Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS2971916 A
Publication typeGrant
Publication dateFeb 14, 1961
Filing dateJan 30, 1957
Priority dateJan 30, 1957
Publication numberUS 2971916 A, US 2971916A, US-A-2971916, US2971916 A, US2971916A
InventorsSchleicher Lowell, Charles S Baughman
Original AssigneeNcr Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Microscopic capsules containing magnetizable material
US 2971916 A
Images(2)
Previous page
Next page
Description  (OCR text may contain errors)

Feb. 14, 19.61 L. SCHLEICHER ETAL 2,971,916

MICROSCOPIC CAPSULES CONTAINING MAGNETIZABLE MATERIAL Filed Jan. 30, 1957 2 Sheets-Sheet 1 FIG. I

INVENTORS LOWELL SCHLEICHER CHARLES S. BAUGHMAN BY Wm Ma THEIR ATTORNEYS Feb. 14, 1961 L. SCHLEICHER ET'AL 2,971,915

' MICROSCOPIC CAPSULES cormmmc MAGNETIZABLE. MATERIAL Filed Jan. 30. 1957 2 Sheets-Sheet 2 FIG. 3

THEIR ATTORNEYS United States Patent MICROSCOPIC CAPSULES CONTAINING MAG- NETIZABLE MATERIAL Filed In. 30, 1957, Ser. No. 637,270

1 Claim. (Cl. 252-625) This invention relates to pressure-rupturable microscopic capsules having contained therein, suspended in a liquid vehicle, micro fine particles of magnetic material.

The magnetic material may be of any desired kind. Some examples of magnetic material are black or redmagnetic iron oxide, carbonyl iron, ferro magnetic alloys, nickel and its magnetic alloys, cobalt and its magnetic alloys, or any mixture of the aforementioned. The naming of these materials is not to be deemed to limit the invention, as other solid magnetic powders will do. These magnetic powders may be permanently magnetized in the capsules, or they may be magnetized by magnetic fields applied to the capsules.

In the preferred form of the invention hydrophyllic colloid capsule walls enclose an oily vehicle, in which vehicle the magnetic particles are suspended. Among the preferred oils, because of their inertness, are chlorinated diphenyl, light petroleum fractions, or any equivalent nonpolar oily solvent, which will not attack the particles of magnetic material.

As much as 50% by volume of the magnetic powder, as compared to the oil, may be included within the capsule walls. The oily vehicle may also have included therein dyes and pigments for purposes to be stated later on.

The microscopic capsules have been made from individual diameters of 3 microns to 150 microns, although this is not to be deemed to limit the diametrical size of these magnetic-material-containing capsules.

These capsules may be used in connection with printing by magnetic means. lta sheet of record material having a magnetizable coating is magnetized in spots to represent data, the capsules provided by this invention, it applied to the coating, will cling to the magnetized spots. The sheet may then be placed on a receiving sheet of paper and pressure applied. The capsules will rupture leaving an imprint of the data on the receiving sheet by virtue of the intrinsic color of the magnetic powder or by virtue of any dye or pigment carried by the oily vehicle.

With these and incidental objects in view, the invention includes certain novel features, a preferred form or embodiment of which is hereinafter described with reference to the drawings which accompany and form a part of this specification.

Of the drawings:

Figs. 1 to 4 inclusive each show the same array of capsules, as viewed under a microscope wherein the magnification was of the order of 1000 diameters, the larger capsules being of the order of 150 microns and the smaller capsules of the order of 50 to 75 microns in diameter. In Figs. 1 to 4 the orientation of the magnetic material within has been changed by use of a magnetic field to four different directions, showing the mobility of the magnetic material within the capsules.

First, the method of making the capsules shown in the drawings will be described, and it may be considered the preferred method. The magnetic material 20 to 25,

2,971,916 Patented Feb. 14, 1961 inclusive, shown in the figures of the drawings, are chains of magnetic iron oxide particles, the individual magnetic material particles being of the order of one micron in diameter. The fluid vehicle is trichloro-diphenyl, which bears the reference numerals 26 to 31 inclusive in the various figures of the drawings. The capsule walls which have been given the reference numbers 32 to 37, inclusive, are of a complex of gelatin and gum arabic, which being treated by the process to be described, is oil-impermeable. The liquid vehicle has dissolved in it certain wetting and dispersing agents. The particular wetting and dispersing agents used in making the capsules shown in the drawings are oleic acid, zinc stearate, and dioctylphthalate.

In making these capsules shown in the drawings, the liquid with the magnetic iron oxide suspension is prepared first in the following manner:

Mill thoroughly together 160 grams of trichloro-diphenyl 30 grams of black magnetic iron oxide of an average particle size of one micron 1 gram of oleic acid A gram of zinc stearate 1 gram of dioctylphthalate until the agglomerate size of the magnetic iron oxide particles averages about three microns. Next, a first solution of pigskin gelatin in water is made, the gelatin having its isoelectric point at pH 8. The solution is made and kept at a temperature of approximately degrees Fahrenheit. The first solution contains 20 grams of the pigskin gelatin and grams of water. Next, a second solution is made, consisting of gum arabic in water at 135 degrees Fahrenheit, there being used 20 grams of gum arabic and 160 grams of water. Both of the colloid solutions are adjusted to pH 6.5.

