EP0373110B1 - Pressure-sensitive or heat-sensitive recording material - Google Patents

Description

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. When exposed to heat, a chemical reaction of the chromogenic compound with the color developer takes place in the coating, with color formation. In the case of the pressure-sensitive recording materials, 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.

It has now been found that a pressure-sensitive or heat-sensitive recording material is obtained if, instead of the leuco dye, the starting components suitable for forming the desired dye are used, whereupon the color is formed when pressure or heat is applied.

• (A) eine polycyclische Verbindung der Formel
  
  worin
  X einen monocyclischen oder polycyclischen aromatischen oder heteroaromatischen Rest,
  Y einen als Anion abspaltbaren Substituenten,
  Q₁ -O-, -S-, 〉N-R oder 〉N-NH-R,
  Q₂ -CH₂-, -CO-, -CS- oder -SO₂- und
  R Wasserstoff, C₁-C₁₂-Alkyl, C₅-C₁₀-Cycloalkyl, Aryl, wie Phenyl oder Aralkyl wie Benzyl bedeuten und der Ring A einen aromatischen oder heterocyclischen Rest mit 6 Ringatomen darstellt, der einen aromatischen annellierten Ring aufweisen kann, wobei sowohl der Ring A als auch der annellierte Ring substituiert sein können,
• (B) eine organische Kondensationskomponente und
• (C) eine elektronenanziehende und farbentwickelnde Komponente enthält.

The present invention therefore relates to pressure-sensitive or heat-sensitive recording material

• (A) 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,
  Q₁ -O-, -S-,〉 NR or〉 N-NH-R,
  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 and
• (C) contains an electron attracting and color developing component.

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). By a suitable combination of the individual components, the desired colors, e.g. yellow, orange, red, violet, blue, green, gray, black or mixed colors can be generated. Another possible combination is that 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, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, Triarylmethane leuco dyes used.

The compounds of formula (1) (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) 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.

In formula (1) 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.

As a heteroaromatic radical, 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, hydroxy, lower alkyl, lower alkoxy, lower alkylamino or lower alkoxycarbonyl.

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.

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.

dar.As an aromatic radical, X preferably represents a substituted phenyl radical of the formula

represents.

Here 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.

As alkyl, R, R₁, R₂ and R₃ represent, for example, the substituents listed above for alkyl radicals.

If the 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.

Examples of 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.

As aralkyl or phenalkyl 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. Examples of such 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. As a C₁-C₁₂ alkoxy radical, 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.

If 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.

The substituents R₁ and R₂ are preferably cyclohexyl, benzyl, phenethyl, cyano-lower alkyl e.g. β-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. Such 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. Examples of 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.

As a 6-membered aromatic ring, 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. As a 6-membered heterocyclic ring, 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.

worin A₁ einen gegebenenfalls durch Halogen, Cyano, Niederalkyl, Niederalkoxy oder Diniederalkylamino substituierten Benzol- oder Pyridinring, Y₁ Halogen, Acyloxy und besonders Niederalkylcarbonyloxy oder Benzoyloxy und
X₁ einen 3-Indolylrest der Formel

oder einen substituierten Phenylrest der Formel

bedeuten, wobei W₁ Wasserstoff, unsubstituiertes oder durch Cyano oder Niederalkoxy substituiertes C₁-C₈-Alkyl, Acetyl, Propionyl oder Benzyl,
W₂ Wasserstoff, Niederalkyl, vor allem Methyl, oder Phenyl,
R₄, R₅ und R₆ unabhängig voneinander, je unsubstituiertes oder durch Hydroxy, Cyano oder Niederalkoxy substituiertes Alkyl mit höchstens 12 Kohlenstoffatomen, C₅-C₆-Cycloalkyl, Benzyl, Phenethyl oder Phenyl, oder (R₅ und R₆) zusammen mit dem sie verbindenden Stickstoffatom Pyrrolidino, Piperidino oder Morpholino,
V₁ Wasserstoff, Halogen, Niederalkyl, C₁-C₈-Alkoxy, Benzyloxy oder die Gruppe -NT₃T₄,
T₃ und T₄, unabhängig voneinander, je Wasserstoff, Niederalkyl, Niederalkylcarbonyl oder unsubstituiertes oder durch Halogen, Methyl oder Methoxy substituiertes Benzoyl bedeuten, und der Ring B unsubstituiert oder durch Halogen, Niederalkyl, wie Methyl oder Isopropyl oder durch Diniederalkylamino, wie Dimethylamino substituiert ist.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-cycloalkyl, benzyl, phenethyl or phenyl, or (R₅ and R₆) together with the nitrogen atom pyrrolidino connecting them, Piperidino or morpholino,
V₁ is hydrogen, halogen, lower alkyl, C₁-C₈ alkoxy, benzyloxy or the group -NT₃T₄,
T₃ and T₄, independently of one another, each represent hydrogen, lower alkyl, lower alkylcarbonyl or unsubstituted or substituted by halogen, methyl or methoxy, and the ring B is unsubstituted or substituted by halogen, lower alkyl, such as methyl or isopropyl or by di-lower alkylamino, such as dimethylamino.

