DE1245320B - Making small capsules - Google Patents

Making small capsules

Info

Publication number
DE1245320B
DE1245320B DEN17701A DEN0017701A DE1245320B DE 1245320 B DE1245320 B DE 1245320B DE N17701 A DEN17701 A DE N17701A DE N0017701 A DEN0017701 A DE N0017701A DE 1245320 B DE1245320 B DE 1245320B
Authority
DE
Germany
Prior art keywords
coacervation
dispersion
capsules
liquid
colloid
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.)
Pending
Application number
DEN17701A
Other languages
German (de)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NCR Voyix Corp
Original Assignee
NCR Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NCR Corp filed Critical NCR Corp
Publication of DE1245320B publication Critical patent/DE1245320B/en
Pending legal-status Critical Current

Links

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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • 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
    • B01J13/08—Simple coacervation, i.e. addition of highly hydrophilic material
    • 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
    • B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
    • 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]
    • 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
    • Y10T428/2987—Addition polymer from unsaturated monomers only
    • 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.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]

Description

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Deutsche KlGerman class

Nummer
Aktenzeichen
Anmeldetag
Auslegetagnumber
File number
Filing date
Display day

12c-312c-3

1 245 320
N17701IVC/12C
29 Dezember 1959
27 Juh 19671 245 320
N17701IVC / 12C
29 December 1959
27 June 1967

XJ 1*-Λ f* Λ XJ 1 * -Λ f * Λ

Erfindungsgegenstand ist ein Verfahren zum Herstellen von kleinen Kapseln mit einem in Wasser unlöslichen Kern, der durch Koazervteren einer Emulsion oder Dispersion eines wässerigen Sols mit einem hydrophilen Kolloid umhüllt wird Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß man wie üblich die Koazervierung einleitet, sodann unterbricht, überschüssiges Kolloid dekoazerviert und nach Zusetzen weiteren Kolloids wieder koazervieitThe subject matter of the invention is a method of production of small capsules with a water-insoluble core that coacerves an emulsion or dispersion of an aqueous sol is coated with a hydrophilic colloid The method is characterized in that the coacervation is initiated as usual, then interrupts, decoacerves excess colloid and coacerve again after adding more colloids

Das eifindungsgemaße Verfahren besteht im ersten Schritt in der Ablagerung eines filmbildend en hydrophilen Kolloids in einer wasserigen Lösung durch Koazervierung auf den weitgehend in Wasser unlöslichen kleinsten Teilchen, die die in der genannten Losung dispergierten Kerne bilden, welche entweder flussig oder fest oder Dispersionen eines festen pulverisierten Stoffes in emei Flüssigkeit sein können V01 der zweiten Ablagerung ist es notwendig daß der pH-Wert der reaktivierten wässerigen Losung und lhier Bestandteile über dem Koazervierungsbereich hegt, damit die Koazervierung mcht zu früh erfolgt Die Vorbereitung der wasserigen Losung zur zweiten Ablagerung wird durch Zusetzen von weiterem filmbildenden hydrophilen Kolloid erreicht, wobei dei pH-Wert der Losung über dem Koazervierungsbereich hegt, wodurch das zugesetzte filmbildende hydrophile Kolloid untei diesen Bedingungen die geeigneten Voraussetzungen fur eine Koazei vierung schafft Die Erfindung bezieht sich nicht auf die Bildung von Kapseln, deren Kern aus verschiedenen Stoffen bestehtThe method according to the invention consists in the first Step in the deposition of a film-forming hydrophilic colloid in an aqueous solution Coacervation on the largely insoluble in water smallest particles that form the nuclei dispersed in said solution, which either Liquid or solid or dispersions of a solid powdered substance in a liquid can be V01 the second deposit it is necessary that the pH of the reactivated aqueous solution and Here components over the coacervation area so that the coacervation does not occur too early The preparation of the aqueous solution for the second Deposition is formed by adding further film-forming hydrophilic colloid, with the pH of the solution above the coacervation range which makes the added film-forming hydrophilic colloid suitable under these conditions Die creates the prerequisites for co-operation The invention does not relate to the formation of capsules, the core of which consists of different substances

