EP0697293B1 - Neues organisches Lösungsmittel für Mikrokapseln, die besonders für ein druckempfindliches Aufzeichnungspapier geeigent sind, und ein mit diesen Mikrokapseln beschichtetes druckempfindliches Aufzeichnungspapier - Google Patents

Neues organisches Lösungsmittel für Mikrokapseln, die besonders für ein druckempfindliches Aufzeichnungspapier geeigent sind, und ein mit diesen Mikrokapseln beschichtetes druckempfindliches Aufzeichnungspapier Download PDF

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Publication number
EP0697293B1
EP0697293B1 EP19950401746 EP95401746A EP0697293B1 EP 0697293 B1 EP0697293 B1 EP 0697293B1 EP 19950401746 EP19950401746 EP 19950401746 EP 95401746 A EP95401746 A EP 95401746A EP 0697293 B1 EP0697293 B1 EP 0697293B1
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EP
European Patent Office
Prior art keywords
microcapsules
pressure
microcapsule according
transesterification
vegetable oil
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19950401746
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English (en)
French (fr)
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EP0697293A1 (de
Inventor
Gérard Habar
Alain Le Pape
Catherine Descusse
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COPIGRAPH
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COPIGRAPH
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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

Definitions

  • the present invention relates to useful microcapsules especially for making carbonless pressure-sensitive paper, containing an organic solution of a hydrophobic dye including the solvent is at least partly of plant origin.
  • the invention also relates to pressure-sensitive paper. coated on one side with a layer of such microcapsules and a bundle of paper pressure sensitive comprising at least one paper according to the invention.
  • the invention relates generally to CB, CFB and autonomous.
  • the operating principle of carbonless paper sensitive to pressure consists in bursting the microcapsules under the pressure of a pen or shock caused by typing or typing needles of a dot matrix printer or more generally by all so-called "impact" printing processes.
  • the internal phase contained in the microcapsules thus released flows onto the CF receiving layer and the agents chromogens react with the developer to form the colored image.
  • solvents are most often mixed with diluents such as kerosene, light mineral oil or alkylbenzene (for example dodecylbenzene) etc.
  • solvents of natural origin such as vegetable oils (soy, rapeseed, olive, peanut, palm kernel, corn, sunflower, copra, sesame, castor, palm, babassu, jojoba etc.) especially in US Pat. Nos. 2,712,507, 2,730,457, 3,016,308, 4,783 196, 4 923 641 and European patent applications No. 86 636, 155 593, 262 569.
  • microcapsules according to the invention make it possible to overcome the disadvantages mentioned above and are characterized in that the solvent of the hydrophobic chromogenic agent comprises an ester capable of being obtained by transesterification of a vegetable oil.
  • microcapsules it will be advantageous to mention, but not exclusively, those formed of a cross-linked gelatin wall.
  • esters is generally meant the mixture obtained by transesterification, comprising at least 95% fatty acid esters of natural origin.
  • Transesterification is the chemical operation which consists of exchange glycerol in an acidic or basic medium with a monoalcohol, general short chain, which leads to ester formation and then to eliminate glycerol.
  • the solvent must contain sufficient ester obtained by transesterification of a vegetable oil to meet the conditions set out above.
  • oils palm kernel, rapeseed, soybean, flax, copra, palm, corn, sunflower, olive and peanut there may be mentioned by way of non-limiting example, oils palm kernel, rapeseed, soybean, flax, copra, palm, corn, sunflower, olive and peanut. It is also possible to use the triglycerides called from the English term "tall oil” containing a high proportion of trioleate glycerol.
  • oils can be used alone or in mixture.
  • the alcohol part of the ester resulting from the transesterification is a lower linear or branched alcohol residue, that is to say of which the carbon number ranges from C 1 to C 10 .
  • the alcohol residue is a C 1 to C 8 residue.
  • alcohol residues there may be mentioned the alcohol residues following: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexanol.
  • phthalic derivatives such as 3,3-bis (4-dimethylaminophenyl) -6-dimethylamino-phthalide (CVL) and 3,3-bis (1-octyl-2-methylindole-3-yl) phthalide or fluorane derivatives such as 2-anilino-3 methyl-6 dialkylamino -2 '- (N'-ethyl-N-phenylamino-4'-methylfluorane) or 2'-anilino-3' 6-methyl-diethylamino fluorane, 6'-dimethylamino-2 '- (N-ethyl-N-phenylamino-4'-methylfluorane), 3'-chloro-6'-cyclohexylaminofluorane or 3,7-bis (dimethylamino) -10-benzoylphenotiazine (BLMB) and bisarylcarb
  • the solution of chromogenic agent in the solvent is around 5% by weight.
  • the solvent comprises at least 30% by weight of ester obtained by transesterification of a vegetable oil.
  • the solvent may contain mineral oils.
  • mineral oils that can be used in combination with the esters, mention may be made, for example, of kerosene, paraffinic or naphthenic oils.
