EP0463987A1 - Pressure sensitive recording material - Google Patents

Abstract

The pressure-sensitive recording material has a coating containing (A) a polycyclic compound of the formula <IMAGE> in which X is a monocyclic or polycyclic, aromatic or heteroaromatic radical, Y is a substituent which can be removed as an anion, Q1 is -O-, -S-, <2bL>N-R or <2bL>N-NH-R, Q2 is -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 which has 6 ring atoms and may contain a fused aromatic ring, where both the ring A and the fused ring may be substituted, and (B) an organic condensation component and (C) an electron-withdrawing and colour-developing component incorporated into the base material.

Description

In the case of pressure-sensitive recording materials, the color images are usually 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 recording material is obtained if, instead of the leuco dye, the starting components which are suitable for forming the desired dye are used and carrier material is used, into which the color developer is incorporated during the production of the carrier material. The color is then formed under pressure.

• (A) eine polycyclische Verbindung der Formel
  
  worin
  X einen monocyclischen oder polycyclischen aromatischen oder heteroaromatischen Rest,
  Y einen als Anion abspaltbaren Substituenten,
  
  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 und
• (B) eine organische Kondensationskomponente und mit
• (C) einer elektronenanziehenden und farbentwickelnden Komponente, die im Trägermaterial eingebaut ist.

The present invention therefore relates to a pressure-sensitive recording material having a coating

• (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,
  
  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 represents an aromatic or heterocyclic radical with 6 ring atoms, which may have an aromatic fused ring, where both the ring A and the fused ring can be substituted and
• (B) an organic condensation component and with
• (C) an electron-attracting and color-developing component which is built into the carrier material.

Components (A), (B) and (C) come into contact with each other by pressure 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, phenoxazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothiazines, phenothazines -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) 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.

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, for example, a thienyl, acridinyl, benzofuranyl, benzothienyl, naphthothienyl or phenothiazinyl radical, but advantageously a pyrrolyl, indolyl, carbazolyl, julolidinyl, kairolinyl, indolinyl, dihydroquinolchinyl or tetrahydrovinyl 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, sec-butyl, t-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.

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 Naphthylrest mean.

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 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.

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

Are the alkyl radicals in R₁, R₂ and R₃ substituted, it is mainly Cyanoalkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl each preferably with a total of 2 to 8 carbon atoms, such as 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, triluormethyl, 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, for example β-cyanoethyl or primarily lower alkyl, such as 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. 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.

darstellt, so ist R vorzugsweise Wasserstoff, Methyl oder Phenyl.Q₁ preferably represents an oxygen atom, while Q₂ preferably represents -SO₂- or especially -CO. If

represents, then 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

einen substituierten Phenylrest der Formel

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

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 lower alkylcarbonyloxy or benzoyloxy and
X₁ is a 3-indolyl radical of the formula

a substituted phenyl radical of the formula

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 Benzoyloxy oder insbesondere Acetyloxy,
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 benzoyloxy or in particular acetyloxy,
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 vor allem Ethyl oder n-Butyl 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, especially ethyl or n-butyl.

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 the hydroxyl group of the carbinol compound of formula (i) replaced by 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. 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 (1916) 2101-2119 and Helvetica Chimica Acta 42 (1959) 1085-1100
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-acetylox y-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′-di-n-pentylamino-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- (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, 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, aminoanilines, anilinsulfoniaryoleoleilaminilanesilonilaminilanesilaneilineilonilethaneilineililaminolethaneilineilaneilineilineilanilethililethanilethanilethaneilaneilineilineilanilethaneilineilanilethilethanilethanilethanilethanilethanilethilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethanilethaneol Pyrrolidines, piperidines, piperazines, aminopyrazoles, pyrazolones, thiophenes, aminopyrimidines, acridines, aminothiazoles, pyridones, indoles, indolizines, quinolones, pyrimidones, barbituric acids, carbazoles, benzomorpholines, 2-methylene-benzopyrans, dihydro-quinolines, toline-tetrahydroquinolines, tine-tetrahydroquinolines, tine-tetrahydroquinolines, tetra-pyridine, tolines, tetra-hydrolines, tetra-hydrolines, tetra-pyridine, tolines

