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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
  • B41M5/1655—Solvents
• • 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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/136—Organic colour formers, e.g. leuco dyes
  • B41M5/1366—Organic colour formers, e.g. leuco dyes characterised solely by tri (aryl or hetaryl)methane derivatives

Definitions

• Nonionic substituents common in dye chemistry are e.g. Halogen, hydroxy, alkoxy, alkenyloxy, aryloxy, aralkoxy, cycloalkyloxy, heteryloxy, aryl, heteryl, alkylmercapto, arylmercapto, aralkylmercapto, alkylsulfonyl, cyano, carbamoyl, alkoxycarbonyl, amino, which is substituted by 1 or 2 alkyl, cycloalkyl, aryl or Aralkyl groups can be substituted, preferably to a 5- or 6-membered ring, or the substituents of which can be ring-closed, acylamino, alkenyloxy, alkylcarbonyloxy and arylcarbonyloxy and, as substituents for the rings, also alkyl, aryl, aralkyl, nitro, alkenyl or arylvinyl.
• Alkyl represents C 1 -C 30 alkyl, in particular Ci-C 12 alkyl.
• alkyl radicals and the alkyl radicals in alkoxy, alkylthio, alkylamino, alkanoylamino, alkylsulfonyl and alkoxycarbonyl groups can be branched and for example by fluorine, chlorine, C 1 - to C 4 -alkoxy, cyano or C 1 -C 4 -alkoxycarbonyl be.
• Aralkyl is in particular phenyl-C 1 - to C 4 -alkyl, which in the phenyl ring by halogen, C 1 - to C 4 -alkoxy - to C 4 -alkyl and / or C. 1
• Cycloalkyl is in particular cyclopentyl or cyclohexyl optionally substituted by methyl.
• Alkenyl is in particular C 2 -C 5 alkenyl, which can be monosubstituted by hydroxy C 1 - to C 4 -alkoxy, cyano, C 1 - to C 4 -alkoxycarbonyl, chlorine or bromine. Vinyl and allyl are preferred.
• Halogen is especially fluorine, chlorine and bromine, preferably chlorine.
• Aryl is, in particular optionally substituted by one to three C1 - to C4 -alkyl, chlorine, bromine, cyano, C 1 - to C 4 -alkoxycarbonyl or C 1 - to C 4 -alkoxy-substituted phenyl or naphthyl.
• Alkoxy is in particular C 1 -C 12 alkoxy optionally substituted by chlorine or C 1 -C 4 alkoxy.
• Acyl is preferably C 1 - to C 4 alkylcarbonyl and C 1 - to C 4 -alkoxycarbonyl, optionally substituted by C 1 -C 4 alkyl, phenyl or benzyl, mono- or di-substituted aminocarbonyl or aminosulphonyl.
• Alkoxycarbonyl is in particular C 1 - to C 4 -alkoxycarbonyl optionally substituted by hydroxy, halogen or cyano.
• Heteryl is in particular pyridyl, pyrimidyl, pyrazinyl, triazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, thiadiazolyl or tetrazolyl, which can be benzanellated, and their partially hydrogenated or fully hydrogenated derivatives.
• the rings can be substituted by nonionic substituents, in particular by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyano, nitro or halogen.
• radicals substituted in the saturated ring are:
• Suitable (chlorine) hydrocarbons for the solutions according to the invention are high-boiling (150-400 ° C.) (chlorine) hydrocarbons which are liquid at room temperature, for example paraffins, in particular C 10 -C 20 -n-paraffins, C 10 -C 20 - iso-paraffins and C 10 -C 17 -chloroparaffins with 15-70% by weight chlorine content as well as their technical mixtures, eg kerosene (C 10 -C 16 -paraffin) or white oils (50-70% paraffins and 30-50% naphthenes ), aromatic hydrocarbons which contain alkyl groups with preferably 1-18 carbon atoms, such as alkyl-biphenyl, in particular iso-propylbiphenyl, tert-butylbiphenyl, dialkyl-biphenyl, in particular di-isopropylbiphenyl and di-tert.-butyl-biphenyl
• Suitable esters of phthalic acid are, for example, those of C 2 -C 18 -aliphatic alcohols, especially dibutyl phthalate.
• Preferred highly concentrated solutions contain 10-50% by weight, in particular 10-35% by weight, of color former.
• Suitable reaction media are polar solvents such as dimethylformamide, dimethyl sulfoxide, hexamethyl-phosphoric acid triamide and alkanols. Dimethylformamide and C 1 -C 18 alkanols are preferred.
• Suitable reaction temperatures are between 20 and 120 ° C, preferably 30-80 ° C.
• a particularly advantageous production process consists in ketones of the formula in a one-pot reaction with amines of the formula or ketones of the formula with compound of the formula in the presence of a condensing agent which provides an anion An (-) which condenses to the color salts of the formula (IV), these are reacted with the bases (V) as described above without intermediate isolation.
• Phosphorus oxychloride and / or diphosphorus pentoxide are preferably used as condensing agents.
• the color former solutions obtained can be brought onto the market without further purification and can be used in pressure-sensitive recording materials, in particular in microencapsulated materials.
• the color former solutions are preferably encased in microcapsules, the walls of which are produced by interfacial reaction processes.
• Interface reactions for example the condensation from organic acid chlorides and amines, are known.
• a compilation of the interface reactions which have become known to date is from G. Baxter, Microencapsulation Processes and Applications, published by J.E. Vandegaer.
• Microcapsules are particularly preferably used, the shells of which consist of polyadducts of polyisocyanates and polyamines.