  • naphthenic oils or light paraffinics Preferably naphthenic oils or light paraffinics.
  • the alcohol part of these esters is mostly chosen from the alcohol residues already mentioned above for the esters obtained by transesterification vegetable oil.
  • the oils will be preferred mineral.
  • the invention also relates to a process for the preparation of such microcapsules.
  • an emulsion of a phase is formed hydrophobic consisting of an organic solution as described previously of a chromogenic substance, in an aqueous phase basic comprising several colloids including gelatin and one or more other anionic colloids among which we can cite the carboxymethylcellulose (CMC) and a copolymer of maleic anhydride such than a copolymer of methyl ethervin and maleic anhydride (PVMMA) or a copolymer of ethylene and maleic anhydride (EMA).
  • CMC carboxymethylcellulose
  • PVMMA copolymer of methyl ethervin and maleic anhydride
  • EMA copolymer of ethylene and maleic anhydride
  • Liquid-walled microcapsules thus constitute by formation of the coacervate around the oil droplets emulsified. Cooling the mixture down to around 10 ° C causes solidification of the liquid coacervate walls.
  • a curing agent such as formalin or glutaraldehyde in order to crosslink said solid coacervate walls and obtain the desired microcapsules.
  • the emulsion obtained is of the oil in water type and contains droplets of the hydrophobic phase whose diameter is between 1 and 12 micrometers (preferably 3 to 8 micrometers).
  • microcapsules obtained are mixed with binders starch or latex, a spacer, usually calibrated wheat starch and various additives such as optical brightener, water retention etc.
  • the subject of the invention is also a paper sensitive to the pressure coated on one side with a layer of microcapsules such as have been described previously.
  • This paper support constituting the emitting sheet, called CB, of a grammage generally between 40 to 90 g / m 2 was coated by coating the suspension of microcapsules, then these microcapsules were dried to obtain the paper according to the invention .
  • the coating method and the formulation of the coating bath are not critical to the invention.
  • the invention also relates to a bundle of paper sensitive to pressure comprising as described in the preamble to the present description a transmitting sheet and a receiving sheet, and possibly one or more intermediate sheets (CFB) and also so-called autonomous sheets obtained by coating the front of a mixture of microcapsules and receptor layers.
  • a bundle of paper sensitive to pressure comprising as described in the preamble to the present description a transmitting sheet and a receiving sheet, and possibly one or more intermediate sheets (CFB) and also so-called autonomous sheets obtained by coating the front of a mixture of microcapsules and receptor layers.
  • CFRB intermediate sheets
  • the CF receiving paper associated with the CB sheet is preferably "activated clay" type as described in French patents 2,581,350 or US 4,422,670, but it is also possible to use a phenolic type CF such as those described in US Patents 4,559,242 or 4,769,305, or a CF of the salycilate type zinc.
  • the organic phase and the aqueous phase are mixed with stirring and emulsified using an Ultra-TURRAX type device until obtaining particles with an average diameter of between 5 and 6 ⁇ m (the diameter measurement is carried out using a Coulter LS laser granulometer 100).
  • the carboxymethylcellulose has a degree of substitution of the order of 0.8 and a viscosity in 3% aqueous solution at 20 ° C between 60 and 100 mPas measured using a Haake VT 181 viscometer with MVI coaxial cylinders at 180 rpm.
  • the temperature is raised to 60 ° C. and acetic acid is added in 30 minutes to adjust the pH to 4.3.
  • the coacervate is cooled to 8 ° C. and this temperature is maintained for 10 hours.
  • Example 1 is repeated, replacing the rapeseed methyl ester. obtained by transesterification manufactured by Novamont by the same type of product manufactured by the company Robbe under the brand Estorob or Lubrirob 926.
  • Example 2 is reproduced but with the rapeseed methyl ester manufactured by the company Henkel.
  • Example 1 is repeated, replacing the rapeseed methyl ester. by a soy isopropyl ester obtained by transesterification manufactured by Stéarinerie Dubois et Fils.
  • Example 4 is reproduced by replacing the soybean oil with a “tall” oil “(product manufactured by Stéarinerie Dubois et Fils) from wood.
  • Example 1 is repeated, replacing the solvent mixture with 400 g of Novamont rapeseed methyl ester + 445 g of isopropyl palmitate purified (Kessco IPP brand from Akzo).
  • Example 1 is repeated, replacing the solvent mixture with 400 g of Novamont rapeseed methyl ester + 445 g of methyl stearate purified (Edenol W750 brand from Henkel).
  • Example 1 is repeated, replacing the rapeseed methyl ester. with refined virgin rapeseed oil (produced by the company CEREOL).
  • the loss of reactivity of the CB is measured by crushing with the calender before and after aging.
  • the loss of whiteness of the CF due to the migration of part of the chromogenic agents present in the microcapsules is measured compared to a blank test on the same CF.

