EP0112291B1 - Heat-sensitive registration material - Google Patents

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Publication number
EP0112291B1
EP0112291B1 EP83810570A EP83810570A EP0112291B1 EP 0112291 B1 EP0112291 B1 EP 0112291B1 EP 83810570 A EP83810570 A EP 83810570A EP 83810570 A EP83810570 A EP 83810570A EP 0112291 B1 EP0112291 B1 EP 0112291B1
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Prior art keywords
developer
zinc
formula
recording material
hydroxy
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German (de)
French (fr)
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EP0112291A2 (en
EP0112291A3 (en
Inventor
Hermann Nachbur
Christel Tempel
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Novartis AG
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Ciba Geigy AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

  • the double and triple substituents R and X can be the same or different. They are preferably identical in each case.
  • Lower alkyl and lower alkoxy are groups which have 1 to 5, in particular 1 to 3, carbon atoms, e.g. Methyl, ethyl, isopropyl, sec-butyl, tert-butyl or methoxy, ethoxy, isopropoxy, n-butoxy or tert-butoxy.
  • X is preferably halogen, methyl, methoxy, ethoxy or especially hydrogen.
  • R represents an alkyl group, this can be straight-chain or branched.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, isooctyl, nonyl, isononyl or dodecyl.
  • R is, for example, cyclopentyl or preferably cyclohexyl.
  • Preferred substituents in the phenyl group of the R radical are chlorine, methyl or methoxy.
  • R is preferably phenyl or phenyl substituted by halogen, methyl, methoxy or ethoxy, e.g. Chlorophenyl, methylphenyl, dimethylphenyl or methoxyphenyl.
  • Halogen means for example fluorine, bromine or preferably chlorine.
  • Preferred phenolsulfonyl compounds of the formula (1) are those in which R is methylphenyl, methoxyphenyl or in particular phenyl and X is hydrogen.
  • the aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) used according to the invention represent a new class of color developers or electron acceptors for color formers.
  • the zinc phenates are preferably prepared by reacting 2 moles of a phenolsulfonyl compound of the formula (1) with 1 mole of the zinc salt of an inorganic acid or a lower aliphatic or aromatic carboxylic acid.
  • the zinc phenates thus obtained correspond to the formula where R and X have the meaning given.
  • the substituents defined for R and X can be the same or different.
  • the reaction is advantageously carried out in a melt or in an alkaline solution of the phenolsulfonyl compound used, advantageously at 60 to 90 ° C and preferably in the presence of an alkali compound, e.g. Alkali metal hydroxides, carbonates or bicarbonates or ammonium hydroxide, ammonium carbonate or ammonium hydrogen carbonate.
  • an alkali compound e.g. Alkali metal hydroxides, carbonates or bicarbonates or ammonium hydroxide, ammonium carbonate or ammonium hydrogen carbonate.
  • Zinc chloride, zinc sulfate or zinc nitrate may be mentioned as examples of inorganic zinc salts.
  • Organic zinc salts are e.g. Zinc diacetate, zinc oxalate, zinc hydrogen benzoate or especially zinc dibenzoate.
  • zinc oxide or zinc carbonate can also be used, in which case the reaction with the phenolsulfonyl compound is carried out, preferably in the presence of ammonium formate.
  • the aluminum phenates are obtained by condensing 3 moles of a phenolsulfonyl compound of the formula (1) or its alkali metal salts with a water-soluble aluminum salt of an inorganic or organic acid.
  • the preparation is preferably carried out by reacting 3 moles of a phenolsulfonyl compound of the formula (1) with the aluminum salt of a lower, preferably secondary aliphatic or cycloaliphatic alcohol, in particular with aluminum triisopropoxide, aluminum sec-butoxide or aluminum cyclohexoxide.
  • the aluminum phenates thus obtained correspond to the formula where R and X have the meaning given.
  • the reaction is expediently carried out by heating the reactants at a temperature of 80 to 200 ° C., whereupon the lower aliphatic or cycloaliphatic alcohol released is removed by distillation.
  • Phenolsulfonyl compounds of formula (1) and their preparation are e.g. in Beilstein, E II 6, pp. 852-855 and E III 6, pp. 4445-55.
  • a preferred method for the preparation of the phenolsulfonyl compounds of formula (1) is that a compound of formula
  • X and R have the meaning given and Hal means halogen, such as chlorine, bromine or fluorine.
  • the reaction is carried out in an anhydrous medium in the presence of Lewis acids, such as, for example, AICI 3 , FeCl 3 , ZnCl 2 , SnC1 4 , SbC1 5 or BF 3 and advantageously at a temperature of 50 to 200 ° C., preferably 80 to 130 ° C.
  • Lewis acids such as, for example, AICI 3 , FeCl 3 , ZnCl 2 , SnC1 4 , SbC1 5 or BF 3 and advantageously at a temperature of 50 to 200 ° C., preferably 80 to 130 ° C.
  • Another method is that you have a compound of formula wherein R, X and Hal have the meaning given, heated to 200 to 220 ° C. with aqueous potassium hydroxide solution.
  • the aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) used according to the invention are practically colorless and odorless and very reactive with the conventional color formers, so that spontaneous, stable and non-fading recordings or copies are obtained.
  • the aluminum and zinc phenates used are characterized in particular by the fact that the records or copies thus obtained have excellent storage stability up to 60 ° C.
  • the color formers which can be used in the recording material or copying material according to the invention are known colorless or slightly colored chromogenic substances which, if they come into contact with the zinc phenates of the formula (2) or with the aluminum phenates of the formula (3), become colored or change color .
  • Color formers or mixtures thereof can be used, which z. B.
  • azomethines fluorans, benzofluoranes, phthalides, azaphthalides, spiropyrans, spirodipyrans, leucoauramines, triarylmethane leuco dyes, carbazolylmethanes, chromenoindoles, chromenopyrazoles, phenoxazines, phenothiazines as well as the chromeno- or chromano-color former.
  • suitable color formers are:
  • Crystal violet lactone 3,3- (bisaminophenyl) phthalide, 3,3- (bis-substituted-indolyl) phthalide, 3- (aminophenyl) -3-indolyl phthalide, 3- (aminophenyl) -3-indolyl azaphthalide, 6-dialkylamino-2-n-octylaminofluorane, 6-dialkylamino-2-arylaminofluorane, 6-dialkylamino-3-methyl-2-arylamino-fluorane, 6-dialkylamino-2- or -3-lower alkyl-fluorane, 6-dialkylamino- 2-dibenzylamino-fluoranes, 6-N-cyclohexyl-N-lower alkyl-3-methyl-2-arylamino-fluoranes, 6-pyrrolidino-2-arylamino-fluoranes, bis- (aminophenyl) -furyl
  • Aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) are suitable as color developers for heat-sensitive or thermoreactive recording material.
  • This usually contains at least one carrier, a color former, a developer and optionally also a binder and / or wax.
  • Thermoreactive recording systems include e.g. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. used in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, e.g. Electrocardiograph.
  • the imaging (marking) can also be done manually with a heated spring.
  • Another device for generating markings using heat is laser beams.
  • thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in one binder layer and the developer is dissolved or dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer.
  • the binder is softened by heat in specific areas and at those points where heat is applied, the color former comes into contact with the developer and the desired color develops immediately.
  • the aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) can be used alone in heat-sensitive recording materials, as mixtures or in a mixture with known developers.
  • Typical examples of known developers are Active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, for example acid-activated bentonite or montmorillonite; also halloysite, zeolite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, kaolin or any clay or acid-reacting organic compounds, such as optionally ring-substituted salicylic acid or salicylic acid esters and their metal salts; also an acidic polymeric material such as a phenolic polymer, an alkylphenol acetylene resin, a maleic rosin resin or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene.
  • Active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, for example acid-
  • the aluminum and zinc phenates which can be used according to the invention can advantageously also in combination with metal-free phenolic compounds, such as e.g. 4-tert-butylphenol, 4-phenylphenol, methylene-bis- (p-phenylphenol), 4-hydroxydiphenyl ether, a-naphthol, ⁇ -naphthol, 4-hydroxybenzoic acid methyl, ethyl, n-butyl or especially benzyl ester , 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, 4-hydroxydiphenylsulfone, 4,4'-isopropyldiphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4'-bis (hydroxyphenyl) valeric acid, Hydroquinone, pyrogallol, phloroglucinol, p-, m-, o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naph
  • Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water soluble, while the color former and developer are insoluble in water. The binder should be able to disperse and fix the color former and developer at room temperature.
  • Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or etherified corn starch.
  • hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or etherified corn starch.
  • water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
  • binders soluble in non-polar or only weakly polar solvents
  • Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
  • the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.
  • thermoreactive layers can contain further additives.
  • further additives for example, talc, titanium dioxide, zinc oxide, aluminum hydroxide, calcium carbonate (eg chalk), clays such as kaolin, as well as organic pigments, such as Contain urea formaldehyde or melamine formaldehyde polymers.
  • thermographic recording materials contain waxes, for example carnauba wax, montana wax, paraffin wax, polyethylene wax or condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
  • the two dispersions are then mixed.
  • the colorless mixture is applied to a paper with a basis weight of 50 g / m 2 using a doctor blade.
  • the proportion of the mixture applied is 3 g / m 2 (dry weight).
  • thermographic recording paper thus produced has a colorless surface. At 80 ° C, a blue hue quickly develops, the saturation of which is already at around 150 ° C.
  • the two dispersions are then mixed.
  • the colorless mixture is applied to a paper with a basis weight of 50 g / m 2 using a doctor blade.
  • the proportion of the mixture applied is 3 g / m 2 (dry weight).
  • thermographic recording paper thus produced has a colorless surface. At 80 ° C, a black color develops rapidly, the saturation of which takes place at 175-200 ° C.
  • An intense and storage-stable black color can also be obtained using any of the other color developers in accordance with regulations A and C to G.