Among the compounds of the formula (2), 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.

worin der Ring D unsubstituiert oder durch 4 Chloratome substituiert ist,
Y₂ Acetyloxy oder Benzoyloxy und
W₃ C₁-C₈-Alkyl, wie z.B. Ethyl, n-Butyl oder n-Octyl bedeuten.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.

worin D und Y₂ die in Formel (3) angegebene Bedeutung haben und R₇, R₈ und R₉ jeweils Niederalkyl darstellen.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.

worin A, Q₁, Q₂ und X die angegebene Bedeutung haben, mit einem Acylierungsmittel umsetzt.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. 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. The halogenating agent can also be used in excess without a solvent.

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.

Compounds of formula (1) in which Y represents an ether group as removable substituents can also be obtained by etherification of the compounds of formula (i) with an alkylating agent or aralkylating agent.

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.

For specific examples of the compounds of the formulas (1) to (4), as described inter alia in J. Am. Chem. Soc. 38 2101-2119 and Helvetica Chimica Acta 42 (1959) 1085-1100 are mentioned
3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxyphthalide,
3- (4'-diethylaminophenyl) -3-acetyloxyphthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxyphthalide,
3- (4'-dimethylaminophenyl) -3-acetyloxy-6-dimethylaminophthalide,
3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxyphthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-5'6-dichlorophthalide,
3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-5,6-dichlorophthalide,
3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-5-methylphthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4-azaphthalide,
3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-4-azaphthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-propionyloxy-4,5,6,7-tetrachlorophthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-benzoyloxy-4,5,6,7-tetrachlorophthalide,
3- (1'-methyl-2'-phenylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-7-azaphthalide,
3- (4'-diethylamino-2'-acetyloxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (4'-N-cyclohexyl-N-methylamino-2'-ethoxyphenyl) -3-acetyloxyphthalide,
3- (4'-N-cyclohexyl-N-methylamino-2'-methoxyphenyl) -3-acetyloxy-4-azaphthalide,
3- (4'-N-ethyl-Np-toluidino-2'-methoxyphenyl) -3-acetyloxyphthalide,
3- (4'-N-ethyl-N-isoamylamino-2'-methoxyphenyl) -3-acetyloxyphthalide,
3- (4'-pyrrolidino-2'-methoxyphenyl) -3-acetyloxyphthalide,
3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4-azaphthalide,
3- (4'-dimethylamino-5'-methylphenyl) -3-acetyloxyphthalide,
3- (4'-diethylamino-5'-methylphenyl) -3-acetyloxyphthalide,
3- (2'-acetyloxy-4'-dimethylamino-5'-methylphenyl) -3-acetyloxyphthalide,
3- (4'-di-n-butylamino-2'-n-butoxyphenyl) -3-acetyloxyphthalide,
3- (4'-di-n-butylamino-2'-ethoxyphenyl) -3-acetyloxyphthalide,
3- (4'-diethylamino-2'-n-propoxyphenyl) -3-acetyloxyphthalide,
3- (3'-methoxyphenyl) -3-acetyloxy-6-dimethylaminophthalide,
3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (4'-di-n-butylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (4'-diethylamino-2'-acetyloxyphenyl) -3-acetyloxyphthalide,
3- (4'-diethylamino-5'-methyl-2'-acetyloxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide,
3- (4'-di-n-butylaminophenyl) -3-acetyloxyphthalide,
3- (4'-dimethylaminophenyl) -3-acetyloxy-6-chlorophthalide,
3- (4'-di-2˝-cyclohexylethylaminophenyl) -3-acetyloxyphthalide,
3- (Julolidin-6'-yl) -3-acetyloxyphthalide,
3-kairolinyl-3-acetyloxyphthalide,
3- (2 ', 4-bis-dimethylaminophenyl) -3-acetyloxyphthalide,
3- (2'-acetylamino-4'-dimethylaminophenyl) -3-acetyloxyphthalide,
3- (N-ethyl-carbazol- (3 ') - yl) -3-acetyloxyphthalide,
3- (1'-ethyl-2'-methylindole- (3 ') - yl) -3-chlorophthalide,
3- (1'-ethyl-2'-methylindole- (3 ') - yl) -3-chloro-benzoxathiol-1,1-dioxide,
3- (4'-diethylamino-2'-ethoxyphenyl) -3-chlorophthalide,
3- (4'-dimethylaminophenyl) -3-methoxy-6-dimethylaminophthalide,
3- (1'-ethyl-2'-methylindole- (3 ') - yl) -3-methoxy-4,5,6,7-tetrachlorophthalide,
3- (1'-ethyl-2'-methylindol-3'-yl) -3-benzyloxy-4,5,6,7-tetrachlorophthalide,
3- (2'-methylindol-3'-yl) -3-methoxyphthalide,
3- (1'-n-butyl-2'-methyl-indol-3'-yl) -3-methoxyphthalide,
3- (2'-acetyloxy-5'-bromophenyl) -3-acetyloxyphthalide,
3- (3'-diacetylamino-4'-methylphenyl) -3-acetyloxyphthalide,
3- (4'-chlorophenyl) -3-chlorophthalide.