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. 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, 4-isopropylaniline, N, N-diethylaniline, N, N-dibenzylaniline, 3-n-butoxy -N, N-di-n-butylaniline, 2-methyl-5-acetyloxy-N, N-diethylaniline, 4-ethoxydiphenylamine, 4-aminodiphenylamine, 3-ethoxy-N, N-dimethylaniline, N, N'-diphenyl-p-phenylenediamine, m-phenetidine, 3-ethoxy -N, N-diethylaniline, 1,3-bis-dimethylaminobenzene, 4-aminotoluene-2-sulfonic acid anilide, 4-aminotoluene-2-sulfonic acid-N-ethylanilide, 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-methyl indole, 2-phenyl indole, 1,2-dimethyl indole, 1-ethyl-2-methyl indole, 1-n-octyl-2-methyl indole , 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, α- or β-naphthylamine, 1- Amino-7-naphthol, 3-cyanoacetylaminophenol, thionaphthene, 3-methyl -5-amino-pyrazole, ethyl pyrimidyl-2-acetate, imino-dibenzyl, 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-methyl-thiazole, 2-dimethylamino-4-phenyl-thiazole 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.butylfluoran,
2-chloro-3,7-dimethyl-6-ethylamino-5 ′ (6 ′) - tert.butylfluoran,
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.

As organic color developers, solid carboxylic acids, advantageously aliphatic dicarboxylic acids, such as 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 can be used with styrene, ethylene or vinyl methyl ether.

Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be substituted by halogen atoms, carboxyl groups, alkyl radicals, aralkyl radicals such as 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-methyl-diphenyl 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, 4-hydroxy-phthalic acid dimethyl ester 1-hydroxy-2-naphthoic acid or alkylphenol-formaldehyde polymers, phenylphenol forma Idehyde resins 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 or zinc salicylates, such as zinc 3,5-bis (α-methylbenzyl) salicylate.

Both components (A) and (B) and in particular component (C) can additionally also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as retention agents, silica gel or UV absorbers, such as, for example 2- (2'-Hydroxyphenyl) benzotriazoles, 2-hydroxyphenyltriazines, benzophenones, cyanoacrylates, salicylic acid phenyl esters can be used. Examples of pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, magnesium carbonate, clays such as kaolin, and organic pigments, for example urea-formaldehyde condensates (BET surface area 2-75 m² / g) or melamine-formaldehyde condensation products.

The ratio of component (C) to components (A) and (B) depends on the type of the three components, the type of color change and of course also on the desired color concentration. Satisfactory results are achieved if the color-developing component (C) in amounts of 0.1 part by weight, expediently at least 0.5 part to 100 parts by weight, preferably 1 to 20 parts by weight, per part of the components (A ) and (B) can be used together.

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. 2 712 507, 2 800 457, 3 016 308, 3 429 827, 4 100 103 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 from polyester, polycarbonate, polysulfonamide, polysulfonate, but especially from polyamide, polyurea or polyurethane. In some cases it is sufficient that only component (A) is encapsulated. Encapsulation is usually required to prevent early 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-solvent 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, aromatic hydrocarbons, for example derivatives of benzene, diphenyl, naphthalene or terphenyl, dibenzyltoluene, partially hydrogenated terphenyl alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl, mono- to tetra-C₁-C₃-alkylated diphenylalkanes, dodecylbenzene, benzylated xylenes, phenylxylylethane or other chlorinated or hydrogenated, condensed, aromatic hydrocarbons. Mixtures of various solvents, in particular mixtures of paraffin oils or kerosene or alkylbenzenes and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for the color formers, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.