Description

Die vorliegende Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial, welches in seinem Farbreaktantensystem als Farbentwickler für den Farbbildner mindestens ein Aluminiumphenat oder vorzugsweise ein Zinkphenat einer Phenolsulfonylverbindung der Formel

Figure imgb0001
enthält, worin

  • R Alkyl mit 1 bis 12, vorzugsweise 1 bis 4 Kohlenstoffatomen, Cycloalkyl, Phenyl, Benzyl oder durch Halogen, Niederalkyl, Niederalkoxy, Nitro oder Methylendioxy substituiertes Phenyl und
  • X Wasserstoff, Halogen, Niederalkyl oder Niederalkoxy bedeuten.
The present invention relates to a heat-sensitive recording material which, in its color reactant system as a color developer for the color former, comprises at least one aluminum phenate or preferably a zinc phenate of a phenolsulfonyl compound of the formula
Figure imgb0001
 contains what
  • R alkyl having 1 to 12, preferably 1 to 4 carbon atoms, cycloalkyl, phenyl, benzyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, nitro or methylenedioxy and
  • X is hydrogen, halogen, lower alkyl or lower alkoxy.

Sowohl bei den Zinkphenaten als auch bei den Aluminiumphenaten können die zweifach bzw. dreifach vorkommenden Substituenten R und X gleich oder verschieden sein. Vorzugsweise sind sie jeweils identisch.Both in the zinc phenates and in the aluminum phenates, the double and triple substituents R and X can be the same or different. They are preferably identical in each case.

Niederalkyl und Niederalkoxy stellen Gruppen dar, die 1 bis 5, insbesondere 1 bis 3 Kohlenstoffatome aufweisen, wie z.B. Methyl, Ethyl, Isopropyl, sek.-Butyl, tert.-Butyl bzw. Methoxy, Ethoxy, Isopropoxy, n-Butoxyodertert.-Butoxy.Lower alkyl and lower alkoxy are groups which have 1 to 5, in particular 1 to 3, carbon atoms, e.g. Methyl, ethyl, isopropyl, sec-butyl, tert-butyl or methoxy, ethoxy, isopropoxy, n-butoxy or tert-butoxy.

X ist vorzugsweise Halogen, Methyl, Methoxy, Ethoxy oder vor allem Wasserstoff.X is preferably halogen, methyl, methoxy, ethoxy or especially hydrogen.

Stellt R eine Alkylgruppe dar, so kann diese geradkettig oder verzweigt sein. Beispiele für solche Alkylreste sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sek.-Butyl, Hexyl, Octyl, Isooctyl, Nonyl, Isononyl oder Dodecyl.If R represents an alkyl group, this can be straight-chain or branched. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, isooctyl, nonyl, isononyl or dodecyl.

Als Cycloalkyl bedeutet R beispielsweise Cyclopentyl oder vorzugsweise Cyclohexyl.As cycloalkyl, R is, for example, cyclopentyl or preferably cyclohexyl.

Bevorzugte Substituenten in der Phenylgruppe des R-Restes sind Chlor, Methyl oder Methoxy. R ist vorzugsweise Phenyl oder durch Halogen, Methyl, Methoxy oder Ethoxy substituiertes Phenyl, wie z.B. Chlorphenyl, Methylphenyl, Dimethylphenyl oder Methoxyphenyl.Preferred substituents in the phenyl group of the R radical are chlorine, methyl or methoxy. R is preferably phenyl or phenyl substituted by halogen, methyl, methoxy or ethoxy, e.g. Chlorophenyl, methylphenyl, dimethylphenyl or methoxyphenyl.

Halogen bedeutet beispielsweise Fluor, Brom oder vorzugsweise Chlor.Halogen means for example fluorine, bromine or preferably chlorine.

Unter den Phenolsulfonylverbindungen der Formel (1) sind diejenigen, in denen R Methylphenyl, Methoxyphenyl oder insbesondere Phenyl und X Wasserstoff bedeuten, bevorzugt.Preferred phenolsulfonyl compounds of the formula (1) are those in which R is methylphenyl, methoxyphenyl or in particular phenyl and X is hydrogen.

Die erfindungsgemäss eingesetzten Aluminium- und Zinkphenate der Phenolsulfonylverbindungen der Formel (1) stellen eine neue Klasse von Farbentwicklern oder Elektronenakzeptoren für Farbbildner dar.The aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) used according to the invention represent a new class of color developers or electron acceptors for color formers.

Die Herstellung der Zinkphenate erfolgt vorzugsweise dadurch, dass man 2 Mol einer Phenolsulfonylverbindung der Formel (1) mit 1 Mol des Zinksalzes einer anorganischen Säure oder einer niederen aliphatischen oder aromatischen Carbonsäure umsetzt. Die damit erhaltenen Zinkphenate entsprechen der Formel

Figure imgb0002
worin R und X die angegebene Bedeutung haben. Dabei können jeweils die für R und X definierten Substituenten gleich oder verschieden sein.The zinc phenates are preferably prepared by reacting 2 moles of a phenolsulfonyl compound of the formula (1) with 1 mole of the zinc salt of an inorganic acid or a lower aliphatic or aromatic carboxylic acid. The zinc phenates thus obtained correspond to the formula
Figure imgb0002
 where R and X have the meaning given. The substituents defined for R and X can be the same or different.