The condensation components (component B) 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.

From the multitude of possibilities, there may be mentioned, for example: condensation components of the benzene series, the naphthalene series, the open-chain methylene-active compounds and the heterocyclic series.

Examples of 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, kairolines.

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.

Specific examples of 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-pyrazolone, 1-phenyl-5-methyl-3-pyrazolone, 1- (2'-chlorophenyl) -5-methyl-3-pyrazolone, N-ethylcarbazole, N-methylpyrrole, 2-methylindole, 2- Phenylindole, 1,2-dimethylindole, 1-ethyl-2-methylindole, 1-n-octyl-2-methylindole, 1-methyl-2-phenylindole, 1-ethyl-2-phenylindole, 2- (4'- Methoxyphenyl) -5-methoxyindole, 3-methyl-6-methoxyindole, 3-methyl-6-dimethylaminoindole, 1-ethyl-3-methyl-6-methoxyindole, 1-ethyl-3-methyl-6-dimethylaminoindole, 2- ( 4'-methoxyphenyl) -5-methoxyindole, α-naphthol, β-naphthol, naphthylamine, 1-amino-7-naphthol, 3-cyanoacetylaminophenol, thionaphthene, phenothiazine, 3-methyl-5-amino-pyrazole, pyrimidyl-2-acetic acid ethyl ester, iminodibenzyl, 1-benzyl-2-methylindoline, 2,3,3-trimethylindolenine, Benzothiazol-2-yl-acetonitrile, 1,3,3-trimethyl-2-methylene-indoline, 1-ethyl-3-cyano-4-methyl-6-hydroxy-2-pyridone, 3-phenyl-4-methylindolizine, 2,3-diphenylindolizine, 1,1-bis (1'-ethyl-2'-methylindol-3'-yl) ethylene, 2-dimethylamino-4-methylthiazole, 2-dimethylamino-4-phenylthiazole and 2-methylene-3-methyl-benzopyran.

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.

Specific examples of such 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') - tert.butylfluorane,
2-chloro-3,7-dimethyl-6-ethylamino-5 '(6') - tert.butylfluorane,
2-tert-butyl-6-ethylamino-7-methyl-5 '(6') - tert.butylfluorane,
3-chloro-6-aminofluorane,
3-chloro-6-cyclohexylaminofluoran,
2,7-dimethyl-3,6-bis-ethylaminofluoran,
2- (2'-chloroanilino) -6-ethylamino-7-methylfluorane,
3,3-bis (4'-dimethylaminophenyl) -6-aminophthalide,
3,3-bis (4'-ethylaminophenyl) -6-dimethylaminophthalide.

The proportions in which components (A) and (B) are used are not critical, but are preferably used in equimolar amounts.

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 (electron acceptors) 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.

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.

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.

Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be substituted by halogen atoms, carboxyl groups, alkyl radicals, aralkyl radicals such as α-methylbenzyl, α, α-dimethylbenzyl, aryl radicals, acyl radicals such as arylsulfonyl, or alkoxycarbonyl radicals or aralkoxycarbonyl radicals such as benzyloxycarbonyl.

Specific examples of phenols suitable as component (C) are 4-tert-butylphenol, 4-phenylphenol, methylene-bis (p-phenylphenol), 4-hydroxydiphenyl ether, α-naphthol, β-naphthol, 4-hydroxybenzoic acid methyl ester or benzyl ester , 2,4-dihydroxybenzoic acid methyl ester, 4-hydroxydiphenyl sulfone, 4'-hydroxy-4-methyldiphenyl sulfone, 4'-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-acetophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxydiphenyl, 2, 4-dihydroxydiphenyl sulfone, 4,4'-cyclohexylidene diphenol, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4-bis- (4-hydroxyphenyl) valeric acid, resorcinol, Hydroquinone, pyrogallol, phloroglucinol, p-, m-, o-hydroxybenzoic acid, 3,5-di- (α-methylbenzyl) -salicylic acid, 3,5-di- (α, α-dimethylbenzyl) -salicylic acid, salicylosalicylic acid, gallic acid alkyl ester, Gallic acid, hydroxyphthalic acid, 1-hydroxy-2-naphthoic acid or phenol-formaldehyde prepolymers which can also be modified with zinc. Of the carboxylic acids listed, the salicylic acid derivatives are preferred, which are preferably used as zinc salts. Particularly preferred zinc salicylates are described in EP-A-181 283 or DE-A-2 242 250.

Organic complexes of zinc thiocyanate and in particular an antipyrine complex of zinc thiocyanate or a pyridine complex of zinc thiocyanate as described in EP-A-97620 are also very suitable as component (C).

Particularly preferred components (C) are active clay, zinc salicylates, metal-free phenols, phenolic resins (novolak resins) or zinc-modified phenolic resins.

The developers can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, e.g. 2- (2'-hydroxyphenyl) benzotriazoles, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used. Examples of such pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, e.g. Urea-formaldehyde condensates (BET surface 2-75 m² / g) or melamine-formaldehyde condensation products.

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).

