EP0372325B1 - Recording material - Google Patents

Description

The present invention relates to machine readable pressure sensitive reaction recording material.

This is understood to mean, in particular, papers on which visual representations can be produced by means of imagewise mechanical printing. These include the well-known reaction carbonless papers (see M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation, 1972, pages 242-277; G. Baxter in Microencapsulation, Processes and Applications, edited by JE Vandegaer, Plenum Press New York, London, Pages 127-143).

Reaction carbon papers consist, for example, of two or more sheets of paper laid loosely on top of one another, the upper one on the back containing a donor layer and the lower one on the front containing a receiver layer. In other words, a donor layer and a receiver layer are in contact with each other. The donor layer contains e.g. B. microcapsules, the core material in a solution of a dye former is an organic solvent, ie a material that converts the dye former to the dye. A copy occurs when the microcapsules are destroyed by the pressure of a writing instrument and the dye former reacts with the color developer in an imagewise manner. Dye formers and color developers can also be applied to the same paper sheet. One then speaks of "self-contained paper". Writing can be created on such material by means of pictorial printing.

Such methods and preparations are known, for example, from US Pat. Nos. 2,800,457, 2,800,458, 2,948,753, 3,096,189 and 3,193,404 and from German Offenlegungsschriften 2,555,080 and 2,700,937.

Recording materials that absorb in the near infrared are required in order to be able to read the recorded information with suitable devices. The proliferation of computers and automatic data processing require devices that can read information from documents. Therefore, devices for optical letter recognition (OCR) have been developed that can read text pages that are written in the respective programmed font. Such devices usually work in the near infrared and, of course, the writing to be read must therefore have absorption in the near infrared. However, conventional pressure- and thermo-sensitive recording materials do not have such absorption in the near infrared.

Recording materials which have such near infrared absorption are e.g. in U.S. Patents 4,020,056, 4,022,771, 4,026,883, 4,107,428 and 4,119,776 and European Application 0,124,377.

Furthermore, it is known that the acid-developed dye formers contained in the recording materials described, such as, for example, crystal violet lactone and 3-diethylamino-6-methyl-7-anilino-fluorane, have only a relatively low light stability. (N. Kuramoto and T. Kitao; Dyes and Pigments, 3 , 49-58 (1982)).

Surprisingly, it has now been found that the use of special tetraindolyl heptamethines as dye formers in combination with metal salicylates as developers results in higher intensities and better lightfastness of the copies in the IR range in reaction copy papers than when using other developer systems. This combination is therefore particularly suitable for producing copies that are to be read by machine (OCR).

• a) der Farbstoffbildner ein Tetraindolylheptamethinether oder -alkohol der Formeln I/1, I/2, I/3 oder I/4
• 
  b) und der Farbentwickler das Salz eines mehrwertigen Metalls und einer aromatischen Carbonsäure mit mindestens 10 Kohlenstoffatomen der Formel (II)
  

ist, wobei in den oben aufgeführten Formeln
A, B, D und E

bedeuten und untereinander gleich oder verschieden sein können,

Q

Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Aralkyl, Aryl oder ein über Alkyl gebundener heterocyclischer Rest,

R¹

Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Aralkyl oder ein über Alkyl gebundener heterocyclischer Rest,

R²

Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Aralkyl Aryl oder ein gegebenenfalls über Alkyl gebundener heterocyclischer Rest,

T¹ bis T⁵

Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Aralkyl, Halogen, Alkoxy, Dialkylamino, Cyano, Hydroxycarbonyl, Alkoxycarbonyl, Aryl, ein gegebenenfalls über Alkyl gebundener heterocyclischer Rest oder jeweils zwei der Reste T¹ bis T⁵ die fehlenden Glieder eines fünf- bis siebengliedrigen Ringes, der aromatisch oder teilhydriert sein und bis zu 2 Heteroatome aus der Reihe O, N oder S enthalten kann,

U¹

Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Aralkyl, Aryl, Hydroxy, Alkoxy, Halogen, Dialkylamino, Nitro, Cyano, Alkylthio, Alkoxycarbonyl, Dialkylaminocarbonyl, Alkoxycarbonyloxy oder Alkylsulfonyl oder zusammen mit R¹ eine C₂- oder C₃-Brücke und

n

1 oder 2,

X₁, X₂, X₃ und X₄ Wasserstoff, Halogen, Hydroxyl, Alkyl, Cycloalkyl, Aryl, Alkaryl, Aralkyl, Alkoxy oder Aryloxy bedeuten oder zwei benachbarte Reste X₁, X₂, X₃ und X₄ gemeinsam einen Ring bilden können, und wobei alle cyclischen und nichtcyclischen Reste in der Farbstoffchemie übliche nichtionische Substituenten tragen können.The invention thus relates to a recording material comprising, as characteristic constituents, color formers and color developers, characterized in that

• a) the dye former is a tetraindolylheptamethine ether or alcohol of the formulas I / 1, I / 2, I / 3 or I / 4
• 
  b) and the color developer the salt of a polyvalent metal and an aromatic carboxylic acid with at least 10 carbon atoms of the formula (II)
  

is, in the formulas listed above
A, B, D and E

mean and can be the same or different from one another,

Q

Hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical bonded via alkyl,

R¹

Hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl or a heterocyclic radical bonded via alkyl,

R²

Hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl aryl or a heterocyclic radical optionally bonded via alkyl,

T¹ to T⁵

Hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, halogen, alkoxy, dialkylamino, cyano, hydroxycarbonyl, alkoxycarbonyl, aryl, an optionally heterocyclic radical bonded via alkyl or two of the radicals T¹ to T⁵, the missing members of a five- to seven-membered ring, the be aromatic or partially hydrogenated and can contain up to 2 heteroatoms from the O, N or S series,

U¹

Hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxy, alkoxy, halogen, dialkylamino, nitro, cyano, alkylthio, alkoxycarbonyl, dialkylaminocarbonyl, alkoxycarbonyloxy or alkylsulfonyl or together with R¹ a C₂ or C₃ bridge and

n

1 or 2,

X₁, X₂, X₃ and X₄ are hydrogen, halogen, hydroxyl, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy or aryloxy or two adjacent radicals X₁, X₂, X₃ and X₄ can together form a ring, and all of which are cyclic and noncyclic Residues in dye chemistry can carry customary nonionic substituents.

