EP0000903B1 - Carbonless copying paper and manufacture thereof - Google Patents

Carbonless copying paper and manufacture thereof Download PDF

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Publication number
EP0000903B1
EP0000903B1 EP78100634A EP78100634A EP0000903B1 EP 0000903 B1 EP0000903 B1 EP 0000903B1 EP 78100634 A EP78100634 A EP 78100634A EP 78100634 A EP78100634 A EP 78100634A EP 0000903 B1 EP0000903 B1 EP 0000903B1
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EP
European Patent Office
Prior art keywords
solution
microcapsules
dye
capsule
papers
Prior art date
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
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EP78100634A
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German (de)
French (fr)
Other versions
EP0000903A3 (en
EP0000903A2 (en
Inventor
Günther Dr. Baatz
Walter Dr. Schäfer
Kurt Dr. Findeisen
Manfred Dr. Dahm
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Bayer AG
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Bayer AG
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]
    • Y10T428/2985—Solid-walled microcapsule from synthetic polymer

Definitions

  • Reaction copy papers are also known from US Pat. No. 3,432,327. This is understood to mean papers in which two layers are in contact with one another, each of which contains a color-forming component which reacts with the other to form a dye. At least one of the color formation components is in the form of microcapsules, which break when a writing tool is pressed and release the encapsulated component for reaction with the second.
  • the two color-forming layers can be applied one above the other on a paper surface or separately on two paper surfaces in contact with one another.
  • phase interface polymerization a polyreaction at the phase interface of a hydrophilic and a hydrophobic liquid, is used for the production of the microcapsules.
  • the reaction to the dye must take place in the hydrophilic medium. Therefore, a color-forming component is first dissolved in a hydrophilic liquid, for example water, and then the first component of the capsule wall material is added to this solution.
  • the second component of the capsule wall material is dissolved in a hydrophobic liquid (oil, paraffin, aromatic solvent), and then the hydrophilic solution is dispersed in the hydrophobic.
  • the microcapsule then forms from the two capsule wall components at the phase interfaces of the dispersed hydrophilic droplets.
  • the second color forming component can also be encapsulated; as a rule, however, it is not encapsulated.
  • a large number of pairs of suitable color forming components are given in the US patent; it may a. for inorganic salts (e.g. potassium hexacyanoferrate 11 - ammonium iron (III) sulfate), colored metal complexes (e.g. diacetyl-dioxime-nickel acetate) and organic dyes (e.g. bromocresol purple sodium hydroxide).
  • inorganic salts e.g. potassium hexacyanoferrate 11 - ammonium iron (III) sulfate
  • colored metal complexes e.g. diacetyl-dioxime-nickel acetate
  • organic dyes e.g. bromocresol purple sodium hydroxide
  • Capsule wall-forming components are also given in large numbers, for example the combination of certain selected diisocyanates and water, diol or diamine.
  • US Patent 3,432,327 is directed to encapsulating a solution of a color former in a hydrophilic solvent, preferably water.
  • German Offenlegungsschrift 23 11 712 also discloses the use of reaction products of di- or polyols with a molecular weight of 400-10,000 and di- or polyisocyanates as isocyanate components in microencapsulation.
  • Map can thus encapsulate pre-dye solutions for carbonless papers; these capsules are not impermeable to the mostly aromatic and alkylaromatic solvents necessary for the process, although this is absolutely necessary for the effect of the reaction carbonless papers. They also tend to agglomerate very strongly. Capsule agglomerates cause considerable disruption because individual capsules are destroyed during the manufacture of the paper and a stained paper is thus obtained. Under unfavorable conditions, the writing performance of the papers is even significantly reduced. You therefore need individual capsules for carbonless papers that do not tend to agglomerate.
  • the invention is based on the knowledge that walls of microcapsules containing color former solutions for carbonless papers are obtained from, on the one hand, diisocyanates of the formula (I) wherein R is an alkylene radical having 2 to 10 carbon atoms and, on the other hand, a diamine.
  • the capsule membranes resulting from the reaction product excellently meet the requirements specified above when hydrophobic organic solutions of the color formers are encapsulated.
  • the invention relates to a carbonless reaction paper which contains a solution of a color former in microencapsulated form, the color former being encapsulated as a solution in a hydrophobic organic solvent, characterized in that the capsule walls are made from the polyaddition product of a diisocyanate of the formula (I) where R is an alkylene radical having 2 to 10 carbon atoms, and a diamine.
  • Another object of the invention is the use of a solution of a color former in a hydrophobic, organic solvent as the core material in microcapsules, the walls of which consist of the polyaddition product of a diisocyanate of the formula (I) and a diamine, for the preparation of carbonless reaction papers.
  • the diisocyanates of the formula (I) are derivatives of 2,4,6-triketo-1,3,5-oxadiazine with two free isocyanate groups.
  • the compounds in which the radicals R are from butane, hexane and octane are particularly suitable descended.
  • the n-hexane radical is particularly preferred.
  • the products and their manufacture are known from DE-AS 1,670,666.
  • Color formers are essentially colorless, basic products that have different chromophoric groups. Examples of these are bis (p-aminoaryl) phthalides, leucoauramines, acylauramines, ⁇ , ⁇ -unsaturated aryl ketones, basic monoazo dyes, rhodamine B-lactams such as the N- (p-nitrophenyl) rhodamine B-lactams, by amino groups substituted polyarylcarbinols and their reaction products, for example their esters or ethers and various heterocyclic spiranes.
  • Preferred compounds are 3,3-bis (p-dimethylaminophenyl) -6-dimethylamino-phthalide (crystal violet lactone). Benzoyl leukomethylene blue and derivatives from Michlers Hydrol, especially the p-toluenesulfinate from Michlers Hydrol.
  • Solvents for the basic color former component (dye precursor) and for the diisocyanates are generally aromatic hydrocarbons, which can also be substituted by alkyl or halogen.
  • Examples are chlorinated diphenyls, dodecylbenzene, mixtures of partially hydrogenated and unhydrogenated terphenyls, isopropyldiphenyl, diisopropylbenzene, ethyl benzoate, mixtures of diphenyl and diphenyl ether, phthalic acid butyl ester, aralkyl or diaryl ethers, the xylenes in aromatics and aromatics.
  • the solvent for the diamines is generally water.
  • the leaking core material meets the receiver layer, which has a coating on which dyes are formed from the colorless dye precursors, which now make the copy appear.
  • Coating materials are natural and synthetic products such as kaolin, attapulgite, montmorillonite, concreteite, acidic bleaching earth or phenolic resins. You can e.g. in the donor layer, i.e. the microcapsule layer, acid-activated dyes and acid-reacting components in the receiver layer.
  • microcapsules can be produced in various ways. So you can first dissolve the diisocyanate and the dye precursor in a suitable solvent and emulsify this organic phase in an aqueous diamine solution, which may optionally also contain protective colloids. It is also possible to first emulsify the organic phase with or without surfactants and protective colloids in water to a desired particle size and only then to add the diamine necessary for the capsule wall formation to the aqueous phase.
  • emulsifying agents are added to the aqueous phase.
  • examples of such products acting as protective colloids are carboxymethyl cellulose, gelatin and polyvinyl alcohol.
  • examples of emulsifiers are oxyethylated 3-benzylhydroxybiphenyl, reaction products of nonylphenol with different amounts of ethylene oxide and sorbitan fatty acid ester.
  • the course of the capsule wall-forming polyaddition can be followed on the basis of the amine consumption.
  • the oxadiazine ring of the isocyanate can be opened by increasing the temperature, a new isocyanate group being formed which can react with the amine already used or with another amine with crosslinking and curing of the polyaddition product.
  • the microcapsules can be produced continuously or batchwise. Dispersing devices which generate a shear gradient are generally used. Examples include blade, basket, high-speed stirrers, colloid mills, homogenizers, ultrasonic dispersers, nozzles, jet nozzles, and Supraton machines.
  • the strength of the turbulence during mixing is primarily decisive for the diameter of the microcapsules obtained. Capsules from 1 to 2000 ⁇ m in size can be made. Capsules with diameters of 2 to 20 ⁇ m are preferred.
  • the capsules do not agglomerate and have a narrow particle size distribution.
  • the weight ratio of core material to casing material is 50-90 to 50-10.
  • the pressure-sensitive carbonless papers are produced in a known manner (see M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation, 1972, pages 242-277).
  • the microcapsule suspensions obtained primarily contain 10 to 35% by weight of capsules. They need something to cream as long as they do not contain any binding agent. This can be used for concentration.
  • the preferred capsule size is around 10 ⁇ m.
  • the homogenized capsule suspensions, provided with binders and optionally inert fillers such as talc or kaolin, can be applied manually with a floral wire squeegee or mechanically with an air brush in application quantities of 4-8 91 m 2 on base paper (for example from 40 to 100 g / m 2 ).
  • the coating of base papers is described in German Offenlegungsschriften 1,934,457 and 1,955,542.
  • the papers coated in this way contain the first color-forming component; they are called encoder components.
  • the donor component is generally the back of the top sheet for carbonless sets.
  • the front of the next sheet is coated with the second coloring component.
  • This layer is called the slave component.
  • the slave component In the case of carbonless copies, the slave component is the top of the second sheet of paper.
  • the following encoder sheets must have a slave coating on the opposite side.
  • the production of such receiver layers is known and is also described in German Offenlegungsschriften 1,934,457 and 1,955,542.
  • n-hexane-1,6-diisocyanate 2000 g of n-hexane-1,6-diisocyanate are mixed with 1 g of tri-p-tolylarsine oxide in a 2.7 l autoclave and stirred at 50 ° C. for 8 hours at a CO 2 pressure of 3 atm.
  • reaction is interrupted by adding 2 g of phosphorus trichloride and the reaction product is separated from the unreacted starting product in a thin-layer evaporator (two passes, heating temperature 180 ° C. at 1 torr).
  • the IR spectrum shows the characteristic carbonyl absorption bands at 5.5 to 5.71 and 5.82 ⁇ m.
  • the homogeneous organic phase is then emulsified in 300 g of water, which is 1.5 g. Mowiol 56-98 (polyvinyl alcohol from Hoechst AG) as an emulsifying agent.
  • a Kotthoff mixing siren is used for emulsification (8900 rpm, 1 l beaker).
  • the mixing siren is replaced by a Lenart-Rapid laboratory stirrer (500 rpm).
  • a solution of 0.7 g of 1-aminoethylethylenediamine-1,2- (diethylenetriamine) in 70 g of water is added to the batch.
  • the batch is quickly heated to 70 ° C. and kept at this temperature for about 1 hour.
  • the heating phase is only used to form a casing that is as stable as possible.
  • the diameter of the resulting microcapsules is in the order of 3-25 ⁇ m.
  • the organic phase is prepared as described in Example 1 (b) with the change that 25 g of Solvesso 200 (aromatic mixture from Esso AG) are used as the solvent.
  • Example 1 (b) The encapsulation and aftertreatment is also carried out as described in Example 1 (b), with the change that 0.7 g of ethylenediamine in 70 g of water are added as the amine component to the outer phase.
  • microcapsules are 3-25 ⁇ m in size.
  • the resulting organic phase is encapsulated and post-treated as described in Example 1 (b). 0.7 g of diethylenetriamine in 70 g of water are used as the amine component.
  • the resulting microcapsules have a diameter of 2-20 ⁇ m.
  • 1,4-tetramethylene diisocyanate 280 g are saturated by introducing them with dry CO 2 gas and, with stirring and further introducing carbon dioxide at 60 ° C., with 0.7 g of tri-n-butylphosphine (0.25% ) offset. After 2 hours, the NCO value has dropped to 53.8%.
  • the reaction mixture is separated in a thin-film evaporator (heating temperature 180 ° C. at 1 torr), 219 g of 1,4-tetramethylene diisocyanate being recovered and 54 g of a viscous oil being obtained.
  • microcapsules are obtained with a diameter of 1-35 ⁇ m.
  • a microcapsule dispersion with about 30% capsule content can be produced with the aid of an ultrasound homogenizer (type Minisonic from Ultrasonics) with a solution of 4.5 parts of crystal violet lactone and 17 parts of the oxadiazinone described in Example 1 (b) Perform 75 parts of Santosol 340 (partially hydrogenated terphenyl from Monsanto and 25 parts of Solvesso 100 (Esso AG) as the organic phase.
  • ultrasound homogenizer type Minisonic from Ultrasonics
  • aqueous phase 150 parts of the organic phase to 250 parts of aqueous phase are used for emulsification.
  • the aqueous phase contains 0.5% Mowiol 26-88 and 0.1% Tween 80 (emulsifier from Atlas Chemie) as an emulsifying aid.
  • the two phases or the emulsion produced therefrom are passed 5 times through the ultrasonic homogenizer. Immediately afterwards, the resulting emulsion is transferred to a beaker and swiftly stirred with a laboratory stirrer (type Lenart-Rapid, 500 rpm) the amount of ethylenediamine corresponding to the NCO value of the oxadiazinone used stoichiometrically added (as an aqueous 4% solution).
  • a laboratory stirrer type Lenart-Rapid, 500 rpm
  • microcapsule dispersion is stirred at room temperature for about 1 hour.
  • the microcapsules obtained are in the range of 1-30 ⁇ m in diameter.
  • the resulting organic phase is with the aid of a Kotthoff mixing siren at 8900 rpm.
  • a solution of 0.7 g of diethylenetriamine in 70 g of water is added to the mixture.
  • the mixing siren is replaced by a laboratory stirrer (Lenart-Rapid type, 500 rpm) and the microcapsule dispersion is kept at 70 ° C. for about 1 hour with stirring.
  • the microcapsules have a diameter of 3-25 ⁇ m.

Description

Reaktionsdurchschreibepapiere sind bekannt (vergl. M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation 1972, Seiten 242-277; G. Baxter in Microencapsulation, Processes and Applications, herausgegeben von J. E. Vandegaer, Plenum Press, New York, London, Seiten 127-143).Reaction carbon papers are known (see M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation 1972, pages 242-277; G. Baxter in Microencapsulation, Processes and Applications, edited by JE Vandegaer, Plenum Press, New York, London, pages 127 -143).

Reaktionsdurchschreibepapiere sind auch aus der US-PS 3.432.327 bekannt. Man versteht darunter Papiere, in denen zwei Schichten miteinander in Kontakt stehen, von denen jede eine Farbbildungskomponente enthält, die mit der jeweils anderen unter Bildung eines Farbstoffes reagiert. Mindestens eine der Farbbildungskomponenten liegt in Form von Mikrokapseln vor, die durch den Druck eines Schreibwerkzeuges zerbrechen und die eingekapselte Komponente zur Reaktion mit der zweiten freigeben. Die beiden Farbbildungsschichten können übereinander auf einer Papieroberfläche oder getrennt auf zwei miteinander in Kontakt stehenden Papieroberflächen aufgetragen sein.Reaction copy papers are also known from US Pat. No. 3,432,327. This is understood to mean papers in which two layers are in contact with one another, each of which contains a color-forming component which reacts with the other to form a dye. At least one of the color formation components is in the form of microcapsules, which break when a writing tool is pressed and release the encapsulated component for reaction with the second. The two color-forming layers can be applied one above the other on a paper surface or separately on two paper surfaces in contact with one another.

Für die Herstellung der Mikrokapseln benutzt man gemäß US-PS 3.432.327 die Phasengrenzflächenpolymerisation, eine Polyreaktion an der Phasengrenzfläche einer hydrophilen und einer hydrophoben Flüssigkeit. Die Reaktion zum Farbstoff muß nach der US-Patentschrift im hydrophilen Medium ablaufen. Deshalb wird zunächst eine Farbbildungskomponente in einer hydrophilen Flüssigkeit, beispielsweise Wasser, gelöst und dann dieser Lösung die erste Komponente des Kapselwandmaterials zugegeben. Die zweite Komponente des Kapselwandmaterials wird in einer hydrophoben Flüssigkeit (Öl, Paraffin, aromatisches Lösungsmittel) gelöst, und dann die hydrophile Lösung in der hydrophoben dispergiert. An den Phasengrenzflächen der dispergierten hydrophilen Tröpfchen bildet sich dann aus den beiden Kapselwandkomponenten die Mikrokapsel.According to US Pat. No. 3,432,327, phase interface polymerization, a polyreaction at the phase interface of a hydrophilic and a hydrophobic liquid, is used for the production of the microcapsules. According to the US patent, the reaction to the dye must take place in the hydrophilic medium. Therefore, a color-forming component is first dissolved in a hydrophilic liquid, for example water, and then the first component of the capsule wall material is added to this solution. The second component of the capsule wall material is dissolved in a hydrophobic liquid (oil, paraffin, aromatic solvent), and then the hydrophilic solution is dispersed in the hydrophobic. The microcapsule then forms from the two capsule wall components at the phase interfaces of the dispersed hydrophilic droplets.

Die zweite Farbbildungskomponente kann ebenfalls einegekapselt werden; in der Regel ist sie allerdings nicht eingekapselt.The second color forming component can also be encapsulated; as a rule, however, it is not encapsulated.

Paare von geeigneten Farbbildungskomponenten sind in der US-Patentschrift in großer Zahl angegeben; es kann sich u. a. um anorganische Salze (z.B. Kaliumhexacyanoferrat 11 - Ammonium-Eisen-(III)-Sulfat), gefärbte Metallkomplexe (z.B. Diacetyl-dioxim-Nickelacetat) und organische Farbstoffe (z.B. Bromkresol-purpur-Natriumhydroxid) haldeln.A large number of pairs of suitable color forming components are given in the US patent; it may a. for inorganic salts (e.g. potassium hexacyanoferrate 11 - ammonium iron (III) sulfate), colored metal complexes (e.g. diacetyl-dioxime-nickel acetate) and organic dyes (e.g. bromocresol purple sodium hydroxide).

Kapselwandbildungskomponenten sind ebenfalls in großer Zahl angegeben, beispielsweise die Kombination bestimmter ausgewählter Diisocyanate und Wasser, Diol oder Diamin.Capsule wall-forming components are also given in large numbers, for example the combination of certain selected diisocyanates and water, diol or diamine.

Die Arbeitsweise der US-Patentschrift 3.432.327 ist darauf gerichtet, eine Lösung eines Farbbildners in einem hydrophilen Lösungsmittel, bevorzugt Wasser, einezukapseln.The operation of US Patent 3,432,327 is directed to encapsulating a solution of a color former in a hydrophilic solvent, preferably water.

Dieses ist aber von entscheidendem Nachteil, denn für Wasser undurchlässige Kapselfilme sind bisher praktisch nicht herstellbar. Somit sind diese Kapseln nicht lagerstabil, da sie nach mehr oder weniger kurzer Zeit austrocknen. Daraus hergestellte Durchschreibepapiere verlieren somit ihre Durchschreibefähigkeit rasch.However, this is a crucial disadvantage, because capsule films impermeable to water have so far been practically impossible to produce. Thus, these capsules are not stable in storage because they dry out after a more or less short time. Carbonless papers made from it thus quickly lose their carbonless ability.

Aus der Deutschen Offenlegungsschrift 23 11 712 ist weiterhin die Verwendung von Umsetzungsprodukten aus Di- oder Polyolen vom Molekulargewicht 400-10.000 und Di- oder Polyisocyanaten als Isocyanatkomponenten bei der Mikroverkapselung bekannt. Map kann so Lösungen von Farbstoffvorstufen für Durchschreibepapiere einkapseln; diese Kapseln sind für die für das Verfahren notwendigen, meist aromatischen und alkylaromatischen Lösungsmittel nicht undurchlässig, obwohl dies für die Wirkung der Reaktionsdurchschreibepapiere unbedingt erforderlich ist. Sie neigen uch sehr stark zur Agglomeration. Kapselagglomerate stören erheblich, weil einzelne Kapseln schon bei der Herstellung der Papiere zerstört werden und so ein fleckiges Papier erhalten wird. Unter ungünstigen Bedingungen wird sogar die Schreibleistung der Papiere bedeutend herabgesetzt. Man braucht daher einzelne, nicht zur Agglomeration neigende Kapseln für Durchschreibepapiere.German Offenlegungsschrift 23 11 712 also discloses the use of reaction products of di- or polyols with a molecular weight of 400-10,000 and di- or polyisocyanates as isocyanate components in microencapsulation. Map can thus encapsulate pre-dye solutions for carbonless papers; these capsules are not impermeable to the mostly aromatic and alkylaromatic solvents necessary for the process, although this is absolutely necessary for the effect of the reaction carbonless papers. They also tend to agglomerate very strongly. Capsule agglomerates cause considerable disruption because individual capsules are destroyed during the manufacture of the paper and a stained paper is thus obtained. Under unfavorable conditions, the writing performance of the papers is even significantly reduced. You therefore need individual capsules for carbonless papers that do not tend to agglomerate.

Aus der DE-OS 22 51 381 schließlich ist bekannt, Farbbildner in Kapseln einzuschließen, deren Wände aus Polyharnstoff bestehen. Auf Seite 12 wird mitgeteilt, daß gute Ergebnisse nicht immer erhalten werden, sondern insbesondere dann, wenn man Polyisocyanat-Addukte oder Polyamin-Addukte benutzt. In den konkret angegebenen Fällen ist jedoch die Dichtigkeit und die Alterungsbeständigkeit der Mikrokapseln unzureichend.Finally, it is known from DE-OS 22 51 381 to include color formers in capsules, the walls of which consist of polyurea. On page 12 it is stated that good results are not always obtained, but especially when using polyisocyanate adducts or polyamine adducts. In the specifically stated cases, however, the tightness and the aging resistance of the microcapsules are insufficient.

Die Mikrokapseln für die Herstellung von Durchschreibepapieren

  • (1.) müssen für den Farbbildner und sein Lösungsmittel undurchlässig sein. Durchlässigkeit für den Farbbildner führt zur Verfärbung, Durchlässigkeit für das Lösungsmittel zum Eintrocknen des Kapselinhalts und damit zur Wirkungslosigkeit;
  • (2.) dürfen erst unter dem Druck des Schreibgerätes zerbrechen. Die Kapselwand muß also andersartige Belastungen überstehen;
  • (3.) sollen möglichst als individuelle Teilchen vorliegen und nicht als größere Agglomerate;
  • (4.) müssen sich leicht auf die Papieroberfläche aufbringen und sofort fixieren lassen. Dazu müssen sie so temperaturstabil sein, daß sie Temperaturen bis zu 100°C beim Trocknen unbeschadet überstehen.
The microcapsules for the production of carbonless papers
  • (1.) must be impermeable to the color former and its solvent. Permeability to the color former leads to discoloration, permeability to the solvent dries out the capsule content and thus makes it ineffective;
  • (2.) may only break under pressure from the writing instrument. The capsule wall must therefore withstand other types of stress;
  • (3.) should exist as individual particles if possible and not as larger agglomerates;
  • (4.) must be easy to apply to the paper surface and can be fixed immediately. To do this, they must be so temperature-stable that they can withstand temperatures up to 100 ° C when drying without damage.

Weiterhin ist es günstig, möglichst wenig Hüllmaterial zu verwenden, und die Kapselwände möglichst dicht gegenüber äußeren Einflüssen, insbesondere gegen Sauerstoff, Lichteinwirkung und Säuren oder Basen zu machen.Furthermore, it is advantageous to use as little shell material as possible and to make the capsule walls as tight as possible against external influences, in particular against oxygen, exposure to light and acids or bases.

Der Erfindung liegt die Erkenntnis zugrunde, daß Wände von Farbbildnerlösungen enthaltenden Mikrokapseln für Reaktionsdurchschreibepapiere erhalten werden aus, einerseits, Diisocyanaten der Formel (I)

Figure imgb0001
worin R einen Alkylenrest mit 2 bis 10 C-Atomen bedeutet und, andererseits, einem Diamin. Die aus dem Reaktionsprodukt resultierenden Kapselmembranen erfüllen in hervorragender Weise die oben angegebenen Anforderungen, wenn hydrophobe organische Lösungen der Farbbildner eingekapselt werden.The invention is based on the knowledge that walls of microcapsules containing color former solutions for carbonless papers are obtained from, on the one hand, diisocyanates of the formula (I)
Figure imgb0001
 wherein R is an alkylene radical having 2 to 10 carbon atoms and, on the other hand, a diamine. The capsule membranes resulting from the reaction product excellently meet the requirements specified above when hydrophobic organic solutions of the color formers are encapsulated.

Gegenstand der Erfindung ist ein Reaktionsdurchschreibepapier, das eine Lösung eines Farbbildners in mikroverkapselter Form enthält, wobei der Farbbildner als Lösung in einem hydrophoben organischen Lösungsmittel eingekapselt ist, dadurch gekennzeichnet, dass die Kapselwände aus dem Polyadditionsprodukt eines Diisocyanats der Formel (I)

Figure imgb0002
worin R einen AlkyJenrest mit 2 bis 10 C-Atomen bedeutet, und einem Diamin.The invention relates to a carbonless reaction paper which contains a solution of a color former in microencapsulated form, the color former being encapsulated as a solution in a hydrophobic organic solvent, characterized in that the capsule walls are made from the polyaddition product of a diisocyanate of the formula (I)
Figure imgb0002
 where R is an alkylene radical having 2 to 10 carbon atoms, and a diamine.

Ein weiterer Gegenstand der Erfindung ist die Verwendung einer Lösung eines Farbbildners in einem hydrophoben, organischen Lösungsmittel als Kernmaterial in Mikrokapseln, deren Wände aus dem Polyadditionsprodukt eines Diisocyanats der Formel (I) und einem Diamin bestehen, zur Herstellung von Reaktionsdurchschreibepapieren.Another object of the invention is the use of a solution of a color former in a hydrophobic, organic solvent as the core material in microcapsules, the walls of which consist of the polyaddition product of a diisocyanate of the formula (I) and a diamine, for the preparation of carbonless reaction papers.

Neben den schon genannten ergibt sich ein wieterer Vorteil bei Verwendung dieser Isocyanate durch die hervorragende Löslichkeit in vielen Lösungsmitteln, die für die Lösung der Farbstoffvorstufen infrage kommen. Dadurch erhält man einen Freiheitsgrad in der Auswahl der Lösungsmittel, der besonders im Hinblick auf die Umweltbelastung von Bedeutung ist. Man kann so durch Kombination das für die Lösung des Farbstoffes am besten geeignete und gleichzeitig das die Umwelt am wenigsten belastende Lösungsmittel optimal auswählen.In addition to those already mentioned, there is a further advantage when using these isocyanates because of the excellent solubility in many solvents which are suitable for the solution of the dye precursors. This gives you a degree of freedom in the choice of solvents, which is particularly important with regard to environmental pollution. In this way, the most suitable solvent for the solution of the dye and at the same time the least polluting solvent can be optimally selected by combination.

Die Diisocyanate der Formel (I) stellen Derivate des 2,4,6-Triketo-1,3,5-Oxadiazins mit zwei freien Isocyanat-Gruppen dar. Besonders geeignet sind die Verbindungen, in denen die Reste R vom Butan, Hexan und Octan abstammen. Besonders bevorzugt ist der n-Hexanrest. Die Produkte und ihre Herstellung sind aus der DE-AS 1.670.666 bekannt.The diisocyanates of the formula (I) are derivatives of 2,4,6-triketo-1,3,5-oxadiazine with two free isocyanate groups. The compounds in which the radicals R are from butane, hexane and octane are particularly suitable descended. The n-hexane radical is particularly preferred. The products and their manufacture are known from DE-AS 1,670,666.

Geeignete Diamine sind aliphatische primäre oder sekundäre Diamine wie z.B.:

  • Äthylendiamin-(1,2), Bis(3-aminopropyl)-amin, Hydrazin, Hydrazinäthanol-(2), Bis-(2-methylaminoäthyl)-methylamin, 1,4-Diaminobenzol, 4,4'-Diaminodiphenyl-methan, 1,4-Diaminocyclohexan, 3-Amino-1-methyl-aminopropan, N-Hydroxyäthyläthylendiamin, N-Methyl-bis(3-aminopropyl)-amin, 1,4-Diamino-n-butan, 1,6-Diamino-n-hexan, Äthylen-(1,2)-diamin-N-äthan-sulfonsäure (als Alkalisalz), 1-Aminoäthyläthylendiamin-(1,2), Bis-(N,N'-aminoäthyl)-äthylendiamin-(1,2).
Suitable diamines are aliphatic primary or secondary diamines such as:
  • Ethylenediamine (1,2), bis (3-aminopropyl) amine, hydrazine, hydrazine ethanol (2), bis (2-methylaminoethyl) methylamine, 1,4-diaminobenzene, 4,4'-diaminodiphenylmethane, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-hydroxyethylethylenediamine, N-methyl-bis (3-aminopropyl) amine, 1,4-diamino-n-butane, 1,6-diamino-n -hexane, ethylene- (1,2) -diamine-N-ethane-sulfonic acid (as alkali salt), 1-aminoethylethylenediamine- (1,2), bis- (N, N'-aminoethyl) -ethylenediamine- (1,2 ).

Farbbildner sind im wesentlichen farblose, basische Produkte, die verschiedene chromophore Gruppen haben. Beispiele hierfür sind Bis-(p-aminoaryl)-phthalide, Leukoauramine, Acylauramine, a,ß- ungesättigte Arylketone,'basische Monoazofarbstoffe, Rhodamin-B-Lactame wie die N-(p-nitrophenyl)-Rhodamin B-Lactame, durch Aminogruppen substituierte Polyarylcarbinole und deren Umsetzungsprodukte, z.B. deren Ester oder Äther und verschiedene heterocyclische Spirane. Bevorzugte Verbindungen sind 3,3-Bis-(p-dimethylaminophenyl)-6-dimethylamino-phthalid (Kristallviolettlacton). Benzoylleukomethylenblau und Derivate von Michlers Hydrol, insbesondere das p-Toluolsulfinat von Michlers Hydrol.Color formers are essentially colorless, basic products that have different chromophoric groups. Examples of these are bis (p-aminoaryl) phthalides, leucoauramines, acylauramines, α, β-unsaturated aryl ketones, basic monoazo dyes, rhodamine B-lactams such as the N- (p-nitrophenyl) rhodamine B-lactams, by amino groups substituted polyarylcarbinols and their reaction products, for example their esters or ethers and various heterocyclic spiranes. Preferred compounds are 3,3-bis (p-dimethylaminophenyl) -6-dimethylamino-phthalide (crystal violet lactone). Benzoyl leukomethylene blue and derivatives from Michlers Hydrol, especially the p-toluenesulfinate from Michlers Hydrol.

Lösungsmittel für die basische Farbbildnerkomponente (Farbstoffvorstufe) und für die Diisocyanate sind im allgemeinen aromatische Kohlenwasserstoffe, die auch durch Alkyl oder Halogen substituiert sein können.Solvents for the basic color former component (dye precursor) and for the diisocyanates are generally aromatic hydrocarbons, which can also be substituted by alkyl or halogen.

Beispiele sind chlorierte Diphenyle, Dodecylbenzol, Gemische aus teilhydrierten und nichthydrierten Terphenylen, Isopropyldiphenyl, Diisopropylbenzol, Benzoesäureäthylester, Gemische aus Diphenyl und Diphenyläther, Phthalsäurebutylester, Aralkyl- oder Diaryläther, die Xylole od. handelsübliche, in den Aromatisierungsanlagen der Petrochemie und Erdölchemie anfallende Aromatengemische. Lösungsmittel für die Diamine ist im allgemeinen Wasser.Examples are chlorinated diphenyls, dodecylbenzene, mixtures of partially hydrogenated and unhydrogenated terphenyls, isopropyldiphenyl, diisopropylbenzene, ethyl benzoate, mixtures of diphenyl and diphenyl ether, phthalic acid butyl ester, aralkyl or diaryl ethers, the xylenes in aromatics and aromatics. The solvent for the diamines is generally water.

Beim Beschreiben der Reaktionsdurchschreibepapiere trifft das auslaufende Kernmaterial auf die Nehmerschicht, die eine Beschichtung besitzt, auf der aus den farblosen Farbstoffvorstufen Farbstoffe entstehen, die nun die Durchschrift erscheinen lassen. Beschichtungsmaterialien sind dabei natürliche und synthetische Produkte, wie Kaolin, Attapulgit, Montmorillonit, Betonit, saure Bleicherde oder Phenolharze. Man kann z.B. in der Geberschicht, d.h. der Mikrokapselschicht, säure-aktivierbare Farbstoffe und in der Nehmerschicht sauer reagierende Komponenten einsetzen.When writing the reaction carbonless papers, the leaking core material meets the receiver layer, which has a coating on which dyes are formed from the colorless dye precursors, which now make the copy appear. Coating materials are natural and synthetic products such as kaolin, attapulgite, montmorillonite, concreteite, acidic bleaching earth or phenolic resins. You can e.g. in the donor layer, i.e. the microcapsule layer, acid-activated dyes and acid-reacting components in the receiver layer.

Die Herstellung der Mikrokapseln kann in verschiedener Weise erfolgen. So kann man zunächst das Diisocyanat und die Farbstoffvorstufe in einem geeigneten Lösungsmittel lösen und diese organische Phase in einer wäßrigen Diaminlösung, die gegebenenfalls auch Schutzkolloide enthalten kann, emulgieren. Es ist auch möglich, die organische Phase zunächst mit oder ohne Tenside und Schutzkolloide in Wasser bis zu einer gewünschten Teilchengröße zu emulgieren und der wäßrigen Phase erst dann das für die Kapselwandbildung notwendige Diamin zuzusetzen.The microcapsules can be produced in various ways. So you can first dissolve the diisocyanate and the dye precursor in a suitable solvent and emulsify this organic phase in an aqueous diamine solution, which may optionally also contain protective colloids. It is also possible to first emulsify the organic phase with or without surfactants and protective colloids in water to a desired particle size and only then to add the diamine necessary for the capsule wall formation to the aqueous phase.

Zur Emulgierung und Stabilisierung der gebildeten Emulsion werden der wäßrigen Phase Emulgierhilfsmittel zugesetzt. Beispiele für solche, als Schutzkolloide wirkende Produkte sind Carboxymethylcellulose, Gelatine und Polyvinylalkohol. Beispiele für Emulgatoren sind oxäthyliertes 3-Benzylhydroxybiphenyl, Umsetzungsprodukte von Nonylphenol mit unterschiedlichen Mengen Äthylenoxid und Sorbitanfettsäureester.To emulsify and stabilize the emulsion formed, emulsifying agents are added to the aqueous phase. Examples of such products acting as protective colloids are carboxymethyl cellulose, gelatin and polyvinyl alcohol. Examples of emulsifiers are oxyethylated 3-benzylhydroxybiphenyl, reaction products of nonylphenol with different amounts of ethylene oxide and sorbitan fatty acid ester.

Den Verlauf der kapselwandbildenden Polyaddition kann man anhand des Aminverbrauchs verfolgen. Nach vollständiger Umsetzung der freien Isocyanatgruppen kann man durch Temperaturerhöhung den Oxadiazin-Ring des Isocyanats öffnen, wobei sich eine neue Isocyanat-Gruppe bildet, die mit dem bereits benutzten oder einem anderen Amin unter Vernetzung und Härtung des Polyadditionsproduktes reagieren kann.The course of the capsule wall-forming polyaddition can be followed on the basis of the amine consumption. After the free isocyanate groups have been completely reacted, the oxadiazine ring of the isocyanate can be opened by increasing the temperature, a new isocyanate group being formed which can react with the amine already used or with another amine with crosslinking and curing of the polyaddition product.

Die Mikrokapseln können kontinuierlich oder diskontinuierlich hergestellt werden. Man verwendet im allgemeinen Dispergiergeräte, die ein Schergefälle erzeugen. Beispiele hierfür sind Blatt-, Korb-, Schnellrührer, Kolloidmühlen, Homogenisatoren, Ultraschalldispergatoren, Düsen, Strahldüsen, Supratonmaschinen. Die Stärke der Turbulenz beim Vermischen ist in erster Linie bestimmend für den Durchmesser der erhaltenen Mikrokapseln. Kapseln in der Größe von 1 bis 2000,um können hergestellt werden. Bevorzugt sind Kapseln mit Durchmessern von 2 bis 20 ,um. Die Kapseln agglomerieren nicht und haben eine enge Teilchengrößenverteilung. Das Gewichtsverhältnis von Kemmaterial zu Hüllenmaterial ist 50-90 zu 50-10.The microcapsules can be produced continuously or batchwise. Dispersing devices which generate a shear gradient are generally used. Examples include blade, basket, high-speed stirrers, colloid mills, homogenizers, ultrasonic dispersers, nozzles, jet nozzles, and Supraton machines. The strength of the turbulence during mixing is primarily decisive for the diameter of the microcapsules obtained. Capsules from 1 to 2000 µm in size can be made. Capsules with diameters of 2 to 20 μm are preferred. The capsules do not agglomerate and have a narrow particle size distribution. The weight ratio of core material to casing material is 50-90 to 50-10.

Die druckempfindlichen Durchschreibepapiere werden in bekannter Weise hergestellt (vergl. M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation, 1972, Seiten 242-277). Die primär erhaltenen Mikrokapselsuspensionen enthalten im allgemeinen 10 bis 35 Gew.-% Kapseln. Sie niegen etwas zum Aufrahmen, solange sie kein Bindemittel enthalten. Dies läßt sich für eine Konzentration ausnutzen. Die bevorzugte Kapselgröße liegt um 10 ,um. Die homogenisierten, mit Binder und gegebenenfalls inerten Füllstoffen wie Talkum oder Kaolin versehenen Kapselsuspensionen können manuell mit einem Blumendrahtrakel oder maschinell mit einer Luftbürste in Auftragsmengen von 4-8 91m2 auf Rohpapier (z.B. von 40 bis 100 g/m2) aufgetragen werden. Die Beschichtung von Rohpapieren ist beschrieben in den Deutschen Offenlegungsschriften 1.934.457 und 1.955.542. Die so beschichteten Papiere enthalten die erste Farbbildungskomponente; sie werden als Geberkomponenten bezeichnet.The pressure-sensitive carbonless papers are produced in a known manner (see M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation, 1972, pages 242-277). The microcapsule suspensions obtained primarily contain 10 to 35% by weight of capsules. They need something to cream as long as they do not contain any binding agent. This can be used for concentration. The preferred capsule size is around 10 µm. The homogenized capsule suspensions, provided with binders and optionally inert fillers such as talc or kaolin, can be applied manually with a floral wire squeegee or mechanically with an air brush in application quantities of 4-8 91 m 2 on base paper (for example from 40 to 100 g / m 2 ). The coating of base papers is described in German Offenlegungsschriften 1,934,457 and 1,955,542. The papers coated in this way contain the first color-forming component; they are called encoder components.

Die Geberkomponente ist im allgemeinen bei Durchschreibesätzen die Rückseite des obersten Blattes. Die Vorderseite des nächsten Blattes ist mit der zweiten Farbgeberkomponente beschichtet. Man bezeichnet diese Schicht als Nehmerkomponente. Bei Durchschreibesätzen ist die Nehmerkomponente die Oberseite des zweiten Papierblattes. Bei Mehrfachdurchschriebesätzen müssen die folgenden Geberblätter auf der Gegenseite eine Nehmerbeschichtung tragen. Die Herstellung solcher Nehmerschichten ist bekannt und ebenfalls in den Deutschen Offenlegungsschriften 1.934.457 und 1.955.542 beschrieben.The donor component is generally the back of the top sheet for carbonless sets. The front of the next sheet is coated with the second coloring component. This layer is called the slave component. In the case of carbonless copies, the slave component is the top of the second sheet of paper. In the case of multiple copy sets, the following encoder sheets must have a slave coating on the opposite side. The production of such receiver layers is known and is also described in German Offenlegungsschriften 1,934,457 and 1,955,542.

Beispiel 1example 1 (a) Herstellung des wendbildenden Materials(a) Manufacture of the turning material

2000 g n-Hexan-1,6-diisocyanat werden in einem 2,7 1 Autoklaven mit 1 g Tri-p-tolylarsinoxid versetzt und 8 Stunden bei einem CO2-Druck von 3 atü bei 50°C gerührt.2000 g of n-hexane-1,6-diisocyanate are mixed with 1 g of tri-p-tolylarsine oxide in a 2.7 l autoclave and stirred at 50 ° C. for 8 hours at a CO 2 pressure of 3 atm.

Hierbei werden 17,5 I Kohlendioxid aufgenommen. Die Reaktion wird durch Zugabe von 2 g Phosphortrichlorid unterbrochen und das Reaktionsprodukt von nicht umgesetztem Ausgangsprodukt im Dünnschichverdampfer abgetrennt (2-maliger Durchgang, Heiztemperatur 180°C bei 1 Torr).Here 17.5 l of carbon dioxide are absorbed. The reaction is interrupted by adding 2 g of phosphorus trichloride and the reaction product is separated from the unreacted starting product in a thin-layer evaporator (two passes, heating temperature 180 ° C. at 1 torr).

Man erhält 1957 g Oxadiazinon mit einem NCO-Wert von 19,0% und einer Viskosität von 2480 cp/50°C.1957 g of oxadiazinone with an NCO value of 19.0% and a viscosity of 2480 cp / 50 ° C. are obtained.

Das IR-Spektrum zeigt die charakteristischen Carbonyl-Absorptionsbanden bei 5,5 bis 5,71 und 5,82 ,um.The IR spectrum shows the characteristic carbonyl absorption bands at 5.5 to 5.71 and 5.82 µm.

(b) Verkapselung(b) encapsulation

In 25 g Solventnaphtha (Aromatengemisch der BV Aral aus Xylol, Cumol, Tuluol und weiteren Naphthenölen) werden unter Rühren und Erwärmen auf 70°C 0,75 g Kristallviolettlacton und 0,25 g N-Benzoyl-leukomethylenblau gelöst.0.75 g of crystal violet lactone and 0.25 g of N-benzoyl-leukomethylene blue are dissolved in 25 g of solvent naphtha (BV Aral's aromatic mixture of xylene, cumene, tuluene and other naphthenic oils) with stirring and heating to 70 ° C.

Nach dem Abkühlen der Lösung werden 5 g des unter Beispiel 1 (a) beschriebenen Oxadiazinons zugegeben und gelöst.After the solution has cooled, 5 g of the oxadiazinone described in Example 1 (a) are added and dissolved.

Die homogene organische Phase wird anschließend in 300 g Wasser emulgiert, welches 1,5 g. Mowiol 56-98 (Polyvinylalkohol der Hoechst AG) als Emulgierhilfsmittel enthält.The homogeneous organic phase is then emulsified in 300 g of water, which is 1.5 g. Mowiol 56-98 (polyvinyl alcohol from Hoechst AG) as an emulsifying agent.

Zum Emulgieren wird eine Kotthoff-Mischsirene verwendet (8900 U/Min., 1 I Becherglas).A Kotthoff mixing siren is used for emulsification (8900 rpm, 1 l beaker).

Nach ca. 1 Min. Emulgierzeit wird die Mischsirene durch einen Laborrührer vom Typ Lenart-Rapid ersetzt (500 U/Min.). Gleichzeitig wird dem Ansatz eine Lösung von 0,7 g 1-Aminoäthyläthylen-diamin-1,2-(Diäthylentriamin) in 70 g Wasser zugestezt. Unter stetigem Rühren wird der Ansatz schnell auf 70°C erwärmt und ca. 1 Std. auf dieser Temperatur gehalten. Die Heizphase dient lediglich der Ausbildung einer möglichst stabilen Hülle.After an emulsification time of approx. 1 minute, the mixing siren is replaced by a Lenart-Rapid laboratory stirrer (500 rpm). At the same time, a solution of 0.7 g of 1-aminoethylethylenediamine-1,2- (diethylenetriamine) in 70 g of water is added to the batch. With constant stirring, the batch is quickly heated to 70 ° C. and kept at this temperature for about 1 hour. The heating phase is only used to form a casing that is as stable as possible.

Der Durchmesser der resultierenden Mikrokapseln liegt in der Größenordnung von 3-25 µm.The diameter of the resulting microcapsules is in the order of 3-25 µm.

Beispiel 2Example 2

Die organische Phase wird, wie unter Beispiel 1 (b) beschrieben, hergestellt mit der Änderung, daß als Lösungsmittel 25 g Solvesso 200 (Aromatengemisch der Esso AG) eingesetzt werden.The organic phase is prepared as described in Example 1 (b) with the change that 25 g of Solvesso 200 (aromatic mixture from Esso AG) are used as the solvent.

Die Verkapselung und Nachbehandlung wird ebenfalls, wie unter Beispiel 1 (b) beschrieben, durchgeführt mit der Änderung, daß der äußeren Phase 0,7 g Äthylendiamin in 70 g Wasser als Aminkomponente zugegeben werden.The encapsulation and aftertreatment is also carried out as described in Example 1 (b), with the change that 0.7 g of ethylenediamine in 70 g of water are added as the amine component to the outer phase.

Die Mikrokapseln fallen in einer Größe von 3-25 ,um an.The microcapsules are 3-25 µm in size.

Beispiel 3Example 3

In 25 g Phthalsäure-di-n-butylester werden 0,75 g p-Toluolsulfinat von Michlers Hydrol als farbgebende Komponente unter Rühren und Erwärmen auf 80°C gelöst.0.75 g of p-toluenesulfinate from Michlers Hydrol as the coloring component is dissolved in 25 g of phthalic acid di-n-butyl ester with stirring and heating to 80 ° C.

Nach Abkühlen der Lösung werden 5 g des unter Beispiel 1 (a) beschriebenen Oxadiazinons zugegeben und gelöst.After the solution has cooled, 5 g of the oxadiazinone described in Example 1 (a) are added and dissolved.

Die resultierende organische Phase wird, wie unter Beispiel 1 (b) beschrieben, verkapselt und nachbehandelt. Als Aminkomponente werden 0,7 g Diäthylentriamin in 70 g Wasser eingesetzt.The resulting organic phase is encapsulated and post-treated as described in Example 1 (b). 0.7 g of diethylenetriamine in 70 g of water are used as the amine component.

Die resultierenden Mikrokapseln haben Durchmesser von 2-20 µm.The resulting microcapsules have a diameter of 2-20 µm.

Beispiel 4Example 4 (a) Herstellung des wandbildenden Materials(a) Manufacture of the wall-forming material

280 g 1,4-Tetramethy)en-diisocyanat werden durch Einleiten mit trockenem CO2-Gas gesättigt und unter Rühren und weiterem Einleiten von Kohlendioxid bei 60°C mit 0,7 g Tri-n-butyl-phosphin (0,25%) versetzt. Nach 2 Stunden ist der NCO-Wert auf 53,8% gefallen. Die Reaktionsmischung wird in einem Dünnschichtverdampfer (Heiztemperatur 180°C bei 1 Torr) getrennt, wobei 219 g 1,4-Tetramethylendiisocyanat zurückgewonnen und 54 g eines dickflüssigen Oles erhalten werden. Dieses zeigt die für isocyanatgruppenhaltige Oxadiazintrione charakteristischen Banden im IR-Spektrum (4,4; 5,48; 5,71; 5,83; 6,93; 7,06 ,um), weist einen NCO-Wert von 20,2% auf und ein Molekulargewicht von 375.280 g of 1,4-tetramethylene) diisocyanate are saturated by introducing them with dry CO 2 gas and, with stirring and further introducing carbon dioxide at 60 ° C., with 0.7 g of tri-n-butylphosphine (0.25% ) offset. After 2 hours, the NCO value has dropped to 53.8%. The reaction mixture is separated in a thin-film evaporator (heating temperature 180 ° C. at 1 torr), 219 g of 1,4-tetramethylene diisocyanate being recovered and 54 g of a viscous oil being obtained. This shows the bands characteristic of isocyanate group-containing oxadiazinetriones in the IR spectrum (4.4; 5.48; 5.71; 5.83; 6.93; 7.06 µm), and has an NCO value of 20.2% on and a molecular weight of 375.

(b) Verkapselung(b) encapsulation

In 25 g einer Mischung aus 70 Teilen Santosol 340 (teilhydriertes Terphenyl der Firma Monsanto) und 30 Teilen Solvesso 200 (Aromatengemisch der Esso AG) werden 1,1 g Kristallviolettlacton bei einer Temperatur von 80°C unter Rühren gelöst.In 25 g of a mixture of 70 parts of Santosol 340 (partially hydrogenated terphenyl from Monsanto) and 30 parts of Solvesso 200 (aromatic mixture from Esso AG), 1.1 g of crystal violet lactone are dissolved at a temperature of 80 ° C. with stirring.

Nach dem Abkühlen der Lösung werden 5 g des unter 4 (a) beschriebenen Oxadiazinons zugegeben und gelöst. Die Lösung, die die organische Phase darstellt, wird anschließend in 150 g Wasser emulgiert, das 0,75% Mowiol 26-88 (Polyvinylalkohol der Hoechst AG) als Emulgierhilfsmittel enthält. Zum Emulgieren wird eine Kotthoff-Mischsirene verwendet (8900 U/Min., 500 ml Becherglas, Rührzeit ca. 1 Minute). Nach dem Emulgieren wird dem Ansatz eine Lösung von 0,9 g 1-Aminoäthyläthylendiamin-1,2 (Diäthylentriamin) in 50 g Wasser zugesetzt und anschließend die Mischsirene durch einen Laborrührer vom Typ Lenart-Rapid (500 U/min.) ersetzt. Die Nachrührzeit beträgt ca. 1 Std. bei 60°C.After the solution has cooled, 5 g of the oxadiazinone described under 4 (a) are added and dissolved. The solution, which is the organic phase, is then emulsified in 150 g of water which contains 0.75% Mowiol 26-88 (polyvinyl alcohol from Hoechst AG) as an emulsifying aid. A Kotthoff mixing siren is used for emulsification (8900 rpm, 500 ml beaker, stirring time approx. 1 minute). After the emulsification, a solution of 0.9 g of 1-aminoethylethylenediamine-1,2 (diethylenetriamine) in 50 g of water is added to the mixture, and the mixing siren is then replaced by a Lenart-Rapid laboratory stirrer (500 rpm). The stirring time is approx. 1 hour at 60 ° C.

Die Mikrokapsein fallen mit einem Durchmesser von 1-35 µm an.The microcapsules are obtained with a diameter of 1-35 µm.

Beispiel 5Example 5

Die Herstellung einer Mikrokapsel-Dispersion mit ca. 30% Kapselanteil läßt sich mit Hilfe eines Ultraschall-Homogenisators (Typ Minisonic der Fa. Ultrasonics) mit einer Lösung von 4,5 Teilen Kristallviolettlacton und 17 Teilen des unter Beispiel 1 (b) beschreibenen Oxadiazinons in 75 Teilen Santosol 340 (teilhydriertes Terphenyl der Fa. Monsanto und 25 Teilen Solvesso 100 (Esso AG) als organische Phase durchführen.A microcapsule dispersion with about 30% capsule content can be produced with the aid of an ultrasound homogenizer (type Minisonic from Ultrasonics) with a solution of 4.5 parts of crystal violet lactone and 17 parts of the oxadiazinone described in Example 1 (b) Perform 75 parts of Santosol 340 (partially hydrogenated terphenyl from Monsanto and 25 parts of Solvesso 100 (Esso AG) as the organic phase.

Zur Emulgierung werden 150 Teile der organischen Phase auf 250 Teil wäßrige Phase eingesetzt. Die wäßrige Phase enthält 0,5% Mowiol 26-88 und 0,1% Tween 80 (Emulgator der Fa. Atlas Chemie) als Emulgierhilfsmittel.150 parts of the organic phase to 250 parts of aqueous phase are used for emulsification. The aqueous phase contains 0.5% Mowiol 26-88 and 0.1% Tween 80 (emulsifier from Atlas Chemie) as an emulsifying aid.

Insgesamt werden die beiden Phasen bzw. die hieraus hergestellte Emulsion 5mal durch den Ultraschall-Homogenisator gegeben. Unmittelbar anschließend wird die resultierende Emulsion in ein Becherglas überführt und unter Rühren mit einem Laborrührer (Typ Lenart-Rapid, 500 U/Min.) zügig mit der dem NCO-Wert des eingesetzten Oxadiazinons stöchiometrisch entsprechenden Menge Äthylendiamin versetzt (als wäßrige 4%ige Lösung).In total, the two phases or the emulsion produced therefrom are passed 5 times through the ultrasonic homogenizer. Immediately afterwards, the resulting emulsion is transferred to a beaker and swiftly stirred with a laboratory stirrer (type Lenart-Rapid, 500 rpm) the amount of ethylenediamine corresponding to the NCO value of the oxadiazinone used stoichiometrically added (as an aqueous 4% solution).

Die entstehende Mikrokapseldispersion wird bei Raumtemperatur ca. 1 Std. nachgerührt. Die erhaltenen Mikrokapseln liegen im Bereich von 1-30 ,um Durchmesser.The resulting microcapsule dispersion is stirred at room temperature for about 1 hour. The microcapsules obtained are in the range of 1-30 µm in diameter.

Beispiel 6Example 6

In 25 g Benzoesäureäthylester werden unter Rühren und Erwärmen auf 80°C 0,75 g p-Toluolsulfinat von Michlers Hydrol gelöst.0.75 g of p-toluenesulfinate from Michlers Hydrol is dissolved in 25 g of ethyl benzoate with stirring and heating to 80 ° C.

Nach Erkalten des Ansatzes werden 5 g des unter Beispiel 1 (a) beschriebenen Oxadiazinons zugelöst.After the mixture has cooled, 5 g of the oxadiazinone described in Example 1 (a) are added.

Die resultierende organische Phase wird mit Hilfe einer Kotthoff-Mischsirene bei 8900 U/Min. in 300 g Wasser emulgiert, welches 0,5% Mowiol 56-98 als Emulgierhilfsmittel enthält.The resulting organic phase is with the aid of a Kotthoff mixing siren at 8900 rpm. emulsified in 300 g of water, which contains 0.5% Mowiol 56-98 as an emulsifying aid.

Nach ca. 40 Sek. Mischzeit wird dem Ansatz eine Lösung von 0,7 g Diäthylentriamin in 70 g Wasser zugegeben. Nach ca. 1 Min Emulgierzeit wird die Mischsirene durch einen Laborrührer ersetzt (Typ Lenart-Rapid, 500 U/Min.) und die Mikrokapseldispersion ca. 1 Std. unter Rühren auf 70°C gehalten.After a mixing time of about 40 seconds, a solution of 0.7 g of diethylenetriamine in 70 g of water is added to the mixture. After about 1 minute of emulsification, the mixing siren is replaced by a laboratory stirrer (Lenart-Rapid type, 500 rpm) and the microcapsule dispersion is kept at 70 ° C. for about 1 hour with stirring.

Die Mikrokapseln besitzen Durchmesser von 3-25 ,um.The microcapsules have a diameter of 3-25 µm.

Claims (2)

1. Pressure-sensitive copying paper, which contains a solution of a dye-precursor agent in micro- encapsulated form, wherein the dye-precursor agent is encapsulated as a solution in a hydrophobic organic solvent, characterised in that the capsule walls consist of the polyaddition product of a diisocyanate of the formula I
Figure imgb0007
wherein
R denotes an alkylene radical having from 2 to 10 carbon atoms

and a diamine.
2. Use of microcapsules containing as core material a solution of a dye-precursor agent in a hydrophobic organic solvent, the walls of which microcapsules consist of the polyaddition product of a diisocyanate of the formula I
Figure imgb0008
wherein
R denotes an alkylene radical having from 2 to 10 carbon atoms

and a diamine, for the production of pressure-sensitive copying papers.
EP78100634A 1977-08-26 1978-08-09 Carbonless copying paper and manufacture thereof Expired EP0000903B1 (en)

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DE2738509 1977-08-26
DE19772738509 DE2738509A1 (en) 1977-08-26 1977-08-26 RESPONSE COPY

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EP0000903A3 EP0000903A3 (en) 1979-03-21
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JP (1) JPS5444919A (en)
BR (1) BR7805520A (en)
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DE2909950A1 (en) * 1979-03-14 1980-10-02 Bayer Ag MICROCAPSULES
DE2930408A1 (en) * 1979-07-26 1981-02-12 Bayer Ag REACTION COVER PAPER
DE3020148A1 (en) 1980-05-28 1981-12-03 Bayer Ag, 5090 Leverkusen CONCENTRATED MICROCAPSULE SUSPENSIONS FOR REACTION COPY PAPERS
JPS5777589A (en) * 1980-11-04 1982-05-14 Mitsubishi Paper Mills Ltd Capsule sheet for non-carbon copying
DE3623413A1 (en) * 1986-07-11 1988-01-14 Basf Ag COMPOSITE LAYER
JPS6312582U (en) * 1986-07-11 1988-01-27
US5225118A (en) * 1990-08-15 1993-07-06 Boise Cascade Corporation Process for manufacturing polyurea microcapsules and product therefrom
JP2729538B2 (en) * 1991-02-13 1998-03-18 富士写真フイルム株式会社 Manufacturing method of microcapsules
US5164126A (en) * 1991-03-05 1992-11-17 Appleton Papers Inc. Process for microencapsulation
EP0505648B1 (en) * 1991-03-28 1994-06-15 Dainippon Ink And Chemicals, Inc. Microcapsules, encapsulation method therefor, and method of use thereof
EP0573210B2 (en) * 1992-06-04 2005-11-23 Arjo Wiggins Limited Pressure-sensitive record material
GB9522233D0 (en) * 1995-10-31 1996-01-03 Wiggins Teape Group The Limite Pressure-sensitive copying paper
DE19840583A1 (en) 1998-09-05 2000-03-09 Bayer Ag Microcapsule formulations
US6653256B1 (en) 1999-08-24 2003-11-25 Bayer Aktiengesellschaft Microcapsule formulations
KR100514904B1 (en) * 2002-11-18 2005-09-14 한국전자통신연구원 Method for decreasing control information corresponding to modulation and coding scheme on orthogonal frequency division multiple access/frequency division duplex
HUE038015T2 (en) * 2006-03-30 2018-09-28 Fmc Corp Acetylene carbamide derivatives-polyurea polymers and microcapsules and formulations thereof for controlled release
EP2479552B1 (en) * 2007-04-02 2015-09-02 Acoustic Cytometry Systems, Inc. Methods for enhanced analysis of acoustic field focused cells and particles
CN104829976A (en) * 2015-05-27 2015-08-12 陕西科技大学 Method for manufacturing composite dielectric materials from polyvinylidene fluoride and end carboxyl multi-walled carbon nano-tubes

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CH453305A (en) * 1963-10-21 1968-06-14 Pilot Pen Co Ltd Process for encapsulating fine droplets of dispersed liquids
US3432327A (en) * 1964-03-13 1969-03-11 Pilot Pen Co Ltd Pressure sensitive copying sheet and the production thereof
US3748329A (en) * 1970-07-08 1973-07-24 Bayer Ag Compounds containing the 2,4,6-triketo-1,3,5-oxadiazine ring
US3886085A (en) * 1971-08-31 1975-05-27 Fuji Photo Film Co Ltd Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby
BE790373A (en) * 1971-10-21 1973-02-15 Fuji Photo Film Co Ltd PRESSURE SENSITIVE RECORDING SHEET CONTAINING MICRO-CAPSULES WITH POLYURIDE WALLS
DE2221756C3 (en) * 1972-05-04 1980-06-26 Bayer Ag, 5090 Leverkusen Process for the production of solvent-resistant, lightfast, kink and friction-resistant polyurethane coatings on textile substrates, leather or synthetic leather or foils

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DK145888B (en) 1983-04-05
EP0000903A3 (en) 1979-03-21
IT7850838A0 (en) 1978-08-24
DE2738509A1 (en) 1979-03-08
JPS5444919A (en) 1979-04-09
US4253682A (en) 1981-03-03
DE2861546D1 (en) 1982-03-04
DK377578A (en) 1979-02-27
IL55416A (en) 1982-01-31
IL55416A0 (en) 1978-10-31
EP0000903A2 (en) 1979-03-07
DK145888C (en) 1983-09-19
BR7805520A (en) 1979-04-17
CA1121159A (en) 1982-04-06
JPS5647874B2 (en) 1981-11-12

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