For the pressure-sensitive recording material, 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. In some cases it is sufficient that only component (A) is encapsulated. 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.

Examples of 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 diphenylalkanes, dodecylbenzene, alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl , benzylated xylenes, or other chlorinated or hydrogenated, condensed, aromatic hydrocarbons. Mixtures of various solvents, in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.

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.

To achieve the desired color, the capsule mass, which contains components A and B, can be mixed with 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. Since paper is the preferred backing material, this binder is primarily paper coating agents such as e.g. Gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch, starch derivatives or polymer latices. The latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.

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.

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.

The 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.

The 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.

When components (A), (B) and (C) are in two or three separate layers, 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. However, the preferred arrangement is one in which all three components are contained in one layer in a water-soluble binder.

In order to ensure the stability of the heat-sensitive recording material or the image density of the developed image, the material can be provided with an additional protective layer. 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.

Specific examples of 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, stearic acid-copolymeric acid, and / or , Isobutene / maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, casein, water-soluble polyester or carboxyl-modified polyvinyl alcohol.

If necessary, in the protective layer in combination with the water-soluble polymer resins mentioned, 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.

Both the thermoreactive layers and the resin layers can contain further additives. To improve the whiteness or the thermal head suitability of the recording material and to prevent the heated spring or plate from sticking, 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. In order to ensure that the color is formed only within a limited temperature range, 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.

To improve the usability of the thermochromatic materials, the three components (A), (B) and (C) can be enclosed in microcapsules. For this purpose, any of the above-known methods for enclosing color formers or other active substances in microcapsules can be used.

In the following manufacturing instructions and examples, the percentages given are by weight unless otherwise specified. Parts are parts by weight.

Manufacturing regulations Regulation A:

als weisse Kristalle. Nach Umkristallisation aus Toluol/Essigsäureanhydrid weist das reine Produkt einen Schmelzpunkt von 187-188°C (Zersetzung) auf.19.3 g of 3- (1'-ethyl-2'-methyl-indol-3'-yl) -3-hydroxy-4,5,6,7-tetrachlorophthalide (or that of the corresponding keto acid tautomeric form) are added to 25 ° C while stirring in 20 ml of acetic anhydride. The mixture is heated to 117 ° C., kept at this temperature for 2 1/2 hours and 15 ml of glacial acetic acid are added, whereupon the product is filtered off at 80 ° C. The residue is washed with petroleum ether and dried in vacuo. 12.4 g of the lactol ester of the formula are obtained

as white crystals. After recrystallization from toluene / acetic anhydride, the pure product has a melting point of 187-188 ° C. (decomposition).

The IR spectrum shows the acetate-CO band at 1770 cm⁻¹, and the lactone-CO band at 1790 cm⁻¹.

Regulation B:

mit einem Schmelzpunkt von 197-198°C.If the procedure is as described in instruction A, but instead of acetic anhydride, 25 ml of propionic anhydride are used and the temperature is kept 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.

Regulation C:

mit einem Schmelzpunkt von 146-148°C (Z).26.5 g of 3- (1'-n-octyl-2'-methylindol-3'-yl) -3-hydroxy-4,5,6,7-tetrachlorophthalide (or that of the corresponding keto acid tautomeric form) are in 30 ml of acetic anhydride heated to 80-85 ° C and stirred for 3 hours at this temperature. The product precipitates from the resulting solution on cooling, after which it is filtered off. The product is washed with glacial acetic acid and petroleum ether. After recrystallization from toluene, 17.2 g of the lactol ester of the formula are obtained

with a melting point of 146-148 ° C (Z).

Regulation D:

mit einem Schmelzpunkt von 220-221°C (Z).The procedure is as described in instruction A, but 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 g of the lactol ester of the formula are obtained after recrystallization from toluene

with a melting point of 220-221 ° C (Z).

Regulation E:

Nach Reinigung mit Petrolether weist diese Verbindung einen Schmelzpunkt von 185-186°C unter Zersetzung auf.4.5 g of 2- (2'-ethoxy-4'-diethylaminobenzoyl) -3,4,5,6-tetrachlorobenzoic acid are dissolved in 15 g of acetic anhydride at 45 ° C and kept at 65-70 ° C for 7 hours. On cooling, the product crystallizes out and is filtered off at 20 ° C. After drying, 3 g of a lactol ester of the formula are obtained

After cleaning with petroleum ether, this compound has a melting point of 185-186 ° C. with decomposition.

Regulation F:

Nach Umkristallisation aus Toluol und Methanol schmilzt das Produkt bei 184-185°C.4.8 g of the lactol ester of the formula (5) according to instruction A are stirred in 100 ml of methanol under reflux 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.

Regulation G:

Smp. 183-184°C.If the procedure is as described in instruction F, but 50 ml of benzyl alcohol are used instead of methanol, a phthalide compound of the formula is obtained

Mp 183-184 ° C.

Regulation H:

mit einem Schmelzpunkt von 154-155,5°C (Z).If the procedure is as described in instruction C, but using 30 ml of propionic anhydride instead of acetic anhydride, the reaction temperature is kept at 75-78 ° C. for 2 1/2 hours and diluted with 10 ml of propionic anhydride before filtration, then 18.8 is obtained after drying g of the lactol ester of the formula

with a melting point of 154-155.5 ° C (Z).