Die Umsetzung erfolgt vorteilhafterweise in einer Schmelze oder in einer alkalischen Lösung der verwendeten Phenolsulfonylverbindung, zweckmässigerweise bei 60 bis 90 °C und vorzugsweise in Gegenwart einer Alkaliverbindung, wie z.B. Alkalimetallhydroxide, -carbonate oder -bicarbonate oder Ammoniumhydroxid, Ammoniumcarbonat oder Ammoniumhydrogencarbonat.The reaction is advantageously carried out in a melt or in an alkaline solution of the phenolsulfonyl compound used, advantageously at 60 to 90 ° C and preferably in the presence of an alkali compound, e.g. Alkali metal hydroxides, carbonates or bicarbonates or ammonium hydroxide, ammonium carbonate or ammonium hydrogen carbonate.

Typische Vertreter der zur Umsetzung gelangenden Phenolsulfonylverbindungen sind

  • 4-Hydroxy-1 -methylsulfon-benzol,
  • 4-Hydroxy-1-ethylsulfon-benzol,
  • 4-Hydroxy-1-cyclohexylsulfon-benzol,
  • 4-Hydroxy-1-benzylsulfon-benzol,
  • 4-Hydroxydiphenylsulfon,
  • 4'-Nitro-4-hydroxydiphenylsulfon,
  • 2'-Nitro-4-hydroxydiphenyfsulfon,
  • 4'-Chlor-4-hydroxydiphenylsulfon,
  • 4'-Fluor-4-hydroxydiphenyisulfon,
  • 4'-Methyl-4-hydroxydiphenylsulfon,
  • 3',4'-Dimethyl-4-hydroxy-diphenylsulfon,
  • 4'-Methyoxy-4-hydroxy-diphenylsulfon oder
  • 4'-n-Butoxy-4-hydroxy-diphenylsulfon.
Typical representatives of the phenolsulfonyl compounds used for the reaction are
  • 4-hydroxy-1-methylsulfone-benzene,
  • 4-hydroxy-1-ethylsulfone-benzene,
  • 4-hydroxy-1-cyclohexylsulfone-benzene,
  • 4-hydroxy-1-benzylsulfone-benzene,
  • 4-hydroxydiphenyl sulfone,
  • 4'-nitro-4-hydroxydiphenyl sulfone,
  • 2'-nitro-4-hydroxydiphenyf sulfone,
  • 4'-chloro-4-hydroxydiphenyl sulfone,
  • 4'-fluoro-4-hydroxydiphenyisulfone,
  • 4'-methyl-4-hydroxydiphenyl sulfone,
  • 3 ', 4'-dimethyl-4-hydroxy-diphenyl sulfone,
  • 4'-methoxy-4-hydroxy-diphenyl sulfone or
  • 4'-n-butoxy-4-hydroxy-diphenyl sulfone.

Im Vordergrund des Interesses steht 4-Hydroxy-diphenylsulfon und insbesondere 4`-Methyl-4-hydroxy-diphenylsulfon.In the foreground of interest is 4-hydroxy-diphenyl sulfone and especially 4`-methyl-4-hydroxy-diphenyl sulfone.

Als Beispiele für anorganische Zinksalze seien Zinkchlorid, Zinksulfat oder Zinknitrat genannt. Organische Zinksalze sind z.B. Zinkdiacetat, Zinkoxalat, Zinkhydrogenbenzoat oder vor allem Zinkdibenzoat.Zinc chloride, zinc sulfate or zinc nitrate may be mentioned as examples of inorganic zinc salts. Organic zinc salts are e.g. Zinc diacetate, zinc oxalate, zinc hydrogen benzoate or especially zinc dibenzoate.

Anstelle der genannten Zinksalze können auch Zinkoxid oder Zinkcarbonat verwendet werden, wobei in diesem Falle die Umsetzung mit der Phenolsulfonylverbindung, vorzugsweise in Gegenwart von Ammoniumformiat durchgeführt wird.Instead of the zinc salts mentioned, zinc oxide or zinc carbonate can also be used, in which case the reaction with the phenolsulfonyl compound is carried out, preferably in the presence of ammonium formate.

Die Aluminiumphenate erhält man durch Kondensation von 3 Mol einer Phenolsulfonylverbindung der Formel (1) oder deren Alkalimetallsalze mit einem wasserlöslichen Aluminiumsalz einer anorganischen oder organischen Säure.The aluminum phenates are obtained by condensing 3 moles of a phenolsulfonyl compound of the formula (1) or its alkali metal salts with a water-soluble aluminum salt of an inorganic or organic acid.

Vorzugsweise erfolgt die Herstellung dadurch, dass man 3 Mol einer Phenolsulfonylverbindung der Formel (1) mit dem Aluminiumsalz eines niederen, vorzugsweise sekundären aliphatischen oder cycloaliphatischen Alkohols, insbesondere mit Aluminiumtriisopropylat, Aluminium-sek.butylat oder Aluminiumcyclohexylat umsetzt. Die damit erhaltenen Aluminiumphenate entsprechen der Formel

Figure imgb0003
worin R und X die angegebene Bedeutung haben.The preparation is preferably carried out by reacting 3 moles of a phenolsulfonyl compound of the formula (1) with the aluminum salt of a lower, preferably secondary aliphatic or cycloaliphatic alcohol, in particular with aluminum triisopropoxide, aluminum sec-butoxide or aluminum cyclohexoxide. The aluminum phenates thus obtained correspond to the formula
Figure imgb0003
 where R and X have the meaning given.

Die Umsetzung erfolgt zweckmässig unter Erhitzen der Reaktionspartner bei einer Temperatur von 80 bis 200 °C, worauf der freigesetzte niedere aliphatische oder cycloaliphatsiche Alkohol durch Destillation entfernt wird.The reaction is expediently carried out by heating the reactants at a temperature of 80 to 200 ° C., whereupon the lower aliphatic or cycloaliphatic alcohol released is removed by distillation.

Phenolsulfonylverbindungen der Formel (1) und deren Herstellung werden z.B. in Beilstein, E II 6, S. 852-855 und E III 6, S. 4445-55 beschrieben.Phenolsulfonyl compounds of formula (1) and their preparation are e.g. in Beilstein, E II 6, pp. 852-855 and E III 6, pp. 4445-55.