The microcapsules containing the components (A) and (B) are applied to the surface of a support base in the production of the recording materials according to the invention and are preferably bonded thereon with a binder in an amount ensuring sufficient adhesion to the support base. 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, carboxymethyl cellulose, dextrin, starch, starch derivatives or polymer latices and mixtures of these substances. Latices are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers. Carboxylated latices are preferably used.

The paper used is not only normal papers made of cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made of synthetic polymers. The substrate can also be a plastic film.

The support base is generally coated with a coating slip containing binder and coloring reaction components (A) and (B). The coating composition forming the coating can be either in the form of an aqueous or non-aqueous system, i.e. be used in an organic solvent system or in a hotmelt waking system. To prevent premature destruction of the capsules during the manufacture and handling of the carbonless papers, spacers are preferably incorporated into the capsule coating slip to protect them. Cellulose powder and / or insoluble wheat starch are used as spacers. Mixtures of cellulose powder and starch are also used.

To achieve the desired color, the capsule mass which contains components (A) and (B) can be mixed with other capsules which contain conventional color formers. Similar results are achieved if the components (A) and (B) are encapsulated together with one or more of the conventional color formers.

The color developer used as component (C) is not coated on the surface of the paper, but rather is built into the material body during the production of the carrier material. The color developer is thus distributed through the entire thickness of the carrier material or through part of the same. The color developer is preferably added to a suspension of sulfite cellulose, whereupon this stock suspension is used, using a conventional sizing agent and a conventional retention agent, e.g. a polyacrylamide such as Separan PG5 is processed into a paper sheet containing the color developer.

The microcapsules containing components (A) and (B) can either be applied to one or both sides of this paper sheet containing color developer in the form of a capsule layer. A sheet coated only on one side can then be written on or printed from the coated side. If a sheet is coated on both sides with the color-forming capsules, this sheet can be used both as a writing surface and as a transfer sheet in order to produce a copy of the desired image on an underlying sheet.

However, components (A) and (B) can also be used in accordance with a transfer copying system in which the components are dispersed or dissolved in an oil-like solvent, encapsulated individually or together, and applied as a coating to the back of a transfer sheet. Components (A) and (B) are then transferred to the color developer-containing sheet by destroying the capsules. The desired markings are formed at the points at which the microcapsules are destroyed and components (A) and (B) are transferred.

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

Manufacturing regulations

als weisse Kristalle. Nach Umkristallisation aus Toluol/Essigsäureanhydrid weist das reine Produkt einen Schmelzpunkt von 187- 188°C (Zersetzung) auf. Regulation A: 19.3 g3- (1′-ethyl-2′-methyl-indol-3′-yl) -3-hydroxy-4,5,6,7-tetrachlorophthalide (or that of the corresponding keto acid tautomeric form) be at 25 ° C entered with stirring in 20 ml of acetic anhydride. The mixture is heated to 117 ° C., kept at this temperature for 21/2 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.

mit einem Schmelzpunkt von 197- 198°C.Procedure B: If the procedure described in procedure A is followed, but 25 ml of propionic anhydride are used instead of acetic anhydride 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.

mit einem Schmelzpunkt von 146-148 °C (Z). Instructions C: 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 warmed to 80-85 ° C. in 30 ml of acetic anhydride and stirred at this temperature for 3 hours. 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).

mit einem Schmelzpunkt von 220-221 °C (Z).Instructions D: The procedure described in Instructions A, but using 24.6 g of 3- (1'-methyl-2'-phenylindol-3'-yl) -3-hydroxy-4,5,6 instead of the phthalide described there , 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).

Nach Reinigung mit Petrolether weist diese Verbindung einen Schmelzpunkt von 185-186°C unter Zersetzung auf. Instructions E: 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 at 65-70 ° C for 7 hours held. 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.

Nach Umkristallisation aus Toluol und Methanol schmilzt das Produkt bei 184-185°C.Instructions F: 4.8 g of the lactol ester of the formula (5) 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.