Regulation I:

mit einem Schmelzpunkt von 166-168°C.36.9 g of 2- (4'-dibutylamino-2'-hydroxybenzoyl) -benzoic acid are stirred in 240 ml of acetone and 40 ml of diethyl sulfate at 35 ° C. A solution of 16.8 g of potassium hydroxide in 50 ml of water is added dropwise within 4 hours at 35 ° C. (± 2 ° C.) and the mixture is then left to react at this temperature for 20 hours. A further 11.2 g of potassium hydroxide, dissolved in 50 ml of water, are added and the acetone is distilled off azeotropically, up to a bottom temperature of 96 ° C. The mixture is stirred at 90-95 ° C for 2 hours. After cooling to 10 ° C., 18 ml of concentrated hydrochloric acid are added dropwise, the product precipitating out. The mixture is stirred at 15-20 ° C. for 16 hours, filtered off and the product is washed with water. After drying, 39.2 g of the compound of the formula are obtained

with a melting point of 166-168 ° C.

als orange gefärbtes Oel.11.9 g of the compound of formula (ii) are stirred in 36 ml of acetic anhydride, heated and kept at 65-70 ° C. for 1/2 hour. The resulting solution is poured onto a mixture of 150 ml of toluene and 360 ml of sodium carbonate solution 15% with vigorous stirring, the water phase is separated off, washed with water, dried over sodium sulfate and the toluene phase is concentrated under reduced pressure. 13 g of the compound of the formula are obtained

as an orange colored oil.

Regulation K:

mit einem Schmelzpunkt von 95-97°C unter Zersetzung.17 g of 2- (4'-diethylamino-2'-ethoxybenzoyl) benzoic acid are stirred in 60 ml of acetic anhydride for 45 minutes at 65-70, an orange-colored solution being formed. This is poured into a mixture of 250 ml of toluene and 600 ml of 15% sodium carbonate solution while stirring well. The alkaline, aqueous phase is separated off, the toluene phase is washed with water, dried with sodium sulfate and concentrated to dryness. The residue is recrystallized from toluene / petroleum ether 1: 1 and, after drying, gives 13.2 g of the compound of the formula

with a melting point of 95-97 ° C with decomposition.

Regulation L:

welche nach Umkristallisation aus Methylethylketon in reiner Form mit einem Schmelzpunkt von 129-131°C ausfällt.45.2 g of benzoic anhydride are melted at 50 ° C. At this temperature, 8.9 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-hydroxy-4,5,6,7-tetrachlorophthalide (or the form tautomeric of the corresponding keto acid) are worn. on, 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 to crystallize at 20 ° C. for 2 hours. 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, 1.43 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (5) 5 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 2.9 g of water with glass balls ground to a particle size of 2-4 µm.

To prepare a dispersion B, 0.57 g of 2-phenylindole, 2 g of a 10% strength aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 1.1 g of water were ground to a particle size of 2-4 μm.

To prepare a dispersion C, 6 g of the zinc salicylate according to EP-A-181283, Example 1, 21 g of a 10% aqueous solution of polyvinyl alcohol (Polyviol V03 / 140) and 12 g of water with glass balls up to a grain size of 2-4 µm milled.

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. By using the paper in a facsimile device (Infotec 6510), a lightfast, intense, violet color develops.

The 3- (1'-ethyl-2'-methyl-indol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide used in Example 1 is prepared according to procedure A.

Example 2:

If the 2-phenylindole in dispersion B of example 1 is replaced by 0.41 g of 3-amino-4-methoxy-toluene and the procedure is otherwise as described in example 1, a lightfast, intensely yellow color is obtained.

Example 3:

If the 2-phenylindole in dispersion B of example 1 is replaced by 0.53 g of 1-phenyl-3-methyl-5-pyrazolone and the procedure is otherwise as described in example 1, a lightfast, red color is obtained.

Example 4:

If the phthalide compound of the formula (5) in the dispersion A of example 1 is replaced by an equimolar amount of the phthalide compound of the formula (7) according to regulation C and the procedure is otherwise as described in example 1, a violet color is obtained.

Example 5:

If the phthalide compound of the formula (5) in the dispersion A of example 1 is replaced by an equimolar amount of the phthalide compound of the formula (8) according to regulation D and the procedure is otherwise as described in example 1, a violet color is obtained.

Example 6:

If the phthalide compound of the formula (5) in the dispersion A of example 1 is replaced by an equimolar amount of the phthalide compound of the formula (6) according to regulation B and the procedure is otherwise as described in example 1, a violet color is obtained.

Example 7:

If the phthalide compound of the formula (5) in the dispersion A of example 1 is replaced by an equimolar amount of the phthalide compound of the formula (12) according to regulation H and the procedure is otherwise as described in example 1, a violet color is obtained.

Example 8:

If the phthalide compound of the formula (5) in the dispersion A of Example 1 is replaced by an equimolar amount of the phthalide compound of the formula (15) according to regulation L and the procedure is otherwise as described in Example 1, a violet color is obtained.