Die kernbildenden Stoffe, die fur das erfindungsgemaße Verfahren geeignet sind, unterscheiden sich mcht nur durch ihre Zustandsform, da sie fest oder flüssig oder eine Kombmation aus festen und flussigen Stoffen sein können, sondern sie sind eveniuell auch von unterschiedlicher chemischer Zusammensetzung und fur mannigfache Verwendungszwecke geeignet. Beispiele sind Nahrungsmittel, Medikamenie, Brennstoffe, Farbemittel, chemische Reaktanzen, dielektrische und magnetische Stoffe und Parfüms odei Riechstoffe Feste, als Keine verwendbare Stoffe sind ζ B magnetische Materialien wie magnetisches Eisenoxyd, pulverformige, größtenteils in Wassei unlösliche anorganische und organische chemische Verbindungen, elektrostatische Materialien wie ζ Β Druckerschwarze-Pigment und Eisenpulver, und Kombinationen aus solchen Materialien Weiter seien genannt Mineralole, pflanzliche und tierische Öle, synthetische, durch Modifikation naturlicher Öle hergestellte Öle oder Öle rein synthetischen UrsprungsThe nucleus-forming substances that are necessary for the inventive Processes are suitable, may differ only in their state, as they are solid or liquid or a combination of solid and liquid Substances can be, but they may also be of different chemical composition and suitable for a variety of purposes. Examples are food, medicines, fuels, Dyes, chemical reactances, dielectric and magnetic substances and perfumes or the like Fragrances Solid substances that cannot be used are ζ B magnetic materials such as magnetic iron oxide, powdery, mostly insoluble in water inorganic and organic chemical compounds, electrostatic materials such as ζ Β printer black pigment and iron powder, and combinations of such materials. vegetable and animal oils, synthetic oils produced by modifying natural oils or Oils of purely synthetic origin

Die gelierten und erstarrten, dickwandigen Kapseln können, wenn gewünscht, mit in Wasser loslichen Herstellen kleiner KapsemThe gelled and solidified, thick-walled capsules can, if desired, also dissolve in water Making small capsules

AnmelderApplicant

The National Cash Register Company,The National Cash Register Company,

Dayton, Ohio (V St A )Dayton, Ohio (V St A)

Vertreterrepresentative

Dr A Stappert, Rechtsanwalt,Dr A Stappert, lawyer,

Dusseldorf, Feldstr 80Dusseldorf, Feldstrasse 80

Beanspruchte Pnontat
V St ν Amerika vom 31 Dezember 1958
(784 020)Claimed Pnontat
V St ν America of December 31, 1958
(784 020)

Weichmachein, wie Athylenglykol oder äquivalenten Stoffen, die äußerlich angewandt werden, en eicht werdenPlasticizers such as ethylene glycol or equivalent Materials that are used externally are calibrated

Bei der Herstellung von Kapseln mit flussigem Kern kann die Tropfengroße des flussigen Kernes, wie nachfolgend beschrieben, durch die Art des Dispergierens der Flüssigkeit m der wässerigen Losung bestimmt werden, wodurch die Gesamtgroße bereits beeinflußt wird Feste Stoffe in Pulverfoim, die zu Kernen verwendet werden sollen, können durch Sieben auf die gewünschte Große gebracht werdenWhen making capsules with liquid Core can be the droplet size of the liquid core, as described below, through the type of dispersion the liquid m the aqueous solution can be determined, whereby the total size is already influenced Cores to be used can be brought to the desired size by sieving

Es ist bereits bekannt, Mikrokapseln in großen Mengen durch Komplexkoazervierung in einem wässerigen Sol filmbildender Kolloide herzustellen, in denen Tropfen eines Ols dispergiert worden sind Bei der Koazervierung nehmen die Koloide entgegengesetzte elektrische Ladungen an und scheiden sich von der Losung als Komplexe ab, die sich an den Oltropfchen ablagern, die wie Kondensationskerne wirken Die verhältnismäßig niedrige Viskosität der Koazervatphase und die sich aus der bestandigen Bewegung des Systems ergebenden Scherkräfte begrenzen die Dicke der Kapselwande, die noch ihr Kernmaterial einschließen können, so daß die maximale mittels dieses Verfahiens erzielbare Kapselgroße zwischen 2 bis 5 μτη fur einzelne Kapsem und bei 15 (xm fur Kapseltrauben liegtIt is already known to take large microcapsules Quantities by complex coacervation in an aqueous To produce sol of film-forming colloids, in which drops of an oil have been dispersed at the coloids take opposite of coacervation electric charges and separate from the solution as complexes, which are attached to the Deposit oil droplets, which act like condensation nuclei. The relatively low viscosity of the Coacervate phase and that result from the persistent Limit movement of the system resulting in shear forces the thickness of the capsule walls that are still their core material so that the maximum capsule size attainable by this process between 2 to 5 μm for individual capsules and for 15 (xm for capsule grapes

Die standigen Bemühungen, die Kapselgroße und die Wanddicke bei der Massenfertigung zu erhohen, resultierten in dem Vorschlag, doppelwandige Kapsem herzustellen Das altere deutsche Patent 1096 0:
beansprucht ein Verfahren, bei dem kleine Oltrop!The constant efforts to increase the capsule size and the wall thickness in mass production resulted in the proposal to manufacture double-walled capsules. The older German patent 1096 0:
claims a process in which little Oltrop!

709 61i709 61i

zuerst unter Bildung einer festen Polymerhulle durch Polymerisation eines flussigen Monomers eingekapselt und die so erhaltenen Kapseln als Kerne fur eine nachfolgende zweite Einkapselung mittels Koazeivierung verwendet werden Gegenstand des alteren deutschen Patents 1185155 ist ein Verfahren, bei dem eine hydrophobe Schicht um Kernstuckchen gelegt und die beschichteten Stuckchen unter Koazervieiung mittels eines hydrophilen polymeren Materials eingekapselt werdenfirst to form a solid polymer shell Polymerization of a liquid monomer encapsulated and the capsules obtained in this way as cores for a subsequent second encapsulation by means of coazeivation The subject of the older German patent 1185155 is a method in which a hydrophobic layer is placed around core pieces and the coated pieces under coacervation be encapsulated by means of a hydrophilic polymeric material

Ein Verfahren, bei dem zwei verschiedene Emkapselungsschntte notwendig sind, ist zweifellos nachteilig, da es zwei Emkapselungssysteme benotigt mit all den umständlichen Schritten des Waschens und Überfuhrens der embryonalen Kapseln von dem einen System m das andereA process in which two different encapsulation steps is undoubtedly a disadvantage, as it requires two encapsulation systems all the cumbersome steps of washing and transferring the embryonic capsules from one System m the other

Überraschenderweise hat sich nun gezeigt, daß festere Kapselwande in einem einzigen Fertigungssystem hergestellt werden können, was eine Massenfertigung von Kapsem bis zu einer Große von 5 mm mittels Koazervierung einer Emulsion oder Dispersion eines wasserigen Sols eines hydrophilen Kolloids ermöglicht, wenn gemäß der Erfindung die Koazervierung in üblicher Weise eingeleitet, dann jedoch unterbrochen und das überschüssige Kolloid dekoazerviert und nach Zusetzen weiteren Kolloids nochmals koazerviert wird.Surprisingly, it has now been shown that stronger capsule walls can be manufactured in a single manufacturing system, resulting in mass production from capsules up to a size of 5 mm by means of coacervation of an emulsion or dispersion of an aqueous sol of a hydrophilic colloid enables coacervation according to the invention initiated in the usual way, but then interrupted and the excess colloid decoacervated and after adding more colloids, it is coacervated again.

Wenn in einem komplexen wasserigen Sol durch Koazeivierung, ζ B. unter Reduzieren des pH-Wertes des Sols, entgegengesetzte Ladungen in den verschiedenen Kolloiden hervorgerufen werden, dann scheiden sich die Kolloide aus der Losung ab, und es bildet sich eine kolloidreiche komplexe Phase, m der die beiden Kolloide als Komplexe zusammengeführt sind Dieser Vorgang ist reversibel, und beim Anheben des pH-Wertes des Sols trennen sich die komplexen Einheiten, und die Kolloide gehen wieder in Losung Hier soll der Ausdruck »Dekoazervierung« diese Umkehrung des Koazervierungsvorgangs bezeichnen, bei dem em Teil der komplexen Koazervatphase sich aufspaltet und wieder m flussige Phase übergehtIf through in a complex watery sol Coazivation, ζ B. reducing the pH of the sol, opposite charges in the different Colloids are produced, then the colloids separate from the solution and it forms a colloid-rich complex phase, m of the both colloids are merged as complexes. This process is reversible, and when lifting the pH value of the sol, the complex units separate, and the colloids go back into solution here the term "decoacervation" is intended to denote this reversal of the coacervation process in which em Part of the complex coacervate phase splits up and passes back into the liquid phase