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  • Color Printing (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Claims (13)

  1. Mikrokapsel, die besonders für druckempfindliches Aufzeichnungspapier geeignet ist, enthaltend eine organische Lösung eines hydrophoben chromogenen Mittels, dadurch gekennzeichnet, daß das Lösungsmittel eine Mischung enthält, die durch Umesterung eines Pflanzenöls erhalten werden kann.
  2. Mikrokapsel gemäß Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Pflanzenöl um Raps-, Soja-, Lein-, Kopra-, Palm-, Mais-, Sonnenblumen-, Oliven-, Erdnuß- und/oder Zwergpalmenöl handelt.
  3. Mikrokapsel gemäß Anspruch 1, dadurch gekennzeichnet, daß der Alkoholrest des Esters der Mischung ein linearer oder verzweigter Alkoholrest von C1 bis C10 ist.
  4. Mikrokapsel gemäß Anspruch 3, dadurch gekennzeichnet, daß es sich bei dem Alkoholrest um einen Rest der folgenden Alkohole handelt: Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol.
  5. Mikrokapsel gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Lösungsmittel wenigstens 30 Gew.% des durch die Umesterung eines Pflanzenöls erhaltenen Esters enthält.
  6. Mikrokapsel gemäß Anspruch 5, dadurch gekennzeichnet, daß das Lösungsmittel
    30 bis 100 Gew.-% einer durch Umesterung eines Pflanzenöls erhaltenen Mischung
    0 bis 70 Gew.-% eines Mineralöls enthält.
  7. Mikrokapsel gemäß Anspruch 6, dadurch gekennzeichnet, daß das Lösungsmittel
    30 bis 50 Gew.-% einer durch Umesterung eines Pflanzenöls erhaltenen Mischung
    50 bis 70 Gew.-% eines Mineralöls enthält.
  8. Mikrokapsel gemäß Anspruch 6 oder 7, dadurch gekennzeichnet, daß es sich bei dem Mineralöl um ein Kerosin, ein paraffinisches und/oder ein naphtenisches Öl handelt.
  9. Mikrokapsel gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es sich bei dem chromogenen Mittel um ein Derivat des phtalischen Typs, wie 3,3-Bis(4-dimethylaminophenyl)-6-dimethylaminophtalid (CVL) oder 3,3-Bis(1-octyl-2-methylindol-3-yl)phtalid, und/oder ein Fluoranderivat, wie 2-Anilin-3-methyl-6-dialkylamino-2'-(N'-ethyl-N-phenylamino-4'-methylfluoran) oder 2'-Anilin-3'-methyl-6-diethylaminofluoran,6'-Dimethylamino-2'-(N-ethyl-N-phenylamino-4'-methylfluoran), 3'-Chlor-6'-cyclohexyl-aminofluoran oder 3,7-Bis(dimethylamino)-10-benzoylphenotiazin (BLMB) und/oder die Verbindungen des Bisarylcarbazolmethans handelt.
  10. Druckempfindliches Papier, welches auf einer Seite mit einer Schicht aus Mikrokapseln gemäß einem der Ansprüche 1 bis 9 beschichtet ist.
  11. Papierblock, welcher wenigstens ein Papier gemäß Anspruch 10 enthält.
  12. Verfahren zur Herstellung von Mikrokapseln, die für druckempfindliches Aufzeichnungspapier geeignet sind, enthaltend eine organische Lösung eines hydrophoben chromogenen Mittels, dadurch gekennzeichnet, daß:
    man eine Emulsion einer hydrophoben Phase, welche aus einer organischen Lösung einer chromogenen Substanz in einem Lösungsmittel, welches aus wenigstens 30 % eines durch Umesterung eines Mineralöls erhaltenen Pflanzenöls besteht, gebildet wird, in einer basischen wäßrigen Phase, welche mehrere Kolloide enthält, herstellt
    um die emulgierten Öltröpfchen herum ein Koazervat bildet und das Koazervat vernetzt.
  13. Herstellungsverfahren gemäß Anspruch 12, dadurch gekennzeichnet, daß man folgende Stufen durchführt:
    Bildung einer Suspension in einer sauren wäßrigen Phase von Partikeln, welche aus Tröpfchen der zuvor beschriebenen organischen Lösung gebildet wird, wobei die Tröpfchen mit einem aus Gelatine gebildeten Koazervat umhüllt sind, aus einem ersten anionischen Kolloid, welches durch eine Polyacrylsäure gebildet wird, und einem zweiten anionischen Kolloid, welches durch Carboxymethylzellulose gebildet wird, wobei die Partikel einen Durchmesser von etwa 1 bis 12 µm, bevorzugt von 3 bis 8 µm, aufweisen,
    Abkühlung zum Verfestigen der Hülle,
    Vernetzung der Gelatine zur Fixierung der Struktur und Irreversibelmachen des Verfahrens,
    Wiedererwärmung und Neutralisation.
EP19950401746 1994-07-26 1995-07-24 Neues organisches Lösungsmittel für Mikrokapseln, die besonders für ein druckempfindliches Aufzeichnungspapier geeigent sind, und ein mit diesen Mikrokapseln beschichtetes druckempfindliches Aufzeichnungspapier Expired - Lifetime EP0697293B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9409220A FR2723032B1 (fr) 1994-07-26 1994-07-26 Nouveau solvant organique pour microcapsules utiles notamment pour la realisation de papier autocopiant sensible a la pression et papier sensible a lapression revetu de telles microcapsules
FR9409220 1994-07-26