Example 9:

If the phthalide compound of the formula (5) in the dispersion A of example 1 is replaced by an equimolar amount of the phthalide compound of the formula (9) according to regulation E and the procedure is otherwise as described in example 1, a blue color is obtained.

Example 10:

If the phthalide compound of the formula (5) in the dispersion A of example 1 is replaced by an equimolar amount of the phthalide compound of the formula (7) and in the dispersion B of example 1 the 2-phenylindole is replaced by an equimolar amount of 3-methyl-6- dimethylaminoindole and otherwise operates as described in Example 1, a green color is obtained.

Example 11:

If the zinc salicylate in dispersion C of example 1 is replaced by 6 g of the antipyrine complex of zinc thiocyanate (according to EP-A-97620, example 17) and the procedure is otherwise as described in example 1, a lightfast, violet color develops.

Example 12:

A solution of 2.3 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (5) in 98 g of diisopropylnaphthalene is dissolved known way microencapsulated with gelatin and gum arabic by coacervation. The capsule mass A is obtained.

To produce a capsule mass B, 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. By writing by hand or with a typewriter, pressure is exerted on the upper sheet, a blue copy with good lightfastness forming on the lower sheet coated with developer.

Example 13:

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 14:

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 15:

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 16:

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.

Example 17:

3.2 g of 3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (7) and 1.1 g of 2- Phenylindole are dissolved together in a mixture of 130 g diisopropylnaphthalene and 66 g kerosene and microencapsulated in a known manner with gelatin and gum arabic by coacervation. The capsule mass is mixed with starch solution and spread on a sheet of paper. A second sheet of paper is coated on its front with acid-modified bentonite as a developer. If pressure is then exerted on the papers lying opposite with the coated sides by hand or with a typewriter, a blue, light-fast copy is formed on the sheet coated with developer.

Example 18:

werden gemeinsam im Gemisch aus 130 g Diisopropylnaphthalin und 66 g Kerosin gelöst und auf bekannte Weise mit Gelatine und Gummiarabicum durch Koazervatiom mikroverkapselt. Die Kapselmasse wird mit Stärkelösung vermischt und auf ein Blatt Papier gestrichen. Ein zweites Blatt Papier wird auf der Vorderseite mit säuremodifiziertem Bentonit als Entwickler beschichtet. Wird dann auf die mit den beschichteten Seiten gegenüberliegenden Papiere durch Schreiben mit der Hand oder mit der Schreibmaschine Druck ausgeübt, bildet sich auf dem mit Entwickler beschichteten Blatt eine oliv-graue Kopie.3.2 g of 3- (1'-n-octyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (7), 1.1 g of 2- Phenylindole and 1 g of the yellow color former of the formula

are dissolved together in a mixture of 130 g diisopropylnaphthalene and 66 g kerosene and microencapsulated in a known manner with gelatin and gum arabic by coacervation. 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, an olive-gray copy is formed on the sheet coated with developer.

Example 19:

A solution of 2 g of 2-N-methyl-N-phenylamino-6-N-ethyl-Np-tolylaminofluoran in 98 g of diisopropylnaphthalene and a common solution of 0.235 g of 2-methyl indole and 0.875 g of 3- (1'-ethyl-2 '-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (5) in 49 g of diisopropylnaphthalene are mixed and microencapsulated in a known manner with gelatin and gum arabic by coacervation. 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.

Example 20:

A solution of 2 g of 2-phenylamino-3-methyl-6-diethylaminofluoran in 98 g of diisopropylnaphthalene and a solution of 0.58 g of 3-methyl-6-dimethylaminoindole and 1.6 g of 3- (1'-ethyl-2 '-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (5) in 98 g of diisopropylnaphthalene are mixed and encapsulated in a known manner and painted on the back of the paper. If 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.

Example 21:

1.4 g of 3,3-bis (4'-dimethylaminophenyl) -6-dimethylaminophthalide, 1.0 g of N-butylcarbazol-3-yl-bis- (4'-N-methyl-N-phenylaminophenyl) methane, 0.5 g 3,3-bis (Nn-octyl-2'-methylindol-3'-yl) phthalide, 0.34 g 3-amino-4-methoxytoluene and 1.3 g 3- (4'- Diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide of the formula (9) are each separately dissolved in diisopropylnaphthalene, mixed and microencapsulated in a known manner. The paper coated with this capsule mass (= CB sheet) is placed on a paper coated with bentonite (= CF sheet) and labeled by hand or with a typewriter. The pressure exerted creates a lightfast, black copy on the CF sheet.

In the same way as described in 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.