Ein bevorzugtes Verfahren zur Herstellung der Phenolsulfonylverbindungen der Formel (1) besteht darin, dass man eine Verbindung der FormelA preferred method for the preparation of the phenolsulfonyl compounds of formula (1) is that a compound of formula

Figure imgb0004
mit einer Verbindung RH umsetzt oder dass man eine Verbindung der Formel
Figure imgb0005
mit einer Phenolverbindung der Formel
Figure imgb0006
umsetzt. Dabei haben X und R die angegebene Bedeutung und Hal bedeutet Halogen, wie z.B. Chlor, Brom oder Fluor. Die Umsetzung erfolgt in wasserfreiem Medium in Gegenwart von LewisSäuren, wie z.B. AICI3, FeCl3, ZnCl2, SnC14, SbC15 oder BF3 und vorteilhafterweise bei einer Temperatur von 50 bis 200 °C, vorzugsweise 80 bis 130 °C. Ein weiteres Verfahren besteht darin, dass man eine Verbindung der Formel
Figure imgb0007
worin R, X und Hal die angegebene Bedeutung haben, mit wässeriger Kaliumhydroxidlösung auf 200 bis 220 °C erhitzt.
Figure imgb0004
 with a compound RH or that a compound of the formula
Figure imgb0005
 with a phenol compound of the formula
Figure imgb0006
 implements. X and R have the meaning given and Hal means halogen, such as chlorine, bromine or fluorine. The reaction is carried out in an anhydrous medium in the presence of Lewis acids, such as, for example, AICI 3 , FeCl 3 , ZnCl 2 , SnC1 4 , SbC1 5 or BF 3 and advantageously at a temperature of 50 to 200 ° C., preferably 80 to 130 ° C. Another method is that you have a compound of formula
Figure imgb0007
 wherein R, X and Hal have the meaning given, heated to 200 to 220 ° C. with aqueous potassium hydroxide solution.

Die erfindungsgemäss eingesetzten Aluminium- und Zinkphenate der Phenolsulfonylverbindungen der Formel (1) sind praktisch farb- und geruchlos und mit den üblichen Farbbildnern sehr reaktiv, so dass damit spontane, beständige und nicht verblassende Aufzeichnungen oder Kopien erhalten werden.The aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) used according to the invention are practically colorless and odorless and very reactive with the conventional color formers, so that spontaneous, stable and non-fading recordings or copies are obtained.

Die verwendeten Aluminium- und Zinkphenate zeichnen sich insbesondere dadurch aus, dass die damit erhaltenen Aufzeichnungen oder Kopien eine ausgezeichnete Lagerstabilität bis zu 60 °C aufweisen.The aluminum and zinc phenates used are characterized in particular by the fact that the records or copies thus obtained have excellent storage stability up to 60 ° C.

Die im erfindungsgemässen Aufzeichnungsmaterial oder Kopiermaterial in Betracht kommenden Farbbildner sind bekannte farblose oder schwach gefärbte chromogene Stoffe, die, sofern sie mit den Zinkphenaten der Formel (2) oder mit den Aluminiumphenaten der Formel (3) in Kontakt kommen, farbig werden oder die Farbe ändern. Farbbildner oder deren Mischungen können verwendet werden, welche z. B. den Klassen der Azomethine, Fluorane, Benzofluorane, Phthalide, Azaphthalide, Spiropyrane, Spirodipyrane, Leukoauramine, Triarylmethanleukofarbstoffe, Carbazolylmethane, Chromenoindole, Chromenopyrazole, Phenoxazine, Phenothiazine sowie der Chromeno- oder Chromanofarbbildner angehören. Als Beispiele solcher geeigneter Farbbildner seien genannt:The color formers which can be used in the recording material or copying material according to the invention are known colorless or slightly colored chromogenic substances which, if they come into contact with the zinc phenates of the formula (2) or with the aluminum phenates of the formula (3), become colored or change color . Color formers or mixtures thereof can be used, which z. B. the classes of azomethines, fluorans, benzofluoranes, phthalides, azaphthalides, spiropyrans, spirodipyrans, leucoauramines, triarylmethane leuco dyes, carbazolylmethanes, chromenoindoles, chromenopyrazoles, phenoxazines, phenothiazines as well as the chromeno- or chromano-color former. Examples of such suitable color formers are:

Kristallviolettlacton, 3,3-(Bisaminophenyl)-phthalide, 3,3- (Bis-substituierte-Indolyl)-phthalide, 3-(Aminophenyl)- 3- Indolyl-phthalide, 3-(Aminophenyl)- 3-indolyl-azaphthalide, 6-Dialkylamino- 2-n-octylaminofluorane, 6-Dialkylamino- 2-arylaminofluorane, 6-Dialkylamino-3- methyl- 2-arylamino-fluorane, 6-Dialkylamino- 2- oder -3-niederalkyl-fluorane, 6-Dialkylamino-2-dibenzylamino-fluorane, 6-N-Cyclohexyl-N-niederalkyl-3-methyl-2-arylamino- fluorane, 6-Pyrrolidino-2-arylamino- fluorane, Bis-(aminophenyl)-furyl- oder -phenyl- oder -carbazolyl-methane, 3'-Phenyl-7- dialkylamino-2,2'- spirodibenzopyrane, Bisdialkylaminobenzhydrol-alkyl- oder -arylsulfinate, Benzoyldialkylamino-phenothiazine oder -phenoxazine.Crystal violet lactone, 3,3- (bisaminophenyl) phthalide, 3,3- (bis-substituted-indolyl) phthalide, 3- (aminophenyl) -3-indolyl phthalide, 3- (aminophenyl) -3-indolyl azaphthalide, 6-dialkylamino-2-n-octylaminofluorane, 6-dialkylamino-2-arylaminofluorane, 6-dialkylamino-3-methyl-2-arylamino-fluorane, 6-dialkylamino-2- or -3-lower alkyl-fluorane, 6-dialkylamino- 2-dibenzylamino-fluoranes, 6-N-cyclohexyl-N-lower alkyl-3-methyl-2-arylamino-fluoranes, 6-pyrrolidino-2-arylamino-fluoranes, bis- (aminophenyl) -furyl- or -phenyl- or - carbazolyl methanes, 3'-phenyl-7-dialkylamino-2,2'-spirodibenzopyrans, bisdialkylaminobenzhydrol alkyl or aryl sulfinates, benzoyldialkylamino phenothiazines or phenoxazines.

Aluminium- und Zinkphenate der Phenolsulfonylverbindungen der Formel (1) eignen sich als Farbentwickler für wärmeempfindliches oder thermoreaktives Aufzeichnungsmaterial. Dieses enthält in der Regel mindestens einen Träger, einen Farbbildner, einen Entwickler und gegebenenfalls auch ein Bindemittel und/oder Wachs.Aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) are suitable as color developers for heat-sensitive or thermoreactive recording material. This usually contains at least one carrier, a color former, a developer and optionally also a binder and / or wax.

Thermoreaktive Aufzeichnungssysteme umfassen z.B. wärmeempfindliche Aufzeichnungs- und Kopiermaterialien und -papiere. Diese Systeme werden beispielsweise zum Aufzeichnen von Informationen, z.B. in elektronischen Rechnern, Ferndruckern, Fernschreibern oder in Aufzeichnungsgeräten und Messinstrumenten verwendet, wie z.B. Elektrocardiographen. Die Bilderzeugung (Markierung) kann auch manuell mit einer erhitzten Feder erfolgen. Eine weitere Einrichtung zur Erzeugung von Markierungen mittels Wärme sind Laserstrahlen.Thermoreactive recording systems include e.g. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. used in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, e.g. Electrocardiograph. The imaging (marking) can also be done manually with a heated spring. Another device for generating markings using heat is laser beams.