• color formers for example 3,3-bis (aminophenyl) phthalides, 3,3-bis (indolyl) phthalides, 3-aminofluoranes, 2,6-diamino-fluoranes , Leukoauraminen, Spiropyranen, Spirodipyranen, Chromenoindolen, Phenoxazinen, Phenothiazinen, Carbazolyl-methanen or other Tri arylmethane leuco dyes to give green, violet, blue, navy blue, gray or black colors.
• 3-bis (aminophenyl) phthalides 3,3-bis (indolyl) phthalides, 3-aminofluoranes, 2,6-diamino-fluoranes , Leukoauraminen, Spiropyranen, Spirodipyranen, Chromenoindolen, Phenoxazinen, Phenothiazinen, Carbazolyl-methanen or
• Pressure sensitive recording materials are known, for example, from US Pat. Nos. 2,800,457 and 2,800,458.
• the solution can easily be diluted with further diisopropylnaphthalene, chlorinated paraffin (C 12 -C 18 -n-paraffin approx. 45% chlorine), sesame oil or linseed oil to use concentrations in recording materials of 3X, 5% or 7X and in polyamide or gelatin - Work in, polyurethane or polyurea microcapsules. On acid clay or bisphenol A you get strong red-violet shades.
• a solution is allowed to dissolve 10.8 g (0.2 mol) of sodium methylate and 50 g of chlorinated paraffin (C 13 -C 18 -n-paraffin with approx. 45 X chlorine) in 500 ml of methanol at 40 ° C. within 30 minutes of 24.5 g (0.05 mol) of the dye of the formula dropwise in 200 ml of methanol.
• the mixture is stirred for 2 hours at 40 ° C. and then 250 ml of water are added.
• the lower organic phase is separated off, washed with water and the residual water is removed in vacuo at 40.degree.
• the solution can easily be diluted with kersoin (C 10 -C 16 -n-paraffins), dodecylbenzene, diisopropylnaphthalene or other chlorinated paraffin (C 13 -C 18 -n-paraffin with approx. 48 X chlorine) to the desired concentration.
• kersoin C 10 -C 16 -n-paraffins
• dodecylbenzene C isopropylnaphthalene or other chlorinated paraffin (C 13 -C 18 -n-paraffin with approx. 48 X chlorine)
• C 13 -C 18 -n-paraffin chlorinated paraffin
• Encapsulated in gelatin, polyamide, polyurethane or polyurea materials, the compound on acid clay or salicylate provides a colorless green with high light and aging fastness.
• a mixture of the color formers of the formulas (1) and (18) in a ratio of approx. 2: 1 gives a strong, neutral black on acidic clay with high aging and CB stability.
• the solution can easily be mixed with further di-iso-propylnaphthalene, kerosene (C 1 -C 16 -n-paraffin) or white oil (62% n -Paraffin / 38 X Naphthen) to the usual use concentrations in recording materials and work into microcapsules. Strong green shades are obtained on acid clay or bisphenol A. A mixture of the color formers of the formulas (1) and (20) in a ratio of approx. 4: 3 also produces a strong neutral black on acid clay.
• chlorinated paraffin C 13 -C 18 -n-paraffins with approximately 45% by weight of chlorine
• diisopropylnaphthalene or linseed oil from the following Color formers
• a mixture of 10 g of 20% solution in diisopropylnaphthalene of the compound of the formula (1) and 3.6 g of a 28% solution in diisopropylnaphthalene of the compound of the formula (18) are mixed with gelatin with 86.4 g of kerosene in a manner known per se and gum arabic microencapsulated by coacervation, mixed with starch solution and spread on a sheet of paper.
• a second sheet of paper is coated on the front with acid-activated bentonite as a color developer.
• the first sheet and the one adjacent to one another with color developer are pressed by hand or typewriter on the first sheet, and an intense black copy is developed on the sheet coated with the developer, which is excellent in lightfastness.
• Example 12 c 250 ml of the mixture according to Example 12 c. 40% microcapsule dispersion obtained are presented.
• 40 g of cellulose pulp (®Arbocell BE 600/30 from Rettenmeier and Sons) are slowly sprinkled in with vigorous stirring.
• 40 ml of 50% SBR latex (®Baystal D 1600 from BAYER AG) are added.
• the resulting 48.5% coating color is diluted with water to a solids content of 30% and coated with an air brush on the back of a commercially available base paper.
• the application after drying is 5 g / m 2 . If you write on this paper, you get an intensely black major copy on a commercially available carbon-free paper.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Color Printing (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Applications Claiming Priority (2)

Publications (3)

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Family Applications (1)

Country Status (4)

Cited By (8)

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Citations (5)

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• 1986
  • 1986-02-21 DE DE19863605552 patent/DE3605552A1/de not_active Withdrawn
• 1987
  • 1987-02-05 US US07/010,932 patent/US4783196A/en not_active Expired - Fee Related
  • 1987-02-10 EP EP87101795A patent/EP0234394B1/fr not_active Expired - Lifetime
  • 1987-02-10 DE DE8787101795T patent/DE3769494D1/de not_active Expired - Lifetime
  • 1987-02-19 JP JP62034699A patent/JP2566938B2/ja not_active Expired - Lifetime
• 1988
  • 1988-09-20 US US07/247,125 patent/US4923641A/en not_active Expired - Fee Related

Patent Citations (5)

Non-Patent Citations (1)

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