Smp. 183-184°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.

mit einem Schmelzpunkt von 154-155,5°C (Z).Procedure H: Proceeding 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 2 1/2 hours and diluting with 10 ml of propionic anhydride before filtration, this is obtained after drying 18.8 g of the lactol ester of the formula

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

mit einem Schmelzpunkt von 166-168°C. Instructions I: 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 into a mixture of 150 ml of toluene and 360 ml of soda solution 15% with vigorous stirring, the water phase is separated off, washed with water and dried over sodium sulfate and concentrates the toluene phase under reduced pressure. 13 g of the compound of the formula are obtained

as an orange colored oil.

mit einem Schmelzpunkt von 95-97°C unter Zersetzung. Instructions K: 17 g of 2- (4'-diethylamino-2'-ethoxybenzoyl) benzoic acid are stirred in 60 ml of acetic anhydride for 45 minutes at 65-70 ° C, resulting in an orange colored solution. 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.

welche nach Umkristallisation aus Methylethylketon in reiner Form mit einem Schmelzpunkt von 129-131°C ausfällt. 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 carried ) on, heated 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 are obtained of the formula

which precipitates after recrystallization from methyl ethyl ketone in pure form with a melting point of 129-131 ° C.

Example 1: 1.7 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 0.6 g of 2-phenylindole are in 97 , 7 g of diisopropylnaphthalene dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation. The capsule mass is mixed with starch solution and cellulose flour and applied to a recording paper of 50 g / m² in which 5 g / m² of the zinc salicylate according to EP-A-181289 Example 1 are incorporated in the paper body. The application weight atro is 7 g / m². Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness. 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: 1.7 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 0.6 g of 1-n-octyl- 2-methylindole are dissolved in 97.7 g of 1-phenyl-1-xylylethane and microencapsulated in a known manner with gelatin and carboxymethylcellulose by coacervation.
The capsule mass is mixed with starch solution and cellulose powder and applied to a recording paper of 50 g / m² in which 5 g / m² zinc 3,5-di-α-methylbenzylsalicylate are distributed, which have been incorporated into the paper mass. The application weight atro is 7 g / m². Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness forms.

Example 3: 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 1.3 g of 1-n-octyl-2-methylindole are in 96.1 g of isopropyldiphenyl dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation.
The capsule mass is mixed with starch solution and cellulose flour and applied to a recording paper of 50 g / m², in which 5 g / m² of active clay are distributed, which were incorporated in the manufacture of the paper. The application weight atro is 7 g / m². Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness. The 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide used in Example 3 is prepared according to regulation E.

Example 4: 3.4 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 96.6 g of diisopropylnaphthalene and known Microencapsulated with gelatin and carboxymethyl cellulose by coacervation. 1.1 g of 2-phenylindole are dissolved in 98.9 g of diisopropylnaphthalene and likewise subjected to the encapsulation process.
The microcapsules obtained are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and cellulose flour. The latter is applied to 50 g / m² acceptor paper containing 5 g / m² of activated clay that has been incorporated into the mass. The application weight atro is 7 g / m².
Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness.

Example 5: 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 97.4 g of diisopropylnaphthalene and in a known manner with gelatin and carboxymethyl cellulose microencapsulated by coacervation. 1.3 g of 1-n-octyl-2-methylindole are dissolved in 98.7 g of diisopropylnaphthalene and also subjected to the encapsulation process.
The microcapsules produced are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and carboxymethyl cellulose. The latter is applied to an acceptor paper of 50 g / m², which contains 5 g / m² of zinc 3,5-di-α-methylbenzylsalicylate, which is added to the mass during manufacture of the paper is installed. The application weight atro is 7 g / m².
Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness.

Example 6: 4.9 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 95.1 g of 1-phenyl-1 -xylylethane dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation.
1.8 g of 1-n-octyl-2-methylindole are dissolved in 98.2 g of 1-phenyl-1-xylylethane and likewise subjected to the encapsulation process.
The microcapsules produced are mixed together in a ratio of 1: 1, whereupon the capsule mixture is processed into a coating slip by adding an acrylic acid ester copolymer and cellulose flour. The latter is applied to an acceptor paper of 50 g / m 2, which contains 5 g / m 2 of a zinc salicylate according to EP-A-181289, example 1, which was incorporated in the manufacture of the paper. The application weight atro is 7 g / m².
Writing on the paper by hand or typewriter exerts pressure, creating a blue typeface with good lightfastness.

Example 7: 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 97.4 g of diisopropylnaphthalene and in a known manner with gelatin and carboxymethyl cellulose microencapsulated by coacervation. 1.3 g of 1-n-octyl-2-methylindole are dissolved in 98.7 g of diisopropylnaphthalene and also subjected to the encapsulation process.
The microcapsules produced are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and carboxymethyl cellulose. The latter is applied to the back of a base paper of 50 g / m² so that the applied mass corresponds to 7 g / m² dry weight.
At the same time, an acceptor paper is prepared in which 5 g / m² of zinc 3,5-di-α-methylbenzyl salicylate is present, which is incorporated into the mass during the manufacture of the paper. The two sheets of paper are placed next to each other. By writing by hand or with a typewriter, pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.

Example 8: 3.4 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide are dissolved in 96.6 g of diisopropylnaphthalene and known Way with gelatin and Carboxymethyl cellulose microencapsulated by coacervation.
1.1 g of 2-phenylindole are dissolved in 98.9 g of diisopropylnaphthalene and likewise subjected to the encapsulation process.
The microcapsules obtained are mixed together in a ratio of 1: 1, whereupon the mixture is made into a coating slip by adding a starch solution and cellulose flour. The latter is applied to the back of a base paper of 50 g / m² so that the applied mass corresponds to 7 g / m² dry weight.
At the same time, an acceptor paper is prepared in which 5 g / m² of active clay is present, which is built into the paper pulp during the manufacture of the paper. The two sheets of paper are placed next to each other. By writing by hand or with a typewriter, pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.

Example 9: 2.6 g of 3- (4'-diethylamino-2'-ethoxyphenyl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 1.3 g of 1-n-octyl-2-methylindole are in 96.1 g of isopropyldiphenyl dissolved and microencapsulated in a known manner with gelatin and carboxymethyl cellulose by coacervation.
The capsule mass is mixed with starch solution and cellulose flour and applied to the back of a backing paper so that the application weight is 7 g / m².
At the same time, an acceptor paper is prepared in which 5 g / m² of zinc 3,5-di-α-methylbenzyl salicylate is present, which is built into the mass during the manufacture of the paper. The two sheets of paper are placed next to each other. By writing by hand or with a typewriter, pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.

Example 10: 1.7 g of 3- (1'-ethyl-2'-methylindol-3'-yl) -3-acetyloxy-4,5,6,7-tetrachlorophthalide and 0.6 g of 1-n-octyl- 2-methylindole are dissolved in 97.7 g of 1-phenyl-1-xylylethane and microencapsulated in a known manner with gelatin and carboxymethylcellulose by coacervation.
The capsule mass is mixed with starch solution and cellulose powder and applied to the back of a paper carrier so that the mass applied corresponds to 7 g / m² dry weight.
At the same time, an acceptor paper is prepared in which 5 g / m² of a zinc salicylate according to EP-A-181 289 Example 1 are distributed, which are added to the paper pulp during the Production of the paper can be added. The two sheets of paper are placed next to each other. By writing by hand or with a typewriter, pressure is applied to the upper sheet coated on the back, and a purple image is formed on the lower sheet containing the developer.

Claims (28)

Containing pressure-sensitive recording material with a coating (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,

R is hydrogen, C₁-C₁₂-alkyl, C₅-C₁₀-cycloalkyl, aryl or aralkyl and the ring A represents an aromatic or heterocyclic radical with 6 ring atoms, which may have an aromatic fused ring, both the ring A and the fused ring Ring can be substituted and (B) an organic condensation component and with (C) an electron-attracting and color-developing component which is built into the carrier material. Material according to claim 1, characterized in that in formula (1) X is a pyrrolyl, thienyl, indolyl, carbazolyl, acridinyl, benzofuranyl, benzothienyl, naphthothienyl, phenothiazinyl, indolinyl, julolidinyl, kairolyl - represents dihydroquinolyl or tetrahydroquinolyl radical. Material according to one of claims 1 and 2, characterized in that in formula (1) X denotes a pyrrolyl, indolyl, carbazolyl, indolinyl, julolidinyl, kairolyl, dihydroquinolyl or tetrahydroquinolyl radical. Material according to one of claims 1 to 3, characterized in that in formula (1) X denotes a substituted 2-pyrrolyl, 3-pyrrolyl or 3-indolyl radical. Material according to one of claims 1 to 4, characterized in that in formula (1) X is an 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 rest means. Material according to claim 1, characterized in that in formula (1) X is a phenyl or naphthyl radical which is unsubstituted or substituted by halogen, cyano, lower alkyl, C₅-C₆-cycloalkyl, C₁-C₈-acyl, -NR₁R₂, -OR₃ or -SR₃ means, wherein 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 , Cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X˝ or 4-NX'X˝-phenylamino ring-substituted phenylalkyl or phenyl, where X 'and X˝, independently of one another, each represent hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R₁ and R₂ together with the nitrogen atom connecting them represent a five- or six-membered, heterocyclic radical. Material according to claim 1, characterized in that in formula (1) X is a substituted phenyl radical of the formula

wherein 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, cyano , Lower alkyl, lower alkoxy, lower alkoxycarbonyl, -NX'X˝ or 4-NX'X˝-phenylamino ring-substituted phenalkyl or phenyl, wherein X 'and X˝, independently of one another, each represent hydrogen, lower alkyl, cyclohexyl, benzyl or phenyl, or R₁ and R₂ together with the nitrogen atom connecting them represent a five- or six-membered heterocyclic radical and V is hydrogen, halogen, lower alkyl, C₁-C₁₂-alkoxy, C₁-C₁₂-acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, by halogen, cyano, Lower alkyl or lower alkoxy substituted benzyl or benzyloxy, or the group -NT₁T₂, T₁ and T₂, independently from each other, each hydrogen, lower alkyl, C₅-C₆-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-phenyl and m 1 or 2 mean. Material according to one of claims 1 to 7, characterized in that in formula (1) Y is halogen, an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic ether group or an acyloxy group. Material according to one of claims 1 to 8, characterized in that in formula (1) Y is an acyloxy group of the formula

(1c) R ′ - (NH-) _n-1 -Q′-O-

represents in which R 'is unsubstituted or substituted C₁-C₂₂-alkyl, cycloalkyl, aryl, aralkyl or heteroaryl, Q'-CO- or -SO₂- and n is 1 or 2. Material according to one of claims 1 to 9, characterized in that in formula (1) Y is an acyloxy group of the formula R˝-CO-O-, wherein R "is lower alkyl or phenyl. Material according to one of claims 1 to 10, characterized in that in formula (1) Q₁ are oxygen and Q₂ are -CO-. Material according to one of claims 1 to 11, characterized in that in formula (1) ring A represents an optionally substituted benzene, naphthalene, pyridine, pyrazine, quinoxaline or quinoline ring. Material according to one of claims 1 to 12, characterized in that in formula (1) ring A represents an unsubstituted or halogen-substituted benzene ring. Material according to claim 1, characterized in that component (A) is a lactone compound of the formula

is 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 lower alkylcarbonyloxy or benzoyloxy and
X₁ is a 3-indolyl radical of the formula