Das thermoreaktive Aufzeichnungsmaterial kann so aufgebaut sein, dass der Farbbildner in einer Bindemittelschicht gelöst oder dispergiert ist und in einer zweiten Schicht der Entwickler in dem Bindemittel gelöst oder dispergiert ist. Eine andere Möglichkeit besteht darin, dass sowohl der Farbbildner als auch der Entwickler in einer Schicht dispergiert sind. Das Bindemittel wird in spezifischen Bezirken mittels Wärme erweicht und an diesen Punkten, an denen Wärme angewendet wird, kommt der Farbbildner mit dem Entwickler in Kontakt und es entwickelt sich sofort die erwünschte Farbe.The thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in one binder layer and the developer is dissolved or dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer. The binder is softened by heat in specific areas and at those points where heat is applied, the color former comes into contact with the developer and the desired color develops immediately.

Die Aluminium- und Zinkphenate der Phenolsulfonylverbindungen der Formel (1 ) können in wärmeempfindlichen Aufzeichnungsmaterialien für sich allein, als Mischungen oder in Mischung mit bekannten Entwicklern eingesetzt werden.The aluminum and zinc phenates of the phenolsulfonyl compounds of the formula (1) can be used alone in heat-sensitive recording materials, as mixtures or in a mixture with known developers.

Typische Beispiele für bekannte Entwickler sind Aktivton-Substanzen, wie Attapulgus-Ton, Säureton, Bentonit, Montmorillonit., aktivierter Ton, z.B. säureaktiviertes Bentonit oder Montmorillonit; ferner Halloysit, Zeolith, Siliciumdioxid, Aluminiumoxid, Aluminiumsulfat, Aluminiumphosphat, Zinkchlorid, Zinknitrat, Kaolin oder irgendein beliebiger Ton oder sauer reagierende, organische Verbindungen, wie z.B. gegebenenfalls ringsubstituierte Salicylsäure oder Salicylsäureester und deren Metallsalze; ferner ein sauer reagierendes, polymeres Material, wie z.B. ein phenolisches Polymerisat, ein Alkylphenolacetylenharz, ein Maleinsäure-Kolophonium-Harz oder ein teilweise oder vollständig hydrolysiertes Polymerisat von Maleinsäureanhydrid mit Styrol, Ethylen oder Vinylmethylether, oder Carboxypolymethylen.Typical examples of known developers are Active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, for example acid-activated bentonite or montmorillonite; also halloysite, zeolite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, kaolin or any clay or acid-reacting organic compounds, such as optionally ring-substituted salicylic acid or salicylic acid esters and their metal salts; also an acidic polymeric material such as a phenolic polymer, an alkylphenol acetylene resin, a maleic rosin resin or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene.

Die erfindungsgemäss verwendbaren Aluminium- und Zinkphenate können vorteilhafterweise auch in Kombination mit metallfreien phenolischen Verbindungen, wie z.B. 4-tert.-Butylphenol, 4-Phenylphenol, Methylen-bis-(p-phenylphenol), 4-Hydroxydiphenylether, a-Naphthol, β-Naphthol, 4-Hydroxybenzoesäuremethyl-, -ethyl-, n-butyl- oder insbesondere -benzylester, 4-Hydroxyacetophenon, 2,2'-Dihydroxydiphenyl, 4-Hydroxydiphenylsulfon, 4,4'-Isopropyldiphenol, 4,4'-lsopropyliden-bis- (2-methylphenol), 4,4'-Bis- (hydroxyphenyl)valeriansäure, Hydrochinon, Pyrogallol, Phloroglucin, p-, m-, o-Hydroxybenzoesäure, Gallussäure, 1-Hydroxy-2-naphthoesäure sowie mit Borsäure oder organischen, vorzugsweise aliphatischen Dicarbonsäuren, wie z.B. Weinsäure, Oxalsäure, Maleinsäure, Zitronensäure, Citraconsäure oder Bernsteinsäure eingesetzt werden.The aluminum and zinc phenates which can be used according to the invention can advantageously also in combination with metal-free phenolic compounds, such as e.g. 4-tert-butylphenol, 4-phenylphenol, methylene-bis- (p-phenylphenol), 4-hydroxydiphenyl ether, a-naphthol, β-naphthol, 4-hydroxybenzoic acid methyl, ethyl, n-butyl or especially benzyl ester , 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, 4-hydroxydiphenylsulfone, 4,4'-isopropyldiphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4'-bis (hydroxyphenyl) valeric acid, Hydroquinone, pyrogallol, phloroglucinol, p-, m-, o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid and with boric acid or organic, preferably aliphatic dicarboxylic acids, such as, for example Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid can be used.

Vorzugsweise werden zur Herstellung des thermoreaktiven Aufzeichnungsmaterials schmelzbare, filmbildende Bindemittel verwendet. Diese Bindemittel sind normalerweise wasserlöslich, während die Farbbildner und der Entwickler in Wasser unlöslich sind. Das Bindemittel sollte in der Lage sein, den Farbbildner und den Entwickler bei Raumtemperatur zu dispergieren und zu fixieren.Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water soluble, while the color former and developer are insoluble in water. The binder should be able to disperse and fix the color former and developer at room temperature.

Bei Einwirkung von Wärme erweicht oder schmilzt das Bindemittel, so dass der Farbbildner mit dem Entwickler in Kontakt kommt und sich eine Farbe bilden kann. Wasserlösliche oder mindestens in Wasser quellbare Bindemittel sind z.B. hydrophile Polymerisate, wie Polyvinylalkohol, Polyacrylsäure, Hydroxyethylcellulose, Methylcellulose, Carboxymethylcellulose, Polyacrylamid, Polyvinylpyrrolidon, Gelatine, Stärke oder veretherte Maisstärke.When exposed to heat, the binder softens or melts so that the color former comes into contact with the developer and a color can form. Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or etherified corn starch.

Wenn der Farbbildner und der Entwickler in zwei getrennten Schichten vorliegen, können in Wasser unlösliche Bindemittel, d.h. in nichtpolaren oder nur schwach polaren Lösungsmitteln lösliche Bindemittel, wie z.B. Naturkautschuk, synthetischer Kautschuk, chlorierter Kautschuk, Alkydharze, Polystyrol, Styrol/Butadien-Mischpolymerisate, Polymethylacrylate, Ethylcellulose, Nitrocellulose und Polyvinylcarbazol verwendet werden. Die bevorzugte Anordnung ist jedoch diejenige, bei der der Farbbildner und der Entwickler in einer Schicht in einem wasserlöslichen Bindemittel enthalten sind.If the color former and developer are in two separate layers, water-insoluble binders, i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used. However, the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.

Die thermoreaktiven Schichten können weitere Zusätze enthalten. Zur Verbesserung des Weiss- grades, zur Erleichterung des Bedruckens der Papiere und zur Verhinderung des Festklebens der erhitzten Feder können diese Schichten, z.B. Talk, Titandioxid, Zinkoxid, Aluminiumhydroxid, Calciumcarbonat (z.B. Kreide), Tone wie Kaolin, sowie organische Pigmente, wie z.B. Harnstofformaldehyd- oder Melaminformaldehydpolymerisate enthalten. Um zu bewirken, dass nur innerhalb eines begrenzten Temperaturbereiches die Farbe gebildet wird, können Substanzen, wie Harnstoff, Thioharnstoff, Diphenylthioharnstoff, Acetamid, Acetanilid, Stearinsäureamid, Phthalsäureanhydrid, Metallchloride, Metallstearate z.B. Zinkstearat, Phthalsäurenitril oder andere entsprechende, schmelzbare Produkte, welche das gleichzeitige Schmelzen des Farbbildners und des Entwicklers induzieren, zugesetzt werden. Gegebenenfalls enthalten thermographische Aufzeichnungsmaterialien Wachse, z.B. Carnaubawachs, Montanawachs, Paraffinwachs, Polyethylenwachs oder Kondensate höherer Fettsäureamide und Formaldehyd oder Kondensate höherer Fettsäuren und Ethylendiamin.The thermoreactive layers can contain further additives. To improve the white - grades, to facilitate the printing of papers and to prevent the sticking of the heated pen layers, for example, talc, titanium dioxide, zinc oxide, aluminum hydroxide, calcium carbonate (eg chalk), clays such as kaolin, as well as organic pigments, such as Contain urea formaldehyde or melamine formaldehyde polymers. In order to ensure that the color is formed only within a limited temperature range, substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal chlorides, metal stearates, for example zinc stearate, phthalic acid nitrile or other corresponding, meltable products which Induce melting of the color former and the developer, are added. If appropriate, thermographic recording materials contain waxes, for example carnauba wax, montana wax, paraffin wax, polyethylene wax or condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.