Claims (31)

1. A pressure-sensitive or heat-sensitive recording material which comprises

   (A) a polycyclic compound of the formula

   

   in which
   X is a monocyclic or polycyclic aromatic or heteroaromatic radical,
   Y is a substituent detachable as an anion,
   Q₁ is -O-, -S-, 〉N-R or 〉N-NH-R,
   Q₂ is -CH₂-, -CO-, -CS- or SO₂- and
   R is hydrogen, C₁-C₁₂alkyl, C₅-C₁₀cycloalkyl, aryl or aralkyl, and ring A is an aromatic or heterocyclic radical having 6 ring atoms, which can have an aromatic fused ring, it being possible for both ring A and the fused ring to be substituted,

   (B) an organic condensation component and

   (C) a colour-developing component.
2. A material according to claim 1, wherein in formula (1) X is a pyrrolyl, thienyl, indolyl, carbazolyl, acridinyl, benzofuranyl, benzothienyl, naphthothienyl, phenothiazinyl, indolinyl, julolidinyl, kairolyl, dihydroquinolyl or tetrahydroquinolyl radical.
3. A material according to any one of claims 1 and 2, wherein in formula (1) X is a pyrrolyl, indolyl, carbazolyl, indolinyl, julolidinyl, kairolyl, dihydroquinolyl or tetrahydroquinolyl radical.
4. A material according to any one of claims 1 to 3, wherein in formula (1) X is a substituted 2-pyrrolyl, 3-pyrrolyl or 3-indolyl radical.
5. A material according to any one of claims 1 to 4, wherein in formula (1) X is an N-C₁-C₈alkyl-2-methylindol-3-yl, N-C₂-C₄alkanoyl-2-methylindol-3-yl or N-C₁-C₈alkyl-2-phenylindol-3-yl radical.
6. A material according to claim 1, wherein in formula (1) X is a phenyl or naphthyl radical which is unsubstituted or substituted by halogen, cyano, lower alkyl, C₅-C₆cycloalkyl, C₁-C₈acyl, -NR₁R₂, -OR₃ or -SR₃, in which R₁, R₂ and R₃, independently of one another, are each hydrogen, unsubstituted or halogen-, hydroxyl-, cyano- or lower alkoxy-substituted alkyl having a maximum number of 12 carbon atoms, acyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or phenalkyl or phenyl which is unsubstituted or ring-substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X˝ or 4-NX'X˝-phenylamino, in which X' and X˝, independently of one another, are each hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R₁ and R₂ together with the nitrogen atom linking them are a five- or six- membered heterocyclic radical.
7. A material according to claim 1, wherein in formula (1) X is a substituted phenyl radical of the formula

   

   in which R₁, R₂ and R₃, independently of one another, are each hydrogen, unsubstituted or halogen-, hydroxyl-, cyano- or lower alkoxy-substituted alkyl having a maximum number of 12 carbon atoms, acyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 10 carbon atoms or phenalkyl or phenyl which is unsubstituted or ring-substituted by halogen, cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X˝ or 4-NX'X˝-phenylamino, in which X' and X˝, independently of one another, are each hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R₁ and R₂ together with the nitrogen atom linking them are a five- or six-membered heterocyclic radical and V is hydrogen, halogen, lower alkyl, C₁-C₁₂alkoxy, C₁-C₁₂acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, halogen-, cyano-, lower alkyl- or lower alkoxy-substituted benzyl or benzyloxy, or is the group -NT₁T₂, T₁ and T₂, independently of one another, are each hydrogen, lower alkyl, C₅-C₆cycloalkyl, unsubstituted or halogen-, cyano-, lower alkyl- or lower alkoxy-substituted benzyl, or acyl having 1 to 8 carbon atoms and T₁ is also unsubstituted or halogen-, cyano-, lower alkyl- or lower alkoxy-substituted phenyl and m is 1 or 2.
8. A material according to any one of claims 1 to 7, wherein in formula (1) Y is halogen, an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether group or an acyloxy group.
9. A material according to any one of claims 1 to 8, wherein in formula (1) Y is an acyloxy group of the formula
   
           (1c)   R'(NH-)_n-1-Q'-O-
   
   in which R' is unsubstituted or substituted C₁-C₂₂alkyl, cycloalkyl, aryl, aralkyl or heteroaryl, Q' is -CO- or -SO₂- and n is 1 or 2.
10. A material according to any one of claims 1 to 9, wherein in formula (1) Y is an acyloxy group of the formula R˝-CO-O- in which R˝ is lower alkyl or phenyl.
11. A material according to any one of claims 1 to 10, wherein in formula (1) Q₁ is oxygen and Q₂ is -CO-.
12. A material according to any one of claims 1 to 11, wherein in formula (1) ring A is a substituted or unsubstituted benzene, naphthalene, pyridine, pyrazine, quinoxaline or quinoline ring.
13. A material according to any one of claims 1 to 12, wherein in formula (1) ring A is an unsubstituted or halogen-substituted benzene ring.
14. A material according to claim 1, wherein component (A) is a lactone compound of the formula

    

    in which A₁ is a benzene or pyridine ring which is unsubstituted or substituted by halogen, cyano, lower alkyl, lower alkoxy or lower dialkylamino, Y₁ is halogen or acyloxy and in particular lower alkylcarbonyloxy or benzoyloxy and X₁ is a 3-indolyl radical of the formula

