9 To prepare dispersion A, 50 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 150 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140) with 500 g glass balls ground to a grain size of 2-4 microns.
• polyvinyl alcohol Polyviol VO3 / 140
• a dispersion B 20 g of 3-amino-4-methoxytoluene are suspended in 100 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol VO3 / 140).
• Dispersion C and dispersion D are mixed in a weight ratio of 6: 1, whereupon the mixture is applied with a doctor blade to a paper of 50 g / m 2 and then dried at 40 ° C.
• a mixture of dispersions A, B and D in a weight ratio of 2: 4: 1 is applied to the surface of the paper thus obtained with a doctor blade and dried at 40.degree.
• the total application weight atro is 6.7 g / m2.
• Example 10 The dispersions B and D prepared according to Example 9 are mixed in a weight ratio of 4: 1, whereupon the mixture is applied to a paper of 50 g / m 2 using a doctor blade and dried at 40 ° C.
• a mixture of dispersions C and D in a weight ratio of 6: 1 is applied to the surface of the paper thus obtained with a doctor blade and dried. Furthermore, a third mixture of dispersions A and D is applied in a weight ratio of 2: 1 and dried at 40 ° C.
• the total application weight atro is 6.8 g / m2.

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• 1991
  • 1991-05-14 EP EP91810367A patent/EP0465402A1/de not_active Withdrawn
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