In den folgenden Herstellungsvorschriften und Beispielen beziehen sich die angegebenen Prozentsätze, wenn nichts anderes angegeben ist, auf das Gewicht und Teile sind Gewichtsteile.In the following manufacturing instructions and examples, the percentages given are by weight and parts are parts by weight unless otherwise specified.

HerstellungsvorschriftenManufacturing regulations Vorschrift A:Regulation A:

23,4g 4-Hydroxydiphenylsulfon werden unter Rühren auf 145 °C erwärmt. Zu der gebildeten Schmelze wird im Verlaufe von 50 Minuten, portionenweise, eine Mischung von 15,4 g Zink-dibenzoat und 7,9 g Ammoniumhydrogencarbonat eingetragen. Hierauf wird die Reaktionsmischung unter Rühren während 31/2 Stunden bei 150°C gehalten, worauf keine Kohlendioxid-Entwicklung mehr zu beobachten ist. Die warme Schmelze wird in eine Porzellanschale gegossen, erkalten gelassen, zerkleinert und mittels eines Mixers in 200 g deionisiertem Wasser suspendiert, abfiltriert, hierauf mit deionisiertem Wasser gewaschen und bei 60 °C im Vakuumschrank getrocknet. Man erhält 25 g eines hellbeigen Rohproduktes, welches dem Zinkphenat der Formel

Figure imgb0008
entspricht. Das Rohprodukt hat einen Schmelzpunkt von 160-225 °C.
Elementaranalyse: 9,6% S 8,46% Zn.23.4 g of 4-hydroxydiphenyl sulfone are heated to 145 ° C. with stirring. A portion of a mixture of 15.4 g of zinc dibenzoate and 7.9 g of ammonium bicarbonate is added to the melt formed over a period of 50 minutes. Then the reaction mixture with stirring for 3 1/2 hours at 150 ° C is maintained, is observed whereupon no more carbon dioxide evolution. The warm melt is poured into a porcelain bowl, left to cool, crushed and suspended in 200 g of deionized water using a mixer, filtered off, then washed with deionized water and dried at 60 ° C. in a vacuum cabinet. 25 g of a light beige raw product are obtained, which is the zinc phenate of the formula
Figure imgb0008
 corresponds. The crude product has a melting point of 160-225 ° C.
Elemental analysis: 9.6% S 8.46% Zn.

Vorschrift B:Regulation B:

35,2g 4-Hydroxydiphenylsulfon und 10,4g Aluminiumtriisopropylat werden unter Rühren auf 150 °C erhitzt. Hierauf wird das freigesetzte Isopropanol im Verlaufe von 30 Minuten abdestilliert, wobei die letzten Reste Isopropanol durch eine Vakuumbehandlung bei 22 mbar entfernt werden. Die verbleibende Schmelze wird in eine Prozellanschale gegossen, erkalten gelassen und pulverisiert. Man erhält 34,6 g (95% der Theorie) eines hellbeigen Rohproduktes, welches dem Aluminiumtriphenat der Formal

Figure imgb0009
entspricht. Dieses Produkt schmilzt bei 115 bis 118°C. Elementaranalvse:
Figure imgb0010
Vorschrift C:35.2 g of 4-hydroxydiphenyl sulfone and 10.4 g of aluminum triisopropoxide are stirred heated to 150 ° C. The isopropanol released is then distilled off over the course of 30 minutes, the last residues of isopropanol being removed by a vacuum treatment at 22 mbar. The remaining melt is poured into a process bowl, allowed to cool and pulverized. 34.6 g (95% of theory) of a light beige crude product, which is the aluminum triphenate of the formal, are obtained
Figure imgb0009
 corresponds. This product melts at 115 to 118 ° C. Elemental analysis:
Figure imgb0010
 Regulation C:

Zu einer Lösung von 2 g Natriumhydroxid in 150 ml Wasser werden 11,7 g 4-Hydroxydiphenylsulfon bei 70 °C im Verlaufe von 5 Minuten unter Rühren zugegeben. Hierauf lässt man zu der farblosen Lösung bei der gleichen Temperatur (70 °C) eine Lösung von 7,19 g ZnS04 7H20 (Zinksulfat 7 Hydrat) in 50 ml Wasser im Verlaufe von 15 Minuten zutropfen. Die entstandene Suspension wird auf 20 °C abgekühlt und filtriert, worauf der Niederschlag mit Wasser bis kein Natriumsulfat mehr nachgewiesen wird, gewaschen und bei 80 °C im Vakuum getrocknet wird. Man erhält 13,6 g eines weissen Produktes, welches dem Zinkphenat der Formel (11) entspricht. Dieses Produkt schmilzt bei > 250 °C. Elementaranalyse: 11,7% S 12,2% Zn.11.7 g of 4-hydroxydiphenyl sulfone are added to a solution of 2 g of sodium hydroxide in 150 ml of water at 70 ° C. in the course of 5 minutes with stirring. A solution of 7.19 g of ZnSO 4 7H 2 O (zinc sulfate 7 hydrate) in 50 ml of water is then added dropwise to the colorless solution at the same temperature (70 ° C.) in the course of 15 minutes. The resulting suspension is cooled to 20 ° C. and filtered, whereupon the precipitate is washed with water until sodium sulfate is no longer detected, washed and dried at 80 ° C. in vacuo. 13.6 g of a white product are obtained, which corresponds to the zinc phenate of the formula (11). This product melts at> 250 ° C. Elemental analysis: 11.7% S 12.2% Zn.

Vorschrift D:Regulation D:

Zu 40 ml einer wässerigen 1-n-Natriumhydroxid-Lösung und 150 ml Wasser werden 10,75 g 4-Hydroxy-4'-chlor -diphenylsulfon bei 70 °C im Verlaufe von 5 Minuten unter Rühren zugegeben. Hierauf lässt man eine Lösung von 5,75 g ZnS04 - 7H20 in 40 ml Wasser im Verlaufe von 15 Minuten zutropfen. Es entsteht eine Suspension, aus der nach dem Filtrieren 12 g einer weissen Substanz der Formel

Figure imgb0011
mit einem Smp. von > 250 °C erhalten wird. Elementaranalyse: 11 % CI 10,4%S 10,8% Zn.10.75 g of 4-hydroxy-4'-chloro-diphenylsulfone are added to 40 ml of an aqueous 1N sodium hydroxide solution and 150 ml of water at 70 ° C. in the course of 5 minutes with stirring. A solution of 5.75 g of ZnS0 4 - 7H 2 0 in 40 ml of water is then added dropwise over the course of 15 minutes. A suspension is formed from which, after filtering, 12 g of a white substance of the formula
Figure imgb0011
 is obtained with a melting point of> 250 ° C. Elemental analysis: 11% CI 10.4% S 10.8% Zn.