Publications (2)

Publication Number Publication Date
EP0697293A1 EP0697293A1 (de) 1996-02-21
EP0697293B1 true EP0697293B1 (de) 1998-09-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19950401746 Expired - Lifetime EP0697293B1 (de) 1994-07-26 1995-07-24 Neues organisches Lösungsmittel für Mikrokapseln, die besonders für ein druckempfindliches Aufzeichnungspapier geeigent sind, und ein mit diesen Mikrokapseln beschichtetes druckempfindliches Aufzeichnungspapier

Country Status (3)

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EP (1) EP0697293B1 (de)
DE (1) DE69504612T2 (de)
FR (1) FR2723032B1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19728899C1 (de) * 1997-07-07 1998-10-22 Henkel Kgaa Verwendung von alkoxylierten Fettsäureniedrigalkylestern
AU2990999A (en) * 1998-09-23 2000-04-10 Mead Corporation, The Microcapsules comprising solvent for chromogenic material
US6310002B1 (en) * 2000-03-07 2001-10-30 Appleton Papers Inc. Record material

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US2730457A (en) 1953-06-30 1956-01-10 Ncr Co Pressure responsive record materials
US2712507A (en) 1953-06-30 1955-07-05 Ncr Co Pressure sensitive record material
US3016308A (en) 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
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GB9221621D0 (en) * 1992-10-15 1992-11-25 Wiggins Teape Group Ltd Solvents for use in pressure-sensitive record material

Also Published As

Publication number Publication date
EP0697293A1 (de) 1996-02-21
DE69504612T2 (de) 1999-05-27
FR2723032B1 (fr) 1996-11-22
DE69504612D1 (de) 1998-10-15
FR2723032A1 (fr) 1996-02-02

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