The hydrocarbon radicals mentioned above in any context have the preferred meanings given below.

Alkyl residues, including those in e.g. Alkoxy, alkylamino or aralkyl can have up to 18 carbon atoms and e.g. be substituted by halogen, alkoxy, nitro, cyano, alkoxycarbonyl or alkylsulfonyl.

Alkenyl residues can have up to 18 carbon atoms and e.g. be substituted by halogen, alkoxy, cyano or alkoxycarbonyl.

Cycloalkyl radicals can have 3 to 8 carbon atoms and can be substituted, for example, by alkyl, alkoxy, halogen, cyano, alkoxycarbonyl or aryl.

Aryl radicals, including those in aralkyl and alkaryl groups, are phenyl, naphthyl or anthracenyl, which e.g. can be substituted by alkyl, alkoxy, halogen, cyano, alkoxycarbonyl, nitro, aryl or heterocyclic radicals, where up to 5 substituents, which need not be the same, are possible.

Heterocyclic radicals, including those which are bonded via alkyl, are 5- to 7-membered aromatic or quasi-aromatic heterocycles or their partially or fully hydrogenated derivatives which contain O, N, S or SO₂ as heteroatoms, with a maximum of 4 such heteroatoms which can also be mixed with one another, occur in a ring and these heterocycles fused by benzene, naphthalene or pyridine and / or substituted by alkyl, alkoxy, halogen, cyano, alkoxycarbonyl, nitro or aryl.

Suitable metal salts of carboxylic acids II are those from the group: zinc, aluminum, calcium, magnesium, titanium, nickel, cobalt, manganese, iron, tin, chromium, copper and vanadium.

The color developers can additionally be used in a mixture with per se unreactive or less reactive pigments or other auxiliaries such as silica gel. Examples of such pigments are: talc, titanium dioxide, zinc oxide, chalk; Clays such as kaolin and organic pigments, e.g. B. urea-formaldehyde or melamine-formaldehyde condensation products.

The color developers can also be mixed with other developers, such as e.g. B. Attapulgus clay, acid clay, bentonite or montmorillonite; Halloysite, zeolite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, kaolin and other clays or acidic organic compounds, such as. B. ring-substituted phenols, acidic polymeric materials such as phenolic polymers, alkylphenol acetylene resins, maleic acid rosin resin or partially or fully hydrolyzed polymers of maleic anhydride and styrene, ethylene or vinyl methyl ester or polyacetals.

Capsule wall materials for coating the dye formers are, for. B. gelatin / gum arabic, polyamides, polyurethanes, polyureas, polysulfonamides, polyesters, polycarbonates, polysulfonates, polyacrylates and phenol, melamine or urea-formaldehyde condensates, as described, for example, in M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation 1972; G. Baxter, Microencapsulation, Processes and Applications, publisher J. E. Vandegaer and German Offenlegungsschriften 2 237 545 and 2 229 933.

worin A¹, B¹, D¹ und E¹

bedeuten und untereinander gleich oder verschieden sein können,

Q¹

Wasserstoff, C₁- bis C₁₈-Alkyl, das durch Chlor, C₁- bis C₄-Alkoxy, Cyano oder C₁- bis C₄-Alkoxycarbonyl substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, gegebenenfalls durch C₁- bis C₄-Alkyl, Chlor und/oder C₁- bis C₄-Alkoxy substituierte Benzyl-, Phenethyl-, Naphthylmethyl-, Picolyl-, Phenyl- oder Naphthylreste,

R³

Wasserstoff, C₁- bis C₁₈-Alkyl, das durch Chlor, C₁- bis C₄-Alkoxy, Cyano oder C₁- bis C₄-Alkoxycarbonyl substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, gegebenenfalls durch C₁- bis C₄-Alkyl, Chlor und/oder C₁- bis C₄-Alkoxy substituierte Benzyl-, Phenethyl-, Naphthylmethyl-, oder Picolylreste,

R⁴

Wasserstoff, C₁- bis C₁₈-Alkyl, das durch Chlor, C₁- bis C₄-Alkoxy, Cyano oder C₁- bis C₄-Alkoxycarbonyl substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, gegebenenfalls durch C₁- bis C₄-Alkyl, Chlor, Brom, C₁- bis C₄-Alkoxy, Cyano, Nitro und/oder C₁- bis C₄-Alkoxycarbonyl substituierte Benzyl-, Phenethyl-, Naphthylmethyl-, Picolyl-, Chinolylmethyl-, Phenyl-, Naphthyl-, Pyridyl-, Pyrimidyl-, Pyrazinyl-, Imidazolyl-, Oxazolyl-, Thiazolyl-, Triazolyl-, Benzimidazolyl-, Benzoxazolyl-, Benzthiazolyl- oder Chinolylreste,

