Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/333—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.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Color Printing (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1983
  • 1983-12-01 US US06/557,013 patent/US4536779A/en not_active Expired - Lifetime
  • 1983-12-05 DE DE8383810570T patent/DE3369484D1/de not_active Expired
  • 1983-12-05 EP EP83810570A patent/EP0112291B1/de not_active Expired
  • 1983-12-09 JP JP58232623A patent/JPS59118491A/ja active Granted
• 1985
  • 1985-06-05 US US06/741,330 patent/US4611072A/en not_active Expired - Lifetime

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