Vorschrift E:Regulation E:

Zu 40 ml einer wässerigen 1-n-Natriumhydroxid-Lösung und 150 ml Wasser werden 9,92g 4-Hydroxy-4'-methyl-diphenylsulfon bei 70 °C im Verlaufe von 5 Minuten unter Rühren zugegeben. Hierauf lässt man eine Lösung von 5,75 g ZnS04 - 7H20 in 40 ml Wasser zutropfen. Es entsteht eine Suspension, aus der 11,3 g einer hellbraunen Substanz der Formel

Figure imgb0012
abfiltriert werden. Dieses Zinkphenat weist einen Smp. von > 250 °C auf. Elementaranalyse: 10,9% S 11,4% Zn.9.92 g of 4-hydroxy-4'-methyl-diphenylsulfone are added to 40 ml of an aqueous 1N sodium hydroxide solution and 150 ml of water at 70 ° C. in the course of 5 minutes with stirring. A solution of 5.75 g of ZnS0 4 - 7H 2 0 in 40 ml of water is then added dropwise. A suspension is formed from which 11.3 g of a light brown substance of the formula
Figure imgb0012
 be filtered off. This zinc phenate has an mp of> 250 ° C. Elemental analysis: 10.9% S 11.4% Zn.

Vorschrift F:Regulation F:

Zu 40 ml 1-n-Natriumhydroxid-Lösung und 150 ml Wasser werden 10,5 g4-Hydroxy-3',4'-dimethyl- diphenylsulfon bei 70 °C im Verlaufe von 5 Minuten unter Rühren zugegeben. Hierauf lässt man bei 80 °C eine Lösung von 5,8 g ZnS04.7H2O in 40 ml Wasser in Verlaufe von 15 Minuten zutropfen. Aus der entstehenden Suspension werden durch Filtrieren 11,9 g einer hellbeigen Substanz der Formel

Figure imgb0013
mit einem Schmelzpunkt von > 250 °C erhalten. Elementaranalyse: 10,4% S 10,5% Zn.10.5 g of 4-hydroxy-3 ', 4'-dimethyldiphenylsulfone are added to 40 ml of 1N sodium hydroxide solution and 150 ml of water at 70 ° C. in the course of 5 minutes with stirring. A solution of 5.8 g of ZnSO 4 .7H 2 O in 40 ml of water is then added dropwise at 80 ° C. over the course of 15 minutes. The resulting suspension becomes 11.9 g of a light beige substance of the formula by filtration
Figure imgb0013
 obtained with a melting point of> 250 ° C. Elemental analysis: 10.4% S 10.5% Zn.

Vorschrift G:Regulation G:

12,4 g 4-Hydroxy-4'-methyl- diphenylsulfon und 3,5 g Aluminiumtriisopropylat werden unter Rühren auf 80 °C erwärmt, worauf Isopropylalkohol langsam abdestilliert wird. Nach 40 Minuten wird das restliche freigesetzte Isopropanol bei reduziertem Druck (23 mbar) entfernt. Der Rückstand wird noch warm in eine Reibschale ausgegossen und nach dem Erkalten pulverisiert. Man erhält 13,8 eines hellbeigen Rohproduktes, welches dem Aluminiumtriphenat der Formel

Figure imgb0014
entspricht. Dieses Produkt schmilzt bei 131-133°C. Elementaranalyse: 3,1 % AI 10,3% S.12.4 g of 4-hydroxy-4'-methyldiphenyl sulfone and 3.5 g of aluminum triisopropoxide are heated to 80 ° C. with stirring, after which isopropyl alcohol is slowly distilled off. After 40 minutes, the remaining isopropanol released is removed under reduced pressure (23 mbar). The residue is poured warm into a grater and pulverized after cooling. 13.8 of a light beige crude product are obtained, which is the aluminum triphenate of the formula
Figure imgb0014
 corresponds. This product melts at 131-133 ° C. Elemental analysis: 3.1% AI 10.3% S.

Beispiel 1example 1

Es werden zunächst zwei Dispersionen (A und B) hergestellt.

  • Zur Herstellung der Dispersion A werden
  • 8 g des gemäss Vorschrift A hergestellten Zinkphenates von 4-Hydroxydiphenylsulfon,
  • 32 g einer 10%igen wässerigen Lösung von Polyvinylalkohol 25/140 und
  • 20 g Wasser

in einer Kugelmühle bis zu einer Korngrösse von 2-4 11m gemahlen.First two dispersions (A and B) are produced.
  • For the preparation of dispersion A.
  • 8 g of the zinc phenate of 4-hydroxydiphenyl sulfone prepared according to regulation A,
  • 32 g of a 10% aqueous solution of polyvinyl alcohol 25/140 and
  • 20 g water

ground in a ball mill up to a grain size of 2-4 11 m.

Zur Herstellung der Dispersion B werden

  • 1 g Kristallviolettlacton,
  • 4 g einer 10%igen wässerigen Lösung von Polyvinylalkohol 25/140 und
  • 2,5 g Wasser

in einer Kugelmühle bis zu einer Korngrösse von 2-4 µm gemahlen.To prepare dispersion B
  • 1 g crystal violet lactone,
  • 4 g of a 10% aqueous solution of polyvinyl alcohol 25/140 and
  • 2.5 g water

ground in a ball mill up to a grain size of 2-4 µm.

Anschliessend werden die beiden Dispersionen vermischt.The two dispersions are then mixed.

Das farblose Gemisch wird auf ein Papier mit einem Flächengewicht von 50 g/m2 mit einem Rakel aufgetragen. Der Anteil des aufgebrachten Gemisches beträgt 3 g/m2 (Trockengewicht).The colorless mixture is applied to a paper with a basis weight of 50 g / m 2 using a doctor blade. The proportion of the mixture applied is 3 g / m 2 (dry weight).

Das so hergestellte thermographische Aufzeichnungspapier besitzt eine farblose Oberfläche. Bei 80 °C entwickelt sich rasch ein blauer Farbton, dessen Sättigung bereits bei zirka 150 °C erfolgt.The thermographic recording paper thus produced has a colorless surface. At 80 ° C, a blue hue quickly develops, the saturation of which is already at around 150 ° C.

Beim Lagern dieses bei 150 °C vollentwickelten Farbmusters bei 58 °C und während einer Stunde ist praktisch keine Farbabnahme sichtbar.When storing this color sample fully developed at 150 ° C at 58 ° C and for one hour, practically no color decrease is visible.

Intensive, lichtechte und lagerbeständige blaue Farben können auch bei Verwendung jeder der anderen Farbentwickler gemäss Vorschriften B bis G erhalten werden.Intense, lightfast and storage-stable blue colors can also be obtained using any of the other color developers in accordance with regulations B to G.

Beispiel 2Example 2

Es werden zunächst zwei Dispersionen (A und B) hergestellt.