T⁶ bis T¹⁰

Wasserstoff, C₁- bis C₈-Alkyl, das durch Chlor, C₁- bis C₄-Alkoxy, Cyano oder C₁- bis C₄-Alkoxycarbonyl substituiert sein kann, Vinyl, Allyl, Cyclohexyl, Cyclopentyl, Fluor, Chlor, Brom, C₁- bis C₈-Alkoxy, das noch durch C₁- bis C₄-Alkoxy substituiert sein kann, C₁- bis C₄-Dialkylamino, Piperidino, Pyrrolidino, Nitro, Cyano, C₁- bis C₄-Alkoxycarbonyl, gegebenenfalls durch C₁- bis C₄-Alkyl, Chlor, C₁- bis C₄-Alkoxy, C₁- bis C₄-Alkylsulfonyl, Cyano und/oder C₁- bis C₄-Alkoxycarbonyl substituierte Benzyl-, Phenethyl-, Naphthylmethyl-, Picolyl-, Phenyl-, Naphthyl-, Pyridyl-, Chinolyl-, Pyrimidyl-, Pyrazinyl-, Indolyl-, Indolenyl-, Indolizinyl-, Imidazolyl-, Oxazolyl-, Thiazolyl-, Triazolyl-, Benzimidazolyl-, Benzoxazolyl- oder Benzthiazolylreste oder jeweils zwei der Reste
T⁶ bis T¹⁰ eine Brücke der Formeln
-CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂SCH₂-,

-CH=CH-CH₂-, -CH=CH-CH=CH,

U²

Wasserstoff, C₁- bis C₈-Alkyl, Allyl, Cyclohexyl, Benzyl, Phenyl, Hydroxy, C₁- bis C₄-Alkoxy, Chlor, Brom, C₁- bis C₄-Dialkylamino, Nitro, Cyano, C₁-bis C₄-Alkylthio, C₁- bis C₄-Alkoxycarbonyl, C₁-bis C₄-Dialkylaminocarbonyl, C₁- bis C₄-Alkoxycarbonyloxy oder C₁- bis C₄-Alkylsulfonyl oder zusammen mit R³ eine -CH₂CH₂- oder -CH₂CH₂CH₂-Brücke, die durch maximal 3 Methylgruppen substituiert sein kann, und

n

1 oder 2 bedeuten.

Preferred dye formers are tetraindolylheptamethine ether or alcohols of the isomeric formulas

wherein A¹, B¹, D¹ and E¹

mean and can be the same or different from one another,

Q¹

Hydrogen, C₁- to C₁ Alkyl-alkyl, which can be substituted by chlorine, C₁- to C₄-alkoxy, cyano or C₁- to C₄-alkoxycarbonyl, allyl, cyclopentyl, cyclohexyl, optionally by C₁- bis C₄-alkyl, chlorine and / or C₁- to C₄-alkoxy substituted benzyl, phenethyl, naphthylmethyl, picolyl, phenyl or naphthyl radicals,

R³

Hydrogen, C₁ to C₁₈ alkyl, which can be substituted by chlorine, C₁ to C₄ alkoxy, cyano or C₁ to C₄ alkoxycarbonyl, allyl, cyclopentyl, cyclohexyl, optionally by C₁ to C₄ alkyl, chlorine and / or C₁ to C₄ alkoxy substituted benzyl, phenethyl, naphthylmethyl, or picolyl radicals,

R⁴

Hydrogen, C₁ to C₁₈ alkyl, which can be substituted by chlorine, C₁ to C₄ alkoxy, cyano or C₁ to C₄ alkoxycarbonyl, allyl, cyclopentyl, cyclohexyl, optionally by C₁ to C₄ alkyl, chlorine, bromine , C₁ to C₄ alkoxy, cyano, nitro and / or C₁ to C₄ alkoxycarbonyl substituted benzyl, phenethyl, naphthylmethyl, picolyl, quinolylmethyl, phenyl, naphthyl, pyridyl, pyrimidyl, pyrazinyl , Imidazolyl, oxazolyl, thiazolyl, triazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl or quinolyl radicals,

T⁶ to T¹⁰

Hydrogen, C₁- to C₈-alkyl, which can be substituted by chlorine, C₁- to C₄-alkoxy, cyano or C₁- to C₄-alkoxycarbonyl, vinyl, allyl, cyclohexyl, cyclopentyl, fluorine, chlorine, bromine, C₁- to C₈-alkoxy, which can also be substituted by C₁- to C₄-alkoxy, C₁- to C₄-dialkylamino, piperidino, pyrrolidino, nitro, cyano, C₁- to C₄-alkoxycarbonyl, optionally by C₁- to C₄-alkyl , Chlorine, C₁ to C₄ alkoxy, C₁ to C₄ alkylsulfonyl, cyano and / or C₁ to C₄ alkoxycarbonyl substituted benzyl, phenethyl, naphthylmethyl, picolyl, phenyl, naphthyl, pyridyl, quinolyl -, Pyrimidyl, pyrazinyl, indolyl, indolenyl, indolizinyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, benzimidazolyl, benzoxazolyl or benzothiazolyl radicals or two each of the radicals
T⁶ to T¹⁰ a bridge of the formulas
-CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂SCH₂-,

-CH = CH-CH₂-, -CH = CH-CH = CH,

U²

Hydrogen, C₁ to C₈ alkyl, allyl, cyclohexyl, benzyl, phenyl, hydroxy, C₁ to C₄ alkoxy, chlorine, bromine, C₁ to C₄ dialkylamino, nitro, cyano, C₁ to C₄ alkylthio, C₁- to C₄-alkoxycarbonyl, C₁-to C₄-dialkylaminocarbonyl, C₁- to C₄-alkoxycarbonyloxy or C₁- to C₄-alkylsulfonyl or together with R³ a -CH₂CH₂- or -CH₂CH₂CH₂ bridge, which can be substituted by a maximum of 3 methyl groups, and

n

1 or 2 mean.