    

    or a substituted phenyl radical of the formula

    

    in which W₁ is hydrogen, unsubstituted or cyano- or lower alkoxy-substituted C₁-C₈alkyl, acetyl, propionyl or benzyl, W₂ is hydrogen, lower alkyl or phenyl, R₄, R₅ and R₆, independently of one another, are each unsubstituted or hydroxy-, cyano- or lower alkoxy-substituted alkyl having a maximum number of 12 carbon atoms, C₅-C₆cycloalkyl, benzyl, phenethyl or phenyl, or (R₅ and R₆) together with the nitrogen atom linking them are pyrrolidino, piperidino or morpholino, V₁ is hydrogen, halogen, lower alkyl, C₁-C₈alkoxy, benzyloxy or the group -NT₃T₄, T₃ and T₄, independently of one another, are each hydrogen, lower alkyl, lower alkylcarbonyl or unsubstituted or halogen-, methyl- or methoxy-substituted benzoyl, and ring B is unsubstituted or substituted by halogen, lower alkyl or lower dialkylamino.
15. A material according to claim 14, wherein in formula (2) X₁ is a 3-indolyl radical of the formula 2(a) in which W₁ is C₁-C₈alkyl, W₂ is methyl or phenyl, and Y₁ is lower alkylcarbonyloxy.
16. A material according to claim 1, wherein component (A) is a lactone compound of the formula

    

    in which ring D is unsubstituted or chlorine-tetrasubstituted, Y₂ is acetoxy or benzoyloxy and W₃ is C₁-C₈alkyl.
17. A material according to claim 1, wherein component (A) is a lactone compound of the formula

    

    in which ring D is unsubstituted or chlorine-tetrasubstituted, Y₂ is acetoxy or benzoyloxy and R₇, R₈ and R₉ are each lower alkyl.
18. A material according to any one of claims 1 to 17, wherein the condensation component (B) is an N-substituted aminophenylethylene, N-substituted aminophenylstyrene, acylacetarylamide, monohydric or polyhydric phenol, phenol ether, 3-aminophenol ether, aniline, naphthylamine, diarylamine, naphthol, naphtholcarboxanilide, aminopyrazole, pyrazolone, thiophene, thionaphthene, phenothiazine, aminothiazole, acridine, pyridone, indole, carbazole, kairoline, indolizine, julolidine, morpholine, pyrrolidine, piperidine, piperazine, indoline, quinolone, pyrimidone, barbituric acid, benzomorpholine, dihydroquinoline or tetrahydroquinoline compound.
19. A material according to any one of claims 1 to 18, wherein the condensation component (B) is a 5-pyrazolone compound, a cresidine, phenetidine or N,N-(lower) dialkylaniline compound, a 3-(lower) alkyl-6-(lower) dialkylaminoindole compound, 2-(lower) alkylindole, 2-phenylindole, a 3-(lower) alkyl-6-(lower) alkoxyindole compound or a C₁-C₈alkyl-N-substituted 2-(lower) alkylindole, 2-phenylindole, 3-(lower) alkyl-6-(lower) alkoxyindole or 3-(lower) alkyl-6-(lower) dialkylaminoindole compound.
20. A material according to any one of claims 1 to 17, wherein the condensation component (B) is a fluoran or phthalide compound which contains at least one amino group which is unsubstituted or monosubstituted by lower alkyl, cyclohexyl or benzyl.
21. A material according to any one of claims 1 to 20, wherein the colour-developing component (C) is a Lewis acid, an acid clay, a solid carboxylic acid or a compound having a phenolic hydroxyl group.
22. A material according to any one of claims 1 to 21, wherein the colour-developing component (C) is an active clay, a zinc salicylate, a metal-free phenol compound, a phenol-formaldehyde resin or a zinc-modified phenol-formaldehyde resin.
23. A material according to any one of claims 1 to 22 which is pressure-sensitive.
24. A material according to claim 23, wherein components (A) and (B) are dissolved in an organic solvent.
25. A material according to claim 24, wherein components (A) and (B) are microencapsulated.
26. A material according to any one of claims 23 to 25, wherein components (A) and (B) are present in the form of one or two layers on the back of a transfer sheet and component (C) is present in the form of a layer on the front of a receptor sheet.
27. A pressure-sensitive material according to any one of claims 23 to 26, wherein component (C) is an active clay or a zinc salicylate.
28. A material according to any one of claims 1 to 21 which is heat-sensitive.
29. A material according to claim 28 which contains 1 to 4 layers in which components (A), (B) and (C) and if necessary a binder and/or wax are present.
30. A material according to any one of claims 1 to 29, wherein components (A) and (B) are present together with one or more conventional colour formers.
31. A material according to claim 30, wherein the conventional colour formers present are 3,3-bis(aminophenyl)phthalide, 3-indolyl-3-aminophenylaza- or -diazaphthalide, 3,3-bis(indolyl)phthalide, 3-aminofluorans, 6-dialkylamino-2-dibenzylaminofluorans, 6-dialkylamino-3-methyl-2-arylaminofluorans, 3,6-bisalkoxyfluorans, 3,6-bis(diarylamino)fluorans, leukoauramines, spiropyrans, spirodipyrans, chromenopyrazoles, chromenoindoles, benzoxazines, phenoxazines, phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes.