EP1054776B1 - Use of alkoxylated fatty acid low alkyl esters - Google Patents

Use of alkoxylated fatty acid low alkyl esters Download PDF

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Publication number
EP1054776B1
EP1054776B1 EP98939554A EP98939554A EP1054776B1 EP 1054776 B1 EP1054776 B1 EP 1054776B1 EP 98939554 A EP98939554 A EP 98939554A EP 98939554 A EP98939554 A EP 98939554A EP 1054776 B1 EP1054776 B1 EP 1054776B1
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EP
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Prior art keywords
fatty acid
colour
microcapsules
sheets
alkoxylated fatty
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EP98939554A
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German (de)
French (fr)
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EP1054776A2 (en
Inventor
Benoít Abribat
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • 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
    • 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
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • 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
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
    • 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
    • B41M5/15—Spiro-pyrans

Definitions

  • the invention relates to the use of alkoxylated fatty acid lower alkyl esters as solvents for color-producing preparations and a process for the production of carbonless papers.
  • CB-sheet On its underside with a microencapsulated color precursor (Reoxid I) and the other (“CF-sheet”) is coated on its top with a color developer composition (Reoxid II).
  • Reactive I When using mechanical pressure, e.g. when writing or by hitting one Typewriter, Reactive I's capsule is crushed, releasing it and engaging with it Reactive II combines in a chemical reaction with color development.
  • European patent application EP-A 0390432 European patent application EP-A 0487347 relates to the use of mixtures of polyglycol ethers and dialkyl esters as solvents for coloring preparations.
  • European patent application EP-A 0593192 (Wiggins Teape Group) also proposes the use of mono- or polybasic esters, especially methyl esters, as solvents. The problem with these esters, however, is that they have an insufficient cloud point and, moreover, can be used only to a very limited extent because of their own odor.
  • the object of the present invention was therefore to create new solvents for color-generating To provide preparations that are free from the disadvantages described above.
  • the invention relates to the use of alkoxylated fatty acid lower alkyl esters as solvents for color-producing preparations in the form of microcapsules for the production of pressure-sensitive Carbonless papers.
  • alkoxylated fatty acid lower alkyl esters are excellent Have dissolving properties for the color-producing preparations and also smell perfect are.
  • fatty acid lower alkyl ester is understood by the person skilled in the art to be esters of fatty acids with lower aliphatic alcohols having 1 to 4 carbon atoms.
  • the alkoxylated esters usually follow the formula (I) R 1 CO (CH 2 CHR 2 O) n R 3 (I) in the R 1 CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 2 for hydrogen or a methyl group, R 3 for linear or branched alkyl radicals with 1 to 4 carbon atoms and n for numbers from 1 to 10, preferably 2 to 5.
  • Typical examples are the addition products of 1 to 10, preferably 2 to 5, mol of ethylene oxide and / or propylene oxide onto esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid , Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures with ethanol, propanol, isopropyl alcohol, butanol, tert-butanol and especially methanol.
  • esters are prepared by the methods of the prior art, for example by inserting the alkylene oxide into the carbonyl ester bond in the presence of calcined hydrotalcites, as described, for example, in European Patent EP-B1 0474644 (Henkel).
  • Reactive I microencapsulated color precursors
  • phthalides such as, for example, 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (CVL) or 3,3-bis (1 octyl-2-methylindole-3-yl) phthalide; Fluoranes such as 2'-anilino-6'diethylamino-3'-methylfluorane, 6'-dimethylamino-2 '- (N-ethyl-N-phenylamino-4'-methylfluorane), 2'-N-methyl-N-phenylaminofluorane -6'-N-ethyl-N (4-methylphenylaminofluoran or 3'-chloro-6'-cyclohexylaminofluoran; spirobipyrans such as 3'-i-propyl-7-dibenzylamino-2,2'-s
  • the reactive amount can be 1 to 10, preferably 4 to 8,% by weight in the solvent, and the microcapsules can be prepared in a manner known per se are, for example by encapsulation in gelatin or other suitable polymers or by in situ polymerization of corresponding monomers, in this connection reference is made to the relevant prior art, which is mentioned on this topic in EP-A 0593192.
  • the microcapsules are then usually with a suitable binder (e.g. starch o which mixes a mixture of starch and carboxymethyl cellulose) to protect them from unwanted opening.
  • the papers can be coated with the microcapsules in a manner known per se, the amount being in the range from 1 to 10, preferably 5 to 7 g / m 2 .
  • Suitable color developers are, for example, acidic clays (US 3,753,761), phenolic resins (US 3,672,935, US 4,612,254) or their salts (US 3,024,927, EP-A 0275107, DE-A 4110354) .
  • Examples 1 to 6 comparative examples V1 to V6.
  • Coconut fatty acid + 2EO methyl ester and coconut fatty acid + 10EO methyl ester were tested as solvents according to the invention; a mixture of diisopropylnaphthalene in kerosene or coconut fatty acid methyl ester served as comparative examples V1 to V6.
  • the coloring components a conventional mixture of green and black fluoranes and red bis-indolyl phthalide
  • the solutions were encapsulated in gelatin at 50 to 55 ° C. and ground to a dispersion.
  • microcapsule dispersions were formulated with starch and ground cellulose as a binder and coated with commercially available paper (50 g / m 2 ) (layer thickness 5 to 7 g / m 2 ). To check the color intensity, the CB paper coated with the microcapsules was sent through a calendering machine together with the corresponding CF paper containing the developer (acidic montmorillonite) in order to break the microcapsules under defined conditions.

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  • Color Printing (AREA)

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft die Verwendung von alkoxylierten Fettsäureniedrigalkylestern als Lösemittel für farberzeugende Zubereitungen sowie einem Verfahren zur Herstellung von Durchschreibpapieren.The invention relates to the use of alkoxylated fatty acid lower alkyl esters as solvents for color-producing preparations and a process for the production of carbonless papers.

Stand der TechnikState of the art

Handelsübliche Durchschreibpapiere bestehen in der Regel aus zwei Blättern, von denen das obere ("CB-sheet") an seiner Unterseite mit einer mikroverkapselten Farbvorstufe (Reaktiv I) und das andere ("CF-sheet") an seiner Oberseite mit einer Farbentwicklerzusammensetzung (Reaktiv II) beschichtet ist. Bei Anwendung von mechanischem Druck, z.B. beim Schreiben oder durch den Anschlag einer Schreibmaschine, wird die Kapsel des Reaktivs I zerdrückt, wodurch es freigesetzt wird und sich mit dem Reaktiv II in einer chemischen Reaktion unter Farbentwicklung verbindet. Als Lösemittel für das mikroverkapselte Reaktiv haben sich Mischungen von Kerosin mit Alkylnaphthalinen, teilhydrierten Terphenylen, Diarylmethanderivaten, Dibenzylderivaten oder Chlorparaffinen zwar bewährt, aus ökotoxikologischen Gründen besteht jedoch Bedarf an weniger bedenklichen Problemlösungen. Pflanzliche Öle sind für den gleichen Anwendungszweck zwar vorgeschlagen worden, haben sich wegen ihrer mangelnden solubilisierenden Eigenschaften jedoch nicht durchsetzen können.Commercial carbonless papers usually consist of two sheets, the upper one ("CB-sheet") on its underside with a microencapsulated color precursor (Reaktiv I) and the other ("CF-sheet") is coated on its top with a color developer composition (Reaktiv II). When using mechanical pressure, e.g. when writing or by hitting one Typewriter, Reactive I's capsule is crushed, releasing it and engaging with it Reactive II combines in a chemical reaction with color development. As a solvent for that Microencapsulated reactive mixtures of kerosene with alkylnaphthalenes have been partially hydrogenated Terphenyls, diarylmethane derivatives, dibenzyl derivatives or chlorinated paraffins have proven themselves from ecotoxicological For reasons, however, there is a need for less problem-solving solutions. vegetable Although oils have been proposed for the same application, they have changed because of their lack of solubilizing properties.

Aus der europäischen Patentanmeldung EP-A 0390432 ist der Einsatz nichtionischer Tenside als Dispergatoren für farbgebende Stoffe in einem hydrophoben Lösemittel bekannt. Gegenstand der europäischen Patentanmeldung EP-A 0487347 ist die Verwendung von Mischungen von Polyglycolethern und Dialkylestern als Lösemittel für farbgebende Zubereitungen. In diesem Zusammenhang wird weiterhin in der europäischen Patentanmeldung EP-A 0593192 (Wiggins Teape Group) die Verwendung von ein- oder mehrbasigen Estern, speziell Methylestern als Lösemittel vorgeschlagen. Bei diesen Estern besteht jedoch das Problem, daß sie einen unzureichenden Trübungspunkt aufweisen und zudem wegen ihres Eigengeruchs nur sehr eingeschränkt eingesetzt werden können. The use of nonionic surfactants as dispersants for coloring substances in a hydrophobic solvent is known from European patent application EP-A 0390432 . European patent application EP-A 0487347 relates to the use of mixtures of polyglycol ethers and dialkyl esters as solvents for coloring preparations. In this context, European patent application EP-A 0593192 (Wiggins Teape Group) also proposes the use of mono- or polybasic esters, especially methyl esters, as solvents. The problem with these esters, however, is that they have an insufficient cloud point and, moreover, can be used only to a very limited extent because of their own odor.

Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, neue Lösungsmittel für farberzeugende Zubereitungen zur Verfügung zu stellen, die frei von den oben geschilderten Nachteilen sind.The object of the present invention was therefore to create new solvents for color-generating To provide preparations that are free from the disadvantages described above.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist die Verwendung von alkoxylierten Fettsäureniedrigalkylestern als Lösemittel für farberzeugende Zubereitungen in Form von Mikrokapseln zur Herstellung von druckempfindlichen Durchschreibpapieren.The invention relates to the use of alkoxylated fatty acid lower alkyl esters as solvents for color-producing preparations in the form of microcapsules for the production of pressure-sensitive Carbonless papers.

Überraschenderweise wurde gefunden, daß alkoxylierte Fettsäureniedrigalkylester ausgezeichnete Löseeigenschaften für die farberzeugenden Zubereitungen aufweisen und zudem geruchlich einwandfrei sind.Surprisingly, it has been found that alkoxylated fatty acid lower alkyl esters are excellent Have dissolving properties for the color-producing preparations and also smell perfect are.

Alkoxylierte FettsäureniedrigalkylesterAlkoxylated fatty acid lower alkyl esters

Unter dem Begriff Fettsäureniedrigalkylester versteht der Fachmann Ester von Fettsäuren mit niederen aliphatischen Alkoholen mit 1 bis 4 Kohlenstoffatomen. Üblicherweise folgen die alkoxylierten Ester der Formel (I), R1CO(CH2CHR2O)nR3   (I) in der R1CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, R2 für Wasserstoff oder eine Methylgruppe, R3 für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und n für Zahlen von 1 bis 10, vorzugsweise 2 bis 5 steht. Typische Beispiele sind die Anlagerungsprodukte von 1 bis 10, vorzugsweise 2 bis 5 Mol Ethylenoxid und/oder Propylenoxid an Ester der Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen mit Ethanol, Propanol, Isopropylalkohol, Butanol, tert-Butanol und insbesondere Methanol. Vorzugsweise werden Anlagerungsprodukte von 2 bis 5 Mol Ethylenoxid an Kokosfettsäuremethylester eingesetzt. Die Herstellung der Ester erfolgt nach den Verfahren des Stands der Technik, beispielsweise durch Insertion des Alkylenoxids in die Carbonylesterbindung in Gegenwart von calcinierten Hydrotalciten, wie dies beispielsweise in der Europäischen Patentschrift EP-B1 0474644 (Henkel) beschrieben wird. The term fatty acid lower alkyl ester is understood by the person skilled in the art to be esters of fatty acids with lower aliphatic alcohols having 1 to 4 carbon atoms. The alkoxylated esters usually follow the formula (I) R 1 CO (CH 2 CHR 2 O) n R 3 (I) in the R 1 CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 2 for hydrogen or a methyl group, R 3 for linear or branched alkyl radicals with 1 to 4 carbon atoms and n for numbers from 1 to 10, preferably 2 to 5. Typical examples are the addition products of 1 to 10, preferably 2 to 5, mol of ethylene oxide and / or propylene oxide onto esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid , Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures with ethanol, propanol, isopropyl alcohol, butanol, tert-butanol and especially methanol. Addition products of 2 to 5 moles of ethylene oxide with coconut fatty acid methyl ester are preferably used. The esters are prepared by the methods of the prior art, for example by inserting the alkylene oxide into the carbonyl ester bond in the presence of calcined hydrotalcites, as described, for example, in European Patent EP-B1 0474644 (Henkel).

Reaktiv I (mikroverkapselte Farbvorstufen)Reactive I (microencapsulated color precursors)

Als mikroverkapselte Reaktive I, welches es im Sinne der Erfindung zu lösen gilt, kommen beispielsweise folgende Stoffe in Frage: Phthalide wie etwa 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalid (CVL) oder 3,3-bis(1-octyl-2-methylindol-3-yl)phthalid; Fluorane wie etwa 2'-anilino-6'diethylamino-3'-methylfluoran, 6'-dimethylamino-2'-(N-ethyl-N-phenylamino-4'-methylfluoran), 2'-N-methyl-N-phenylaminofluoran-6'-N-ethyl-N(4-methylphenylaminofluoran oder 3'-chlor-6'-cyclohexylaminofluoran; Spirobipyrane wie etwa 3'-i-propyl-7-dibenzylamino-2,2'-spirobi-(2H-1-benzopyran). Ebenfalls in Betracht kommen Triphenylmethylverbindungen wie sie beispielsweise in der europäischen Patentanmeldung EP-A 0263569 genannt werden. Die Reaktivmenge kann 1 bis 10, vorzugsweise 4 bis 8 Gew.-% im Lösemittel betragen. Die Mikrokapseln können in an sich bekannter Weise hergestellt werden, beispielsweise durch Verkapselung in Gelatine oder anderen geeigneten Polymeren bzw. durch in situ Polymerisation von entsprechenden Monomeren, in diesem Zusammenhang wird auf den einschlägigen Stand der Technik verwiesen, der zu diesem Thema in der EP-A 0593192 genannt ist. Die Mikrokapseln werden anschließend üblicherweise mit einem geeigneten Bindemittel (z.B. Stärke oder eine Mischung aus Stärke und Carboxymethylcellulose) vermischt, um sie vor einer unerwünschten Öffnung zu schützen. Die Beschichtung der Papiere mit den Mikrokapseln kann in ebenfalls an sich bekannter Weise erfolgen, wobei die Menge in der Größenordnung von 1 bis 10, vorzugsweise 5 bis 7 g/m2 liegt.The following substances are suitable as microencapsulated reactants I, which are to be solved within the meaning of the invention: phthalides such as, for example, 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (CVL) or 3,3-bis (1 octyl-2-methylindole-3-yl) phthalide; Fluoranes such as 2'-anilino-6'diethylamino-3'-methylfluorane, 6'-dimethylamino-2 '- (N-ethyl-N-phenylamino-4'-methylfluorane), 2'-N-methyl-N-phenylaminofluorane -6'-N-ethyl-N (4-methylphenylaminofluoran or 3'-chloro-6'-cyclohexylaminofluoran; spirobipyrans such as 3'-i-propyl-7-dibenzylamino-2,2'-spirobi- (2H-1- Triphenylmethyl compounds such as are mentioned, for example, in European patent application EP-A 0263569. The reactive amount can be 1 to 10, preferably 4 to 8,% by weight in the solvent, and the microcapsules can be prepared in a manner known per se are, for example by encapsulation in gelatin or other suitable polymers or by in situ polymerization of corresponding monomers, in this connection reference is made to the relevant prior art, which is mentioned on this topic in EP-A 0593192. The microcapsules are then usually with a suitable binder (e.g. starch o which mixes a mixture of starch and carboxymethyl cellulose) to protect them from unwanted opening. The papers can be coated with the microcapsules in a manner known per se, the amount being in the range from 1 to 10, preferably 5 to 7 g / m 2 .

Reaktiv II (Entwickler)Reactive II (developer)

Als Farbentwickler kommen beispielsweise saure Tone (US 3,753,761), Phenolharze (US 3,672,935, US 4,612,254) oder deren Salze (US 3,024,927, EP-A 0275107, DE-A 4110354) in Frage.Suitable color developers are, for example, acidic clays (US 3,753,761), phenolic resins (US 3,672,935, US 4,612,254) or their salts (US 3,024,927, EP-A 0275107, DE-A 4110354) .

Verfahrenmethod

Ein weiterer Gegenstand der Erfindung besteht schließlich in einem Verfahren zur Herstellung von Durchschreibpapieren, bestehend aus einer farberzeugenden und einer farbentwickelnden Schicht, bei dem man

  • (a) farberzeugende Zubereitungen (Reaktiv I) in alkoxylierten Fettsäureniedrigalkylestern löst,
  • (b) die Lösungen zu Mikrokapseln verarbeitet und gegebenenfalls mit Bindern formuliert,
  • (c) Blätter ("CB-sheets") einseitig mit den Mikrokapseln beschichtet und
  • (d) jeweils mit Blättern ("CF-sheets") kombiniert, die einseitig eine Entwicklerbeschichtung aufweisen, mit der Maßgabe, daß man die CB- und CF-sheets so zusammenlegt, daß durch mechanischen Druck und Öffnung der Mikrokapseln die farberzeugenden Zubereitungen mit den Entwicklern unter Farbentwickiung abreagieren können. Die Durchschreibpapiere selbst können eine Stärke von 60 bis 90 µm und ein Gewicht von 35 bis 100, vorzugsweise 40 bis 60 g/m2 aufweisen.
    • Another object of the invention finally consists in a process for the production of carbonless papers, consisting of a color-generating and a color-developing layer, in which
  • (a) dissolving color-producing preparations (Reactive I) in alkoxylated fatty acid lower alkyl esters,
  • (b) the solutions are processed into microcapsules and, if appropriate, formulated with binders,
  • (c) sheets ("CB sheets") coated on one side with the microcapsules and
  • (d) combined with sheets ("CF sheets"), which have a developer coating on one side, with the proviso that the CB and CF sheets are put together in such a way that the color-producing preparations with the. by mechanical pressure and opening of the microcapsules Abreact developers under color development. The carbonless papers themselves can have a thickness of 60 to 90 μm and a weight of 35 to 100, preferably 40 to 60 g / m 2 .

    • BeispieleExamples

    Beispiele 1 bis 6, Vergleichsbeispiele V1 bis V6. Als erfindungsgemäße Lösemittel wurden Kokosfettsäure+2EO-methylester und Kokosfettsäure+10EO-methylester (Beispiele 1 bis 6) getestet; als Vergleichsbeispiele V1 bis V6 dienten eine Mischung aus Diisopropylnaphthalin in Kerosin bzw. Kokosfettsäuremethylester. Zunächst wurden die farbgebenden Komponenten (eine konventionelle Mischung aus grünen und schwarzen Fluoranen sowie rotem Bis-indolylphthalid) abgelöst, so daß 5 Gew.-%ige Zubereitungen entstanden. Bei 50 bis 55°C wurden die Lösungen in Gelatine verkapselt und zu einer Dispersion vermahlen. Diese wurde mit Wasser sowie einer Carboxymethylcelluloselösung versetzt und durch Zugabe von Essigsäure auf pH = 4,2 eingestellt, wobei Coazervation eintrat. Danach wurden die fertigen Mikrokapseln durch Zugabe von Base auf einen neutralen pH-Wert gebracht. Schließlich wurden die verschiedenen Mikrokapseldispersionen mit Stärke und gemahlener Cellulose als Binder formuliert und handelsübliches Papier (50 g/m2) damit beschichtet (Schichtdicke 5 bis 7 g/m2). Zur Prüfung auf Farbintensität wurde das mit den Mikrokapseln beschichtete CB-Papier zusammen mit dem entsprechenden, den Entwickler (saurer Montmorillonit) enthaltenden CF-Papier durch eine Kalandriermaschine geschickt, um die Mikrokapseln unter definierten Bedingungen aufzubrechen. Anschließend wurde die Farbintensität (sofort und nach 5 h) photometrisch gegen einen Standard (unbenutztes CF-Papier) bestimmt. Angegeben ist die Reflexion in Prozent der Ausgangsreflexion, d.h. je niedriger die Werte, desto intensiver die Farbe. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Messung der Farbintensität Bsp. Lösemittel Beschichtung [g/m2] Reflexion [%-rel] sofort 5 h 1 C12/14-Kokosfettsäure+2EO-methylester 5 65,5 64,1 2 C12/14-Kokosfettsäure+2EO-methylester 6 63,1 62,0 3 C12/14-Kokosfettsäure+2EO-methylester 7 62,0 61,1 4 C12/18-Kokosfettsäure+10EO-methylester 5 65,3 64,0 5 C12/18-Kokosfettsäure+10EO-methylester 6 63,0 62,8 6 C12/18-Kokosfettsäure+10EO-methylester 7 61,5 61,1 V1 Diisopropylnaphthalin/Kerosin (1:1) 5 66,0 65,8 V2 Diisopropylnaphthalin/Kerosin (1:1) 6 65,0 64,3 V3 Diisopropylnaphthalin/Kerosin (1:1) 7 64,1 63,9 V4 C12/14-Kokosfettsäuremethylester 5 65,8 65,7 V5 C12/14-Kokosfettsäuremethylester 6 64,1 63,8 V6 C12/14-Kokosfettsäuremethylester 7 63,8 63,1 Examples 1 to 6, comparative examples V1 to V6. Coconut fatty acid + 2EO methyl ester and coconut fatty acid + 10EO methyl ester (Examples 1 to 6) were tested as solvents according to the invention; a mixture of diisopropylnaphthalene in kerosene or coconut fatty acid methyl ester served as comparative examples V1 to V6. First, the coloring components (a conventional mixture of green and black fluoranes and red bis-indolyl phthalide) were removed, so that 5% by weight preparations were obtained. The solutions were encapsulated in gelatin at 50 to 55 ° C. and ground to a dispersion. This was mixed with water and a carboxymethyl cellulose solution and adjusted to pH = 4.2 by adding acetic acid, during which coacervation occurred. The finished microcapsules were then brought to a neutral pH by adding base. Finally, the various microcapsule dispersions were formulated with starch and ground cellulose as a binder and coated with commercially available paper (50 g / m 2 ) (layer thickness 5 to 7 g / m 2 ). To check the color intensity, the CB paper coated with the microcapsules was sent through a calendering machine together with the corresponding CF paper containing the developer (acidic montmorillonite) in order to break the microcapsules under defined conditions. Then the color intensity (immediately and after 5 h) was determined photometrically against a standard (unused CF paper). The reflection is given as a percentage of the initial reflection, ie the lower the values, the more intense the color. The results are summarized in Table 1. Measurement of color intensity E.g. solvent Coating [g / m 2 ] Reflection [% -rel] immediately 5 h 1 C 12/14 coconut fatty acid + 2EO methyl ester 5 65.5 64.1 2 C 12/14 coconut fatty acid + 2EO methyl ester 6 63.1 62.0 3 C 12/14 coconut fatty acid + 2EO methyl ester 7 62.0 61.1 4 C 12/18 coconut fatty acid + 10EO methyl ester 5 65.3 64.0 5 C 12/18 coconut fatty acid + 10EO methyl ester 6 63.0 62.8 6 C 12/18 coconut fatty acid + 10EO methyl ester 7 61.5 61.1 V1 Diisopropylnaphthalene / Kerosene (1: 1) 5 66.0 65.8 V2 Diisopropylnaphthalene / Kerosene (1: 1) 6 65.0 64.3 V3 Diisopropylnaphthalene / Kerosene (1: 1) 7 64.1 63.9 V4 C 12/14 coconut fatty acid methyl ester 5 65.8 65.7 V5 C 12/14 coconut fatty acid methyl ester 6 64.1 63.8 V6 C 12/14 coconut fatty acid methyl ester 7 63.8 63.1

    Die Beispiele und Vergleichsbeispiele zeigen, daß die Verwendung der erfindungsgemäßen alkoxylierten Fettsäurealkylester zu Durchschreibpapieren führt, die sich durch eine höhere Farbintensität auszeichnen. Obschon die Ursache hierfür noch nicht geklärt ist, scheint ein Zusammenhang mit dem Trübungspunkt der Lösemittel zu bestehen. Ein weiterer Vorteil besteht darin, daß die unter Einsatz der erfindungsgemäß zu verwendenden Lösemittel hergestellten Papiere geruchlich einwandfrei waren, während die Vergleichspapiere entweder einen deutlichen Kerosin- oder Fettgeruch aufwiesen.The examples and comparative examples show that the use of the alkoxylated according to the invention Fatty acid alkyl esters lead to carbonless papers, which are characterized by a higher color intensity distinguished. Although the cause of this has not yet been clarified, a connection with the seems Cloud point of the solvent. Another advantage is that using the Papers produced according to the invention to be used according to the invention had a perfect odor, while the comparison papers had either a clear kerosene or fat smell.

    Claims (8)

    1. The use of alkoxylated fatty acid lower alkyl esters for colour-producing preparations in the form of microcapsules for the production of pressure-sensitive carbon papers.
    2. The use claimed in claim 1, characterized in that alkoxylated fatty acid esters corresponding to formula (I): R1CO(CH2CHR2O)nR3 in which R1CO is a linear or branched, saturated or unsaturated acyl group containing 6 to 22 carbon atoms, R2 is hydrogen or a methyl group, R3 represents linear or branched alkyl groups containing 1 to 4 carbon atoms and n is a number of 1 to 10,
      are used.
    3. The use claimed in claims 1 and 2, characterized in that fatty acid esters corresponding to formula (I) where R1CO is a linear acyl group containing 12 to 18 carbon atoms are used.
    4. The use claimed in claims 1 to 3, characterized in that fatty acid methyl esters are used.
    5. The use claimed in claims 1 to 4, characterized in that colour-producing preparations (reactive I) selected from the group consisting of phthalides, fluorans, spirobipyrans and triphenyl methyl compounds are used.
    6. The use claimed in claims 1 to 5, characterized in that the colour-producing preparations (reactive I) are used in quantities of 1 to 10% by weight, based on the solvent.
    7. A process for the production of carbon papers consisting of a colour-producing layer and a colour-developing layer, characterized in that
      (a) colour-producing preparations (reactive I) are dissolved in alkoxylated fatty acid lower alkyl esters,
      (b) the solutions are processed to microcapsules,
      (c) CB sheets are coated with the microcapsules on one side and
      (d) are combined with CF sheets having a developer coating on one side,
      with the proviso that the CB and CF sheets are placed together in such a way that, through mechanical pressure and opening of the microcapsules, the colour-producing preparations are able to react off with the developers in a colour-developing reaction.
    8. A process as claimed in claim 7, characterized in that carbon papers with a weight of 35 to 100 g/m2 are produced.
    EP98939554A 1997-07-07 1998-06-29 Use of alkoxylated fatty acid low alkyl esters Expired - Lifetime EP1054776B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19728899 1997-07-07
    DE1997128899 DE19728899C1 (en) 1997-07-07 1997-07-07 Alkoxylated lower alkyl fatty acid ester(s) are useful as solvents
    PCT/EP1998/003963 WO1999002349A2 (en) 1997-07-07 1998-06-29 Use of alkoxylated fatty acid low alkyl esters

    Publications (2)

    Publication Number Publication Date
    EP1054776A2 EP1054776A2 (en) 2000-11-29
    EP1054776B1 true EP1054776B1 (en) 2002-04-10

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    DE (1) DE19728899C1 (en)
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    * Cited by examiner, † Cited by third party
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    DE19748053C2 (en) * 1997-10-30 2000-01-20 Henkel Kgaa Use of alkoxylated triglycerides and method of making carbonless paper
    WO2000016985A1 (en) * 1998-09-23 2000-03-30 The Mead Corporation Microcapsules comprising solvent for chromogenic material

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    DE3635114C1 (en) * 1986-10-15 1988-07-14 Caribonum Ltd Overlap rewritable ribbon and its use in endlessly stuffed cassettes
    DE3914131A1 (en) * 1989-04-28 1990-10-31 Henkel Kgaa USE OF CALCINATED HYDROTALCITES AS CATALYSTS FOR ETHOXYLATION OR PROPOXYLATION OF FATTY ACID ESTERS
    GB9113086D0 (en) * 1991-06-18 1991-08-07 Wiggins Teape Group Ltd Solvent compositions for use in pressure-sensitive copying paper
    GB9221621D0 (en) * 1992-10-15 1992-11-25 Wiggins Teape Group Ltd Solvents for use in pressure-sensitive record material
    FR2723032B1 (en) * 1994-07-26 1996-11-22 Copigraph Sa NOVEL ORGANIC SOLVENT FOR MICROCAPSULES USEFUL IN PARTICULAR FOR PRODUCING PRESSURE SENSITIVE SELF-COPYING PAPER AND LAPRESSION SENSITIVE PAPER COATED WITH SUCH MICROCAPSULES

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    WO1999002349A3 (en) 2000-09-28
    EP1054776A2 (en) 2000-11-29
    DE19728899C1 (en) 1998-10-22
    WO1999002349A2 (en) 1999-01-21

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