Q¹

Wasserstoff, C₁- bis C₈-Alkyl, das durch Chlor, Methoxy, Ethoxy oder Cyano substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, gegebenenfalls durch Methyl, Chlor oder Methoxy substituierte Benzyl-, Phenethyl- oder Picolylreste,

R³

Wasserstoff, C₁- bis C₈-Alkyl, das durch Chlor, Methoxy, Ethoxy, Cyano oder Methoxycarbonyl substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, gegebenenfalls durch Methyl, Chlor oder Methoxy substituierte Benzyl-, Phenethyl- oder Picolylreste,

R⁴

Wasserstoff, C₁- bis C₈-Alkyl, das durch Chlor, Methoxy, Ethoxy, Cyano oder Methoxycarbonyl substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, gegebenenfalls durch Methyl, Chlor, Methoxy, Cyano, Nitro und/oder Methoxycarbonyl substituierte Benzyl-, Phenethyl-, Picolyl-, Phenyl-, Naphthyl-, Pyridyl-, Pyrimidyl-, Benzimidazolyl-, Benzoxazolyl-, Benzthiazolyl- oder Chinolylreste,

T⁶ und T¹⁰

Wasserstoff, C₁- bis C₈-Alkyl, das durch Chlor, Methoxy, Cyano oder Methoxycarbonyl substituiert sein kann, Vinyl, Allyl, Cyclopentyl, Cyclohexyl, Chlor, C₁- bis C₈-Alkoxy, Cyano, Methoxycarbonyl, Nitro, Benzyl, gegebenenfalls durch Methyl, Chlor, Cyano oder Methoxy substituierte Phenyl- oder Pyridylreste,

T⁷ bis T⁹

Wasserstoff, C₁- bis C₈-Alkyl, das durch Chlor, Methoxy, Cyano oder Methoxycarbonyl substituiert sein kann, Allyl, Cyclopentyl, Cyclohexyl, Chlor, Brom, Cyano, Methoxy- und Ethoxycarbonyl, Nitro, C₁- bis C₄-Alkoxy, C₁- bis C₄-Dialkylamino, Benzyl, gegebenenfalls durch Methyl, Ethyl, Chlor, Methoxy, Ethoxy, Cyano, Nitro und/oder Methoxycarbonyl substituierte Phenyl-, Naphthyl-, Pyridyl-, Chinolyl-, Pyrimidyl-, Indolenyl-, Indolizinyl-, Imidazolyl-, Oxazolyl-, Thiazolyl-, Benzimidazolyl-, Benzoxazolyl- oder Benzthiazolylreste oder T⁷ mit T⁸ oder T⁹ oder T⁸ mit T⁹ eine Brücke der Formeln
-CH₂CH₂-, -CH₂CH₂CH₂-,

-CH₂=CH-CH₂-, -CH=CH-CH=CH- oder

U²

Wasserstoff, C₁- bis C₄-Alkyl, Cyclohexyl, Benzyl, C₁- bis C₄-Alkoxy, Chlor, C₁- bis C₄-Dialkylamino, Nitro, Cyano, Methoxy- oder Ethoxycarbonyl oder Methylsulfonyl, wobei U² in 5-, 6- und/oder 7-Position am Indolylrest stehen kann oder ein in 7-Position stehender Rest U² zusammen mit R³ eine Brücke der Formeln
-CH₂CH₂-

-CH₂CH₂CH₂-,

bilden kann, und

n

1 oder 2 bedeuten.

Tetraindolylheptamethine ether or alcohols of the formulas III to VI are particularly preferred

Q¹

Hydrogen, C₁- to C₈-alkyl, which can be substituted by chlorine, methoxy, ethoxy or cyano, allyl, cyclopentyl, cyclohexyl, benzyl, phenethyl or picolyl radicals optionally substituted by methyl, chlorine or methoxy,

R³

Hydrogen, C₁- to C₈-alkyl, which can be substituted by chlorine, methoxy, ethoxy, cyano or methoxycarbonyl, allyl, cyclopentyl, cyclohexyl, benzyl, phenethyl or picolyl radicals optionally substituted by methyl, chlorine or methoxy,

R⁴

Hydrogen, C₁ to C₈ alkyl, which can be substituted by chlorine, methoxy, ethoxy, cyano or methoxycarbonyl, allyl, cyclopentyl, cyclohexyl, optionally substituted by methyl, chlorine, methoxy, cyano, nitro and / or methoxycarbonyl, benzyl, phenethyl -, picolyl, phenyl, naphthyl, pyridyl, pyrimidyl, benzimidazolyl, benzoxazolyl, benzothiazolyl or quinolyl radicals,

T⁶ and T¹⁰

Hydrogen, C₁- to C₈-alkyl, which can be substituted by chlorine, methoxy, cyano or methoxycarbonyl, vinyl, allyl, cyclopentyl, cyclohexyl, chlorine, C₁- to C₈-alkoxy, cyano, methoxycarbonyl, nitro, benzyl, optionally by methyl , Chlorine, cyano or methoxy substituted phenyl or pyridyl radicals,

T⁷ to T⁹

Hydrogen, C₁- to C₈-alkyl, which can be substituted by chlorine, methoxy, cyano or methoxycarbonyl, allyl, cyclopentyl, cyclohexyl, chlorine, bromine, cyano, methoxy- and ethoxycarbonyl, nitro, C₁- to C₄-alkoxy, C₁- to C₄-dialkylamino, benzyl, optionally substituted by methyl, ethyl, chlorine, methoxy, ethoxy, cyano, nitro and / or methoxycarbonyl, phenyl, naphthyl, pyridyl, quinolyl, pyrimidyl, indolenyl, indolizinyl, imidazolyl , Oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl or benzthiazolyl or T⁷ with T⁸ or T⁹ or T⁸ with T⁹ a bridge of the formulas
-CH₂CH₂-, -CH₂CH₂CH₂-,

-CH₂ = CH-CH₂-, -CH = CH-CH = CH- or

U²

Hydrogen, C₁ to C₄ alkyl, cyclohexyl, benzyl, C₁ to C₄ alkoxy, chlorine, C₁ to C₄ dialkylamino, nitro, cyano, methoxy or ethoxycarbonyl or Methylsulfonyl, where U² can be in the 5-, 6- and / or 7-position on the indolyl radical or a 7-position radical U² together with R³ is a bridge of the formulas
-CH₂CH₂-

-CH₂CH₂CH₂-,

can form, and

n

1 or 2 mean.

und ihre bezüglich der Stellung der Q²O-Gruppe isomeren Formen wie sie in den Formeln II bis IV und VI bis VIII wiedergegeben sind, worin

Q²

Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Hexyl, Octyl, Cyclohexyl oder Benzyl,

R⁵

Methyl, Ethyl, Propyl, Butyl, Hexyl, Octyl, 2-Cyanoethyl, 2-Methoxyethyl, 2-Methoxycarbonylethyl, 2-Chlorethyl, 2-Acetoxyethyl, Cyclohexyl, Allyl oder Benzyl,

R⁶

Methyl, Ethyl, Propyl, Butyl, Hexyl, Octyl, Cyclohexyl, Benzyl, Phenyl, 2-, 3- oder 4-Chlor-phenyl, 2-, 3- oder 4-Methoxy-phenyl, 4-Nitro-phenyl, 2,4-Dichlor-phenyl, 2-, 3-oder 4-Tolyl oder 2-, 3- oder 4-Pyridyl,

T¹¹

Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Vinyl, 2-Chlor-ethyl, 2-Cyano-ethyl, Chlor, Cyano, Phenyl, 4-Tolyl oder 4-Chlor-phenyl,

T¹² und T¹³

Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Chlor, Cyano, Methoxycarbonyl, Dimethylamino, Phenyl, 4-Tolyl, 4-Chlor-phenyl, Pyridyl oder T¹² und T¹³ gemeinsam eine Gruppierung der Formeln
-CH₂CH₂-, -CH₂CH₂CH₂-,

T¹⁴

Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Chlor, Brom, Cyano, Phenyl, 4-Tolyl, 4-Chlor-phenyl, 4-Nitro-phenyl, 4-Pyridyl, 3,3-Dimethyl-indolen-2-yl, Indolizin-2-yl, 2-Benzimidazolyl, 2-Benzoxazolyl oder 2-Benzthiazolyl,

U³ und U⁴

Wasserstoff, Methyl, Methoxy, Chlor, Cyano, Methoxycarbonyl oder Nitro bedeuten.

Tetraindolylheptamethine ethers or alcohols of the formula are very particularly preferred

and their isomeric forms with respect to the position of the Q 2 O group as represented in the formulas II to IV and VI to VIII, in which

Q²

Hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, cyclohexyl or benzyl,

R⁵

Methyl, ethyl, propyl, butyl, hexyl, octyl, 2-cyanoethyl, 2-methoxyethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-acetoxyethyl, cyclohexyl, allyl or benzyl,

R⁶

Methyl, ethyl, propyl, butyl, hexyl, octyl, cyclohexyl, benzyl, phenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methoxyphenyl, 4-nitro-phenyl, 2, 4-dichlorophenyl, 2-, 3- or 4-tolyl or 2-, 3- or 4-pyridyl,

T¹¹

Hydrogen, methyl, ethyl, propyl, butyl, vinyl, 2-chloro-ethyl, 2-cyano-ethyl, chlorine, cyano, phenyl, 4-tolyl or 4-chloro-phenyl,

T¹² and T¹³

Hydrogen, methyl, ethyl, propyl, butyl, chlorine, cyano, methoxycarbonyl, dimethylamino, phenyl, 4-tolyl, 4-chlorophenyl, pyridyl or T¹² and T¹³ together form a grouping of the formulas
-CH₂CH₂-, -CH₂CH₂CH₂-,

T¹⁴

Hydrogen, methyl, ethyl, propyl, butyl, chlorine, bromine, cyano, phenyl, 4-tolyl, 4-chlorophenyl, 4-nitro-phenyl, 4-pyridyl, 3,3-dimethyl-indolen-2-yl, Indolizin-2-yl, 2-benzimidazolyl, 2-benzoxazolyl or 2-benzthiazolyl,

U³ and U⁴

Are hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl or nitro.

Preferred color developers are those of the formula II in which at least one of the X¹-X² radicals is aralkyl and the other radicals are H.

worin die Ringe A und B weitere Substituenten aufweisen können und worin bedeuten Y²=H oder CHY³Y⁴ bedeutet und

Y¹, Y³, Y⁴

unabhängig voneinander H oder Alkyl (insbesondere mit 1 bis 4 C-Atomen) oder zusammen mit wenigstens 2 C-Atomen des Ringes A den Rest zur Vervollständigung eines insbesondere carbocyclischen Ringes

Z

M

m-wertiges Metallion, insbesondere Cu²⁺, Zn²⁺, Fe²⁺, Fe³⁺, Al³⁺, Mg²⁺ oder Ca²⁺

m

ganze Zahl, inbesondere 2 oder 3

n

ganze Zahl, wenigstens 1, insbesondere 2 bis 30, speziell 3 bis 6

p

ganze Zahl von 1 bis 4 bedeuten.

Compounds of the formula VIII are particularly preferred as color developers

in which the rings A and B may have further substituents and in which mean Y² = H or CHY³Y⁴ and

Y¹, Y³, Y⁴

independently of one another H or alkyl (in particular with 1 to 4 carbon atoms) or together with at least 2 carbon atoms of the ring A the remainder to complete a particularly carbocyclic ring

Z

M

m-valent metal ion, particularly Cu²⁺, Zn²⁺, Fe²⁺, Fe³⁺, Al³⁺, Mg²⁺ or Ca²⁺

m

integer, especially 2 or 3

n

integer, at least 1, in particular 2 to 30, especially 3 to 6

p

are integers from 1 to 4.

worin

Y¹ bis Y⁴

, Z, M, m, n und p die oben angegebene Bedeutung haben und worin bedeuten

Y⁵ bis Y⁸

unabhängig voneinander Wasserstoff, Alkyl, insbesondere mit 1 bis 18 C-Atomen, Aralkyl, insbesondere Benzyl oder α-Methylbenzyl, Halogen, insbesondere Chlor, Alkoxy, insbesondere mit 1 bis 24 C-Atomen, COOH, COOY⁹, CN, NO₂, oder -O-CO-Y¹² oder Cycloalkyl, wobei Y⁷ und Y⁸ unabhängig voneinander auch

bedeuten können, wobei

Y⁹

Alkyl, insbesondere 1 bis 24 C-Atomen, Aryl, insbesondere Phenyl oder NY¹¹Y¹⁰,

Y¹⁰, Y¹¹

unabhängig voneinander Wasserstoff, Alkyl, insbesondere mit 1 bis 24 C-Atomen,

Y¹²

Alkyl, insbesondere C₁-C₁₈

und wobei vorzugsweise die Gruppe COOZ im Ring B in o-Stellung zur OH-Gruppe steht.In a particularly preferred embodiment, the compounds of the formula VIII given above have the following structure

wherein

Y¹ to Y⁴

, Z, M, m, n and p have the meaning given above and what they mean

Y⁵ to Y⁸

independently of one another hydrogen, alkyl, in particular with 1 to 18 C atoms, aralkyl, in particular benzyl or α-methylbenzyl, halogen, in particular chlorine, alkoxy, in particular with 1 to 24 C atoms, COOH, COOY⁹, CN, NO₂, or - O-CO-Y¹² or cycloalkyl, where Y⁷ and Y⁸ independently

can mean, where

Y⁹

Alkyl, in particular 1 to 24 carbon atoms, aryl, in particular phenyl or NY¹¹Y¹⁰,

Y¹⁰, Y¹¹

independently of one another hydrogen, alkyl, in particular with 1 to 24 carbon atoms,

Y¹²

Alkyl, especially C₁-C₁₈

and preferably the group COOZ in ring B is in the o-position to the OH group.

Such compounds and the preparation of appropriate suspensions are such. B. from DE-OS 3 635 311 and 3 635 742. Preferred are the Al, Mg, Ca and in particular Zn salts.

The color development properties of the color developers according to the invention are particularly favorable when they are used as "hybrid systems", ie when they are combined with chemically modified aluminum layer silicates based on montmorillonite. Furthermore, the coating colors must be provided with binders in order to fix the color developers on a support. Since paper is preferred as a carrier, acts These binders are mainly paper coating compositions such as 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 mono- or copolymers.

The coating compositions containing colorants according to the invention permit the use of various known coating techniques, for example application with a blade coater and other common coating techniques. In addition to aqueous coating colors, incorporation into printing inks for flexo or offset printing is also possible. The coating compositions containing color developers according to the invention permit the use of various known coating techniques, for example application with a blade coater or other common coating techniques.

When producing an offset or letterpress ink, the developer resins according to the invention can be rubbed with a suitable varnish on a three-roll mill. The production of such offset printing inks is known in the art.

In a conventional manner, CB papers which are coated with capsules which contain the dye formers according to the invention dissolved in an organic solvent are brought into contact with CF papers which are coated with the developer substances according to the invention; or
Capsules which contain the dye formers according to the invention dissolved in an organic solvent, applied together with the color developers according to the invention on the top of a sheet in a conventional manner and used as "self-contained papers" in a copy set in the usual manner. The copy is now created by imagewise mechanical pressure on the surface of the CB paper by developing the dye-forming solution emerging from the destroyed capsules on the surface of the CF paper.

To measure the reflectance, for example, a large-scale impression (copy) by z. B. pressure-related destruction of the capsules containing the color former according to the invention on the back of a corresponding CB paper on the front of a CF paper containing the color developer according to the invention, or a large-area impression by z. B. pressure-induced destruction of the capsules containing the color former according to the invention in a mixture with the color developers according to the invention carried out on the front of a base paper.

wobei gilt

%ABS_λ

Absorption bei der Wellenlänge _λ

%RemCF_λ

Remission des CF bei der Wellenlänge _λ (Leerwert)

%RemKopie_λ

Remission der Kopie bei der Wellenlänge _λ

In analoger Weise wird die Intensität einer belichteten Kopie gemessen.The intensity of this copy in the IR range can be determined with the usual optical spectrophotometers such as a Xenocolor LS 100 from Lange or an El Repho 44381 from Carl Zeiss, in which the reflectance at a certain wavelength is in the IR range measures and then the absorption at this Wavelength calculated
by

where applies

% ABS _λ

Absorption at the wavelength _λ

% RemCF _λ

Remission of the CF at the wavelength _λ (blank value)

% Remcopy _λ

Remission of the copy at the wavelength _λ

The intensity of an exposed copy is measured in an analogous manner.

For this purpose, the impression, the intensity of which was determined at a certain wavelength, is irradiated for 48 hours in a box with light emitted by four 18-watt fluorescent tubes (Sylvania-Luxline-ES; daylight de luxe).

The intensities of the copy and the exposed copy are determined in the IR range between 700 and 1200 nm, preferably between 800 and 1000 nm and particularly preferably between 840 and 910 nm.