  • Zur Herstellung der Dispersion A werden
  • 8 g des gemäss Vorschrift B hergestellten Aluminiumphenates von 4-Hydroxydiphenylsulfon,
  • 32 g einer 10%igen wässerigen Lösung von Polyvinylalkohol 25/140 und
  • 20 g Wasser

in einer Kugelmühle bis zu einer Korngrösse von 2-4 µm gemahlen.First two dispersions (A and B) are produced.
  • For the preparation of dispersion A.
  • 8 g of the aluminum phenate of 4-hydroxydiphenyl sulfone prepared according to regulation B,
  • 32 g of a 10% aqueous solution of polyvinyl alcohol 25/140 and
  • 20 g water

ground in a ball mill up to a grain size of 2-4 µm.

Zur Herstellung der Dispersion B werden

  • 1 g 2-Phenylamino-3-methyl-6-N- cyclohexyl-N- methylamino-fluoran
  • 4 g einer 10%igen wässerigen Lösung von Polyvinylalkohol 25/140 und
  • 2,5 g Wasser

in einer Kugelmühle bis zu einer Korngrösse von 2-4 um gemahlen.To prepare dispersion B
  • 1 g of 2-phenylamino-3-methyl-6-N-cyclohexyl-N-methylamino-fluoran
  • 4 g of a 10% aqueous solution of polyvinyl alcohol 25/140 and
  • 2.5 g water

ground in a ball mill up to a grain size of 2-4 µm.

Anschliessend werden die beiden Dispersionen vermischt.The two dispersions are then mixed.

Das farblose Gemisch wird auf ein Papier mit einem Flächengewicht von 50 g/m2 mit einem Rakel aufgetragen. Der Anteil des aufgebrachten Gemisches beträgt 3 g/m2 (Trockengewicht).The colorless mixture is applied to a paper with a basis weight of 50 g / m 2 using a doctor blade. The proportion of the mixture applied is 3 g / m 2 (dry weight).

Das so hergestellte thermographische Aufzeichnungspapier besitzt eine farblose Oberfläche. Bei 80 °C entwickelt sich rasch eine schwarze Farbe, deren Sättigung bei 175-200°C erfolgt.The thermographic recording paper thus produced has a colorless surface. At 80 ° C, a black color develops rapidly, the saturation of which takes place at 175-200 ° C.

Eine intensive und lagerbeständige schwarze Farbe kann auch bei Verwendung jeder der anderen Farbentwickler gemäss Vorschriften A und C bis G erhalten werden.An intense and storage-stable black color can also be obtained using any of the other color developers in accordance with regulations A and C to G.

Claims (10)

1. A heat-sensitive recording material which comprises in its colour reactant system, as developer for the colour former, at least one aluminium or zinc phenate of a phenolsulfonyl compound of the formula
Figure imgb0017
wherein
R is C1-C12 alkyl, cycloalkyl, phenyl, benzyl, or phenyl which is substituted by halogen, C1-Csalkyl, C1-C5alkoxy, nitro or methylenedioxy, and X is hydrogen, halogen, Cl-C5-alkyl or C1-C5 alkoxy.
2. A recording material according to claim 1, wherein the developer is the aluminium or zinc phenate of a phenolsulfonyl compound of the formula (1), wherein X is hydrogen, halogen, methyl, methoxy or ethoxy.
3. A recording material according to either of claims 1 or 2, wherein the developer is the aluminium or zinc phenate of a phenolsulfonyl compound of the formula (1), wherein R is phenyl or phenyl substituted by halogen, methyl, methoxy or ethoxy.
4. A recording material according to any one of claims 1 to 3, wherein the developer is the aluminium or zinc phenate of a phenolsulfonyl compound of the formula (1), wherein R is phenyl, chlorophenyl, methylphenyl, dimethylphenyl or methoxyphenyl, and X is hydrogen.
5. A recording material according to any one of claims 1 to 4, wherein the developer is the zink phenate of 4-hydroxydiphenylsulfone.
6. A recording material according to any one of claims 1 to 4, wherein the developer is the zinc phenate of 4-hydroxy-4'methyldiphenylsulfone.
7. A recording material according to any one of claims 1 to 4, wherein the developer is the aluminium phenate of 4-hydroxydiphenylsulfone or 4-hydroxy-4'- methyldiphenylsulfone.
8. A recording material according to claim 1, which comprises a support which contains at least one colour former, at least one developer and at least one binder in at least one recording layer, wherein the developer is the aluminium or zinc phenate of the phenolsulfonyl compound of the formula (1) as indicated in any one of claims 1 to 4.
9. A recording material according to claim 8, wherein the developer is the zinc phenate of 4-hydroxydiphenylsulfone or 4-hydroxy-4'-methyldiphenylsulfone.
10. A recording material according to claim 8, wherein the develbper is the aluminium phenate of 4-hydroxydiphenylsulfone or 4-hydroxy-4'-methyldiphenylsulfone.
EP83810570A 1982-12-10 1983-12-05 Heat-sensitive registration material Expired EP0112291B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH721582 1982-12-10
CH7215/82 1982-12-10

Publications (3)

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EP0112291A2 EP0112291A2 (en) 1984-06-27
EP0112291A3 EP0112291A3 (en) 1985-01-02
EP0112291B1 true EP0112291B1 (en) 1987-01-28

Family

ID=4321668

Family Applications (1)

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EP83810570A Expired EP0112291B1 (en) 1982-12-10 1983-12-05 Heat-sensitive registration material

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US (2) US4536779A (en)
EP (1) EP0112291B1 (en)
JP (1) JPS59118491A (en)
DE (1) DE3369484D1 (en)

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US4531141A (en) * 1983-01-17 1985-07-23 Minnesota Mining And Manufacturing Company Heat-sensitive composition and imaging sheet incorporating same
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US4630080A (en) * 1984-11-16 1986-12-16 Jujo Paper Co., Ltd. Heat-sensitive recording sheet
JPS61130269A (en) * 1984-11-30 1986-06-18 Kanzaki Paper Mfg Co Ltd Hydroxydiphenylsulfone derivative and heat-sensitive recording material containing said derivative
US4745204A (en) * 1986-06-05 1988-05-17 International Business Machines Corporation Process for producing aluminum alkoxide or aluminum aryloxide
US5503583B1 (en) * 1987-06-26 2000-09-05 Mattel Inc Toy with thermochromic material
US4917643A (en) * 1987-06-26 1990-04-17 Mattel, Inc. Toy vehicle with thermochromic material
US4855208A (en) * 1987-07-09 1989-08-08 Orient Chemical Industries Ltd. Toner for developing electrostatic latent images
US4918046A (en) * 1988-01-07 1990-04-17 Adeka Argus Chemical Co., Ltd. Heat-sensitive recording material
US5043313A (en) * 1989-04-03 1991-08-27 Ricoh Company, Ltd. Thermosensitive recording material
DE4035935A1 (en) * 1990-11-12 1992-05-14 Henkel Kgaa Prodn. of alpha-sulpho fatty acid salt dispersions - with high concn. using surfactant to reduce viscosity
US6585555B2 (en) 2001-10-18 2003-07-01 Prime Time Toys, Ltd. Temperature sensitive color changing water toy

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Also Published As

Publication number Publication date
JPH0344920B2 (en) 1991-07-09
EP0112291A2 (en) 1984-06-27
EP0112291A3 (en) 1985-01-02
JPS59118491A (en) 1984-07-09
US4536779A (en) 1985-08-20
US4611072A (en) 1986-09-09
DE3369484D1 (en) 1987-03-05

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