a substituted phenyl radical of the formula

where W₁ is hydrogen, unsubstituted or substituted by cyano or lower alkoxy C₁-C₈-alkyl, acetyl, propionyl or benzyl,
W₂ is hydrogen, lower alkyl 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, are each 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 or di-lower alkylamino. Material according to claim 14, characterized in that in formula (2) X₁ is a 3-indolyl radical of formula 2 (a) in which W₁ is C₁-C₈-alkyl, W₂ is methyl or phenyl and Y₁ is lower alkylcarbonyloxy. Material according to claim 1, characterized in that component (A) is a lactone compound of the formula

is in which the ring D is unsubstituted or substituted by 4 chlorine atoms, Y₂ is acetyloxy or benzoyloxy and W₃ is C₁-C₈-alkyl. Material according to claim 1, characterized in that component (A) is a lactone compound of the formula

is in which the ring D is unsubstituted or substituted by 4 chlorine atoms, Y₂ is acetyloxy or benzoyloxy and R₇, R₈ and R₉ are each lower alkyl. Material according to one of claims 1 to 17, characterized in that the Condensation component (B) is an N-substituted aminophenylethylene, N-substituted aminophenylstyrene, acylacetarylamide, monovalent or polyvalent phenol, phenol ether, 3-aminophenol ether, aniline, naphthylamine, diarylamine, naphthol, naphtholcarboxylic acid anilide -, pyrazolone, thiophene, thionaphthene, aminothiazole, aminopyrimidine, acridine, pyridone, indole, carbazole, kairolin, indolizine, julolidine, morpholine, pyrrolidine, piperidine, piperazine, Is indoline, quinolone, pyrimidone, barbituric acid, benzomorpholine, dihydroquinoline or tetrahydroquinoline compound. Material according to one of claims 1 to 18, characterized in that the condensation component (B) is a 5-pyrazolone compound, a cresidine, phenetidine or N, N-di-lower alkylaniline compound, a 3-lower alkyl-6-di-lower alkylaminoindole compound, 2-lower alkylindole, 2-phenylindole , a 3-Niedeyl-6-lower alkoxyindole compound or a C₁-C₈alkyl N-substituted 2-lower alkyl, 2-phenylindole, 3-lower alkyl-6-lower alkoxyindole or 3-lower alkyl-6-di-lower alkylaminoindole compound. Material according to one of claims 1 to 17, characterized in that the condensation component (B) is a fluoran or phthalide compound which has at least one unsubstituted or monosubstituted by lower alkyl, cyclohexyl or benzyl amino group. Material according to one of claims 1 to 20, characterized in that the color-developing component (C) is a Lewis acid, an acid clay, a solid carboxylic acid or a compound with a phenolic hydroxyl group. Material according to one of claims 1 to 21, characterized in that the color-developing component (C) is an active clay or a zinc salicylate. Material according to one of claims 1 to 22, characterized in that components (A) and (B) are dissolved in an organic solvent. Material according to claim 23, characterized in that components (A) and (B) are encapsulated in a microcapsule. Material according to one of claims 1 to 24, characterized in that Components (A) and (B) are incorporated in the form of one or two layers on the back of a transfer sheet and component (C) in a receiving sheet. Material according to one of claims 1 to 24, characterized in that components (A) and (B) are present on the front of the carrier material, which at the same time represents an image sheet with an incorporated color-developing component (C). Material according to one of claims 1 to 26, characterized in that components (A) and (B) are present together with one or more conventional color formers. Material according to claim 27, characterized in that as conventional color formers 3,3- (bis-aminophenyl) phthalides, 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-bis-diarylaminofluoranes, leucoauramines, spiropyrans, spirodipyrans, chromenopyrazoles, benzoxinoxazines, chromenoindoxoles, chromenoindoxoles, chromenoindoxoles, chromenoindoles Phenothiazines, quinazolines, rhodamine lactams, carbazolylmethanes or triarylmethanes are present.