Beispielexample

150 g eines llgewichtsprozentigen wasserigen GeIatmesols, 150 g eines llgewichtsprozentigen wasserigen Gummiarabikumsols und 40 g emei 2gewichtsprozentigen wasserigen Dispersion von kopolymerem PoIyathylenmalemsaureanhydrid mit einem Molekulargewicht zwischen etwa 1000 bis 2000 werden 1500 ecm Wasser zugesetzt und der pH-Wert der Dispersion auf 9 eingestellt Zu dieser auf 35 0C erwärmten und in Bewegung gehaltenen Dispersion werden tropfenweise 50 g η-Dekan zugefugt, wobei die Tropfengroße etwa mit 500 μηι bemessen wird150 g of a 11 weight percent aqueous gel mesol, 150 g of a 11 weight percent aqueous gum arabic sol and 40 g of a 2 weight percent aqueous dispersion of copolymeric polyethylene maleic anhydride with a molecular weight between about 1000 and 2000 are added 1500 ecm of water and the pH of the dispersion is adjusted to 9 The dispersion, heated to 0 C and kept in motion, is added dropwise to 50 g of η-decane, the size of the droplets being approximately 500 μm

Der pH-Wert der Dispersion wird duich Zusetzen einer lOgewichtsprozentigen wasserigen Losung von Essigsaure auf etwa 4,8 abgesenkt, hierdurch wird die Koazervierung eingeleitet, und das komplexe Kolloidmatenal lagert sich auf den n-Dekan-Tropfchen ab und bildet flussige Wände um diese Bei der genannten Konzentration ergibt sich eine Wanddicke von etwa 5 μηι, worauf die Ablagerung aufhört, obgleich noch überschüssiges Wandmatenal in Form von Koazervattropfchen unabgelagert in der Dispersion vorhanden istThe pH of the dispersion will be added a 10 weight percent aqueous solution of Acetic acid lowered to about 4.8, this will reduce the Coacervation initiated and the complex colloid material is deposited on the n-decane droplets and forms liquid walls around these Concentration results in a wall thickness of about 5 μm, whereupon the deposition stops, although still Excess wall material in the form of coacervate droplets is not deposited in the dispersion

Nun wird der pH-Wert fur kurze Zeit durch Zusetzen einer lOgewichtsprozentigen wassengen Losung von Natriumhydroxyd auf 6,8 angehoben, was eine Dekoazervierung m der Dispersion zur Folge hat, bei der das überschüssige komplexe Material in seinen anfänglichen, nicht komplexen Zustand zurückkehrt, die Dispersion wird nun durch Zusetzen einer 2gewichtsprozentigen wasserigen Dispersion von 40 g kopolymerem Polyathylenmaleinsaureanhydnd mit einem Molekulargewicht von etwa 60 000 bis 70 000 ergänztNow the pH is adjusted for a short time by adding a 10 weight percent wassengen solution of sodium hydroxide raised to 6.8, which is a Dekoacervierung m the dispersion has the consequence, in which the excess complex material in his the initial, non-complex state returns, the dispersion is now achieved by adding a 2 weight percent aqueous dispersion of 40 g copolymer polyethylene maleic anhydride with a molecular weight of about 60,000 to 70,000

Unter fortgesetztem Ruhren wird nun durch Senken des pH-Wertes auf etwa 5 m der vorstehend genannten Weise die Koazervierung wiedei eingeleitet, das neu zugesetzte kopolymeie Polyathylenmaleinsaureanhydnd und das überschüssige, anfangs zugesetzte Wandmatenal lagern sich nun als komplexe Einheiten als eine zweite flussige Wand um die teilweise fertigen Kapseln Die zweite flussige Wand haftet an dei ersten, und es ergeben sich Kapselwande mit einer Starke von etwa 100 μπι beim Aufhören der zweiten Ablagerung. With continued agitation it is now caused by lowering of the pH to about 5 m in the above-mentioned manner, the coacervation is initiated again, the new added copolymeie polyethylene maleic anhydride and the excess wall material added at the beginning are now stored as complex units as a second liquid wall around the partially finished Capsules The second liquid wall clings to the first and capsule walls with a thickness of about 100 μm result when the second deposition ceases.