The use of the color formers according to the invention in microcapsules in combination with the color developers according to the invention shows, before and after exposure, significantly higher intensities and a lower decrease in intensity than the use of the color formers according to the invention on other color developers, such as clay and phenolic resins.

example 1

enthält, wird auf
200 ml Methanol ausgetragen und mit 50 ml 30 %iger methanolischer Natriummethylatlösung alkalisch gestellt. Das beigebraune Produkt wird abgesaugt, mit Methanol und Wasser gewaschen und getrocknet:
22,0 g (94,6 % der Theorie). Das Produkt wird in 200 ml Methanol 2 Stunden gekocht, abgekühlt, abgesaugt und getrocknet:
18,5 g (79,6 %) bräunlich-beiges Pulver vom Schmelzpunkt 216-218° C.21.9 g of 1,1-bis (1-methyl-2-phenyl-indol-2-yl) ethene and 4.3 g of 1,1,3,3-tetramethoxypropane are mixed in a mixture of 50 ml of acetic anhydride and 2.5 g of methanesulfonic acid stirred at 80 ° C for 1 hour. The black and blue solution containing the dye of the formula

contains is on
200 ml of methanol are discharged and made alkaline with 50 ml of 30% methanolic sodium methylate solution. The beige-brown product is filtered off, washed with methanol and water and dried:
22.0 g (94.6% of theory). The product is boiled in 200 ml of methanol for 2 hours, cooled, suction filtered and dried:
18.5 g (79.6%) of a brownish-beige powder with a melting point of 216-218 ° C.

In an isomeric form, the product corresponds to the formula:

A solution in glacial acetic acid shows a dirty blue color and λ _max = 863 nm. A solution in toluene develops a pale gray-blue color on acid clay. An absorption of 750 to 950 nm can be measured in the infrared.

Example 2

enthält, auf 250 ml Methanol ausgetragen und mit methanolischer Methylatlösung alkalisch gestellt. Es wird abgesaugt, mit Methanol und Wasser gewaschen. Durch Umkristallisieren aus Butanol erhält man 22,3 g (82,8 %) gelbes Pulver vom Schmelzpunkt 217 bis 219° C. In einer isomeren Form entspricht das Produkt der Formel

λ_max in Eisessig: 859 nm
Auf Säureton: grünlichgrau, 750 bis 950 nm.21.9 g 1,1-bis (1-methyl-2-phenylindol-3-yl) ethene and sodium (2- (benzothiazol-2-yl) -3-oxo-prop-1-ene -1-olate) are stirred in a mixture of 50 ml of acetic anhydride and 7.7 g of trifluoromethanesulfonic acid at 90 ° C. for 1 hour. After cooling, the greenish blue solution containing the dye of the formula

contains, poured onto 250 ml of methanol and made alkaline with methanolic methylate solution. It is suctioned off, washed with methanol and water. Recrystallization from butanol gives 22.3 g (82.8%) of yellow powder with a melting point of 217 to 219 ° C. In an isomeric form, the product corresponds to the formula

λ _max in glacial acetic acid: 859 nm
On acid clay: greenish gray, 750 to 950 nm.

Example 3

1038 g (7.5 mol) of salicylic acid, 1012.8 g (8 mol) of benzyl chloride, 63.2 g (0.5 mol) of ZnCl₂ and 50 ml of H₂O are melted in an oil bath while stirring and passing nitrogen through, with 120 ° C a strong cleavage of HCl is used. A further 2785.2 g (22 mol) of benzyl chloride are allowed to run in at 120 to 130 ° C. in the course of 3 hours, and the mixture is subsequently stirred at a constant temperature for 5 hours while passing nitrogen through the melt until the evolution of HCl has ended. Subsequent removal of volatile components in vacuum provides only minor amounts (approx. 10 g) of distillate. The yield is 3789 g (99.9% of theory) of a light yellowish-brownish brittle resin.

When cooling the melt at about 100 ° C. with good stirring using an anchor stirrer, 1990 g of a 10% aqueous solution of a partially saponified polyvinyl acetate and 135 g (about 1.5 mol) of 45% sodium hydroxide solution are run into the resin and stirring is continued 30 minutes at 60-70 ° C until a stable, colorless dispersion has formed. A smooth slurry of 265 g (3.25 mol) of ZnO in 1780 g of H₂O is gradually stirred into this to the extent that a temperature of approximately 40-45 ° C. is established. The mixture is kept at this temperature for about 1 hour with thorough stirring until the Zn complex has fully formed. To remove any specks, roll over a three-roll mill and obtain 7955 g of an almost colorless, viscous but pourable dispersion.

Example 4

Analogously to the procedure in Example 3, styrene is used instead of benzyl chloride, resulting in α-methylbenzylated salicylates according to DE-A 3635742.

Example 5

26 g of 3,5-bis- (6-isocyanato-hexyl) -2H-1,3,5-oxadiazine-2 were added to 174 g of a colorant mixture which contains 3% of the dye former from Example 1 in an isomer mixture of diisopropylnaphthalene , 4,6- (3H, 5H) trione stirred in. This mixture was treated with 251 g of a 0.5% polyvinyl acetate solution (Mowiol) 26/88; Hoechst AG) emulsified on a rotor stator disperser, so that the mean droplet size of the emulsion was 7 μm. 49 g of a 9% diethylenetriamine solution were then added with stirring and the mixture was heated at 60 ° C. for 2 h. A microcapsule dispersion was thus obtained, the dry content determination of which gave a weight fraction of 39.9%.

Example 6

80 g of a 3% color former solution of the color former from Example 2 in an isomer mixture of diisopropylnaphthalene were microencapsulated by a coacervation process as described in German Patent DE 3 008 390 in Example II. The average capsule size was 5.5 μm and the weight fraction of the capsules after the dry weight determination was 45.1%.

Example 7 (Production of CB Paper)

2.1 g of Arbocell ^(R) BE 600/30 (shredded cellulose fibers), 2.0 g of Baystal ^(R) P 1700 (latex based on styrene / butadiene copolymer) and 16 g of capsule dispersion were added to 12.9 g of 40% capsule dispersion. 3 g of water stirred in. This mixture was applied to a base paper (40 g / m²) using a 40 μm doctor blade and dried. This gave a CB paper with a coating weight of approximately 5.5 g / m 2.

Example 8 (Production of CF paper)

312 g of water were mixed with conc. Sodium hydroxide solution adjusted to pH 11. 91.7 g of china clay and 20 g of 5% carboxymethyl cellulose solution were stirred into it. 50 g of developer dispersion according to Example 3 and 16 g of Binder Baystal P 1700 were then added in succession and the pH was adjusted to 9. This mixture was applied to a base paper (40 g / m²) by means of a 40 μm doctor blade and dried, and a CF paper with a coating weight of approx. 5 g / m² was obtained.

Example 9-13

In a conventional manner, the CB papers produced in Example 7 were combined with the CF papers produced in Example 8 and commercially available CF papers coated with various developer substances. The copy is made by printing a roll with a width of 39 mm with a constant force of 680 N over a distance of 20 cm.

% Abs_λ

Absorption bei der Wellenlänge _λ

% Rem. CF_λ

Remission des CF bei der Wellenlänge _λ (Leerwert)

% Rem. Kopie_λ

Remission der Kopie bei der Wellenlänge _λ

Die Absorptionswerte der Kopien auf verschiedenen CF-Papieren sind in Tabelle 1 dargestellt.Now with a Xenocolor LS 100 from Dr. Long the reflectance spectra of the copies from 400 - 1200 nm recorded, the respective absorption being obtained by

% Abs _λ

Absorption at the wavelength _λ

% Rem. CF _λ

Remission of the CF at the wavelength _λ (blank value)

% Rem. Copy _λ

Remission of the copy at the wavelength _λ

The absorption values of the copies on various CF papers are shown in Table 1.

The absorption maximum, either at 850 nm or 900 nm, determines the absorption value given in Table 1. The copy is now exposed in an exposure box with 4 fluorescent tubes (Sylvania-Luxline-ES; 4 x 18 W) and then the absorption value is determined as described above.

Example 14

Analogously to Example 8, the developer according to Example 4 is used to produce a CF paper with a coating weight of approximately 5 g / m².

Examples 15-19

The CF papers produced in Example 14 were tested analogously to Examples 9 to 13. The absorption values of the copies before and after exposure are shown in Table 2.

Claims (4)

1. Pressure-sensitive reactive recording material containing colour-forming agents and colour developers as characteristic constituents, characterised in that

   a) the dyestuff-forming agent is a tetraindolylheptamethine of the formulae I/1, I/2, I/3 or I/4

   

   b) and the colour developer is the salt of a polyvalent metal and an aromatic carboxylic acid having at least 10 carbon atoms, of the formula (II)

   

   wherein, in the abovementioned formulae,
   A, B, D and E denote

   

   and can be identical to or different from one another,

   Q   denotes hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical which is bonded via alkyl,

   R¹   denotes hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl or a heterocyclic radical which is bonded via alkyl,

   R²   denotes hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical which is optionally bonded via alkyl,

   T¹ to T⁵   denote hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, halogen, alkoxy, dialkylamino, cyano, hydroxycarbonyl, alkoxycarbonyl, aryl or a heterocyclic radical which is optionally bonded via alkyl, or in each case two of the radicals T¹ to T⁵ denote the missing members of a 5- to 7-membered ring, which can be aromatic or partly hydrogenated and can contain up to 2 heteroatoms from the series comprising O, N or S,

   U¹   denotes hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxyl, alkoxy, halogen, dialkylamino, nitro, cyano, alkylthio, alkoxycarbonyl, dialkylaminocarbonyl, alkoxycarbonyloxy or alkylsulphonyl, or, together with R¹, denote a C₂- or C₃-bridge, and

   n   denotes 1 or 2,

   X₁, X₂, X₃ and X₄ denote hydrogen, halogen, hydroxyl, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy or aryloxy, or two adjacent radicals X₁, X₂, X₃ and X₄ together can form a ring,
   and wherein all the cyclic and non-cyclic radicals can carry nonionic substituents which are customary in dyestuff chemistry.
2. Pressure-sensitive recording material according to Claim 1, characterised in that the colour developers used are those of the formula II wherein at least one of the radicals X₁ - X₄ represents aralkyl and the other radicals represent H.
3. Pressure-sensitive recording material according to Claim 1 characterised in that the colour developers used are those of the formula VIII

   

   wherein the rings A and B can contain further substituents and wherein Y² denotes H or CHY³Y⁴ and

   Y¹, Y³ and Y⁴   independently of one another denote H or alkyl (in particular having 1 to 4 C atoms) or, together with at least 2 C atoms of the ring A, denote the radical to complete a ring, in particular a carbocyclic ring,

   Z   denotes

   

   M   denotes an m-valent metal ion, in particular Cu²⁺, Zn²⁺, Fe²⁺, Fe³⁺, Al³⁺, Mg² or Ca²⁺,

   m   denotes an integer, in particular 2 or 3,

   n   denotes an integer, at least 1, in particular 2 to 30 and specifically 3 to 6, and

   p   denotes an integer from 1 to 4.
4. Pressure-sensitive recording material according to Claim 1, characterised in that the colour developers used are those of the formula IX

   

   wherein
   Y¹ to Y⁴, Z, M, m, n and p have the abovementioned meaning, and wherein,
   Y⁵ to Y⁸ independently of one another denote hydrogen, alkyl, in particular having 1 to 18 C atoms, aralkyl, in particular benzyl or α-methylbenzyl, halogen, in particular chlorine, alkoxy, in particular having 1 to 24 C atoms, COOH, COOY⁹, CN, NO₂ or -O-CO-Y¹² or cycloalkyl, wherein Y⁷ and Y⁸ independently of one another can also denote

   

   wherein

   Y⁹   denotes alkyl, in particular 1 to 24 C atoms, aryl, in particular phenyl, or NY¹¹Y¹⁰,

   Y¹⁰ and Y¹¹   independently of one another denote hydrogen or alkyl, in particular having 1 to 24 C atoms and

   Y¹²   denotes alkyl, in particular C₁-C₁₈,

   and wherein the group COOZ in ring B is preferably in the o-position relative to the OH group.