Die Temperatur der Dispersion wird nun auf 13°C gesenkt, um die Kapselwande durch Gelatinierung zu festigen Zur Härtung der Kapselwande durch Vernetzen werden 0,19 ecm eines 37gewichtsprozentigen wasserigen Formaldehyds pro Gramm Gelatine zugefugt. The temperature of the dispersion is now at 13 ° C lowered to strengthen the capsule walls through gelatinization. To harden the capsule walls through crosslinking become 0.19 ecm of a 37 weight percent aqueous formaldehyde added per gram of gelatin.

Die so gebildeten Kapseln können aus der wassengen Trageiflussigkeit durch Filtrieren, Zentrifugieren oder durch Sprühtrocknen in einem vorzugsweise heißen Gasmedmm gewonnen werden Wenn sie dann trocken sind, ergibt sich ein gebrauchsfertiger pulverisierter fester StoffThe capsules formed in this way can be removed from the water Carry out liquid by filtering, centrifuging, or can be obtained by spray drying in a preferably hot gas medium when they are then dry is a ready-to-use powdered one hard material

Claims (1)

PatentanspruchClaim Verfahren zum Herstellen von kleinen Kapseln mit einem in Wasser unlöslichen Kern, der durch Koazervieren einer Emulsion oder Dispersion ernes wasserigen Sols mit einem hydrophilen Kolloid umhüllt wird, dadurch gekennzeichnet, daß man wie ubhch die Koazervierung einleitet, sodann unterbiicht, überschüssiges Kolloid dekoazeraert und nach Zusetzen weiteren Kolloids wieder koazerviertProcess for the manufacture of small capsules with a water-insoluble core, which by Coacervation of an emulsion or dispersion of an aqueous sol with a hydrophilic one Colloid is enveloped, characterized in that, like ubhch, the coacervation introduces, then interrupts, excess Colloid is decoated and coacervated again after adding more colloids In Betracht gezogene Druckschriften·
USA.-Patentschriften Nr 2 800 457, 2 800 458Considered publications
U.S. Patent Nos. 2,800,457, 2,800,458 In Betracht gezogene altere Patente.
Deutsche Patente Nr. 1096 038, 1185155Older patents considered.
German patents No. 1096 038, 1185155 709 618/463 7 67 © Bundesdruckerei Berlin709 618/463 7 67 © Bundesdruckerei Berlin
DEN17701A 1958-12-31 1959-12-29 Making small capsules Pending DE1245320B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US784020A US3190837A (en) 1958-12-31 1958-12-31 Making individual capsules by dual deposition

Publications (1)

Publication Number Publication Date
DE1245320B true DE1245320B (en) 1967-07-27

Family

ID=25131105

Family Applications (1)

Application Number Title Priority Date Filing Date
DEN17701A Pending DE1245320B (en) 1958-12-31 1959-12-29 Making small capsules

Country Status (6)

Country Link
US (1) US3190837A (en)
CH (1) CH394131A (en)
DE (1) DE1245320B (en)
FR (1) FR1248178A (en)
GB (1) GB872713A (en)
NL (2) NL246985A (en)

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US3435947A (en) * 1965-11-26 1969-04-01 Ncr Co Article having an expandable and rigidizable compacted flexible material
LU57907A1 (en) * 1969-02-04 1970-08-04
US3627693A (en) * 1970-01-28 1971-12-14 Ncr Co Layered capsule walls and a method for manufacturing them
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US4367170A (en) * 1975-01-24 1983-01-04 American Optical Corporation Stabilized photochromic materials
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US4798741A (en) * 1985-12-13 1989-01-17 E. I. Du Pont De Nemours And Company Preparation of microencapsulated pigment
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CH394131A (en) 1965-06-30
NL129921C (en)
NL246985A (en)
FR1248178A (en) 1960-12-09
US3190837A (en) 1965-06-22
GB872713A (en) 1961-07-12

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