The previously prepared magnetic oxide-containing mixture is emulsified into the gelatin solution until the drop size is of the order of 10 microns; that is to say, the drop size of the oil phase. Next, the solution of gum arabic is added to the emulsion, still keeping the temperature at approximately 135 degrees Fahrenheit. About 400 grams of the resulting'mixture is placed in a container, in a water bath at 135 degrees Fahrenheit, and water at 135 degrees Fahrenheit is added to bring the total volume to one liter. The water-diluted mixture then has its pH adjusted downwardly to approximately 4.7, to bring about coacervation, so that the colloid material will deposit in oriented fashion around each of the oil droplets containing the magnetic particle suspension. This phenomenon of coacervation is clearly explained in application for United States Patent Serial No. 365,105, filed June 20, 1953, by Barrett K. Green and applicant Lowell Schleicher of this application. This application was allowed as of November 26, 1956, and issued July 23, 1957, as United States Patent No. 2,800,457. resulting coacervate mixture is added 2.7 cubic centimeters, of a 37% solution of formaldehyde in water. The foregoing additions of materials to each other is done with constant stirring, to keep the mixtures uniform. While still being stirred, the coacervate mixture is lowered in temperature to near 32 degrees Fahrenheit, approximately, so the deposited colloid material will gel to form capsule walls around each of the included oil droplets. Next, ten grams of a 5% aqueous solution of the polyvinyl-methyl ether of maleic anhydride is added, with continued stirring for a period of several hours, maintaining the temperature below 50 degrees Fahrenheit, to prevent the capsules from agglomerating in the hardening step described next. The capsules are complete at this time, but are dispersed in a substantially colloidtree excess of water. So the capsules will withstand temperatures higher than the ordinary melting point of Into the I the colloid, the pH is then adjusted to 9 or 10 with sodium hydroxide to cause the formaldehyde to react with the colloid to harden it. This dispersion of capsules and the aqueous medium can be coated directly on paper and dried, the individual capsules maintaining their integrity and each having within it the magnetic powder, as described. If desired, the water in which the capsules are dispersed may be eliminated by spray-drying in a hot atmosphere, the resulting product being a very fine powder containing the discrete capsules with the magnetic oxide-floating in the included vehicle.

The capsules shown in the drawings and the described method of making them have not included the addition of coloring matter to increase the marking color of the capsule because to do so would have rendered it impossible to show the magnetic material in the drawings. Any

4 oil soluble dye or oil dispersible pigment can be used as an addition agent to the vehicle in which the magnetic iron oxide is suspended.

What is claimed is:

A microscopic capsule having a wall of hardened organic colloid material enclosing an oily liquid containing a dispersion of magnetic powder.

References Cited in the file of this patent UNITED STATES PATENTS 2,106,882 Betz Feb. 1, 1938 2,671,451 Bolger Mar. 9, 1954 2,680,079 Huebner June 1, 1954 2,730,456 Green et al. Ian. 10, 1956 2,730,457 Green et al. Jan. 10, 1956 2,800,457 Green et a1. July 23, 1957

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2106882 *Dec 12, 1936Feb 1, 1938Magnaflux CorpPaste of paramagnetic particles for use in the examination of paramagnetic materials for flaws by the magnetic method
US2671451 *Jun 16, 1952Mar 9, 1954Bolger Stephen JRemedial pill
US2680079 *Apr 4, 1951Jun 1, 1954Huebner CompanyMethod for making sheet or web material
US2730456 *Jun 30, 1953Jan 10, 1956Ncr CoManifold record material
US2730457 *Jun 30, 1953Jan 10, 1956Ncr CoPressure responsive record materials
US2800457 *Jun 30, 1953Jul 23, 1957Ncr CoOil-containing microscopic capsules and method of making them
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3042616 *Aug 26, 1958Jul 3, 1962IbmProcess of preparing magnetic ink
US3092553 *Apr 11, 1960Jun 4, 1963Jr Carl E FisherPharmaceutical preparations and method and apparatus for making same
US3147991 *Nov 13, 1962Sep 8, 1964Heinz Sr Edward NCheckbook
US3221315 *Jun 25, 1962Nov 30, 1965Ncr CoMagnetic recording medium utilizing microscopic capsules containing magnetic material
US3249458 *Dec 10, 1962May 3, 1966Brunswick CorpPressure responsive material
US3281669 *Apr 2, 1963Oct 25, 1966Trimble Lyne SMeans and method for indicating and visibly permanently recording a magnetic field utilizing a magnetostrictive material and a chemical reaction
US3316119 *Nov 1, 1961Apr 25, 1967Litton Systems IncRecording member for visibly recording radio frequency microwaves
US3320523 *Feb 1, 1965May 16, 1967Trimble Lyne SMethod for visibly indicating and recording magnetic fields
US3330693 *Oct 29, 1962Jul 11, 1967PatecoMethod of making a magnetic record member with encapsulated ferromagnetic particles in a binder and resulting product
US3415186 *Feb 10, 1966Dec 10, 1968Xerox CorpDuplicating system
US3415758 *May 3, 1962Dec 10, 1968Ncr CoProcess of forming minute capsules en masse
US3451545 *Jul 13, 1967Jun 24, 1969Shell Oil CoMethod for separating micro-organisms from earth samples
US3512169 *Oct 20, 1965May 12, 1970Trimble Lyne SMagnetochemical method and means for creating visible displays in color
US3547693 *Sep 20, 1968Dec 15, 1970Eastman Kodak CoMagnetic tape
US3683382 *Sep 25, 1969Aug 8, 1972Honeywell IncRecording medium responsive to force fields and apparatus for recording and reproducing signals on the medium
US3927930 *May 13, 1974Dec 23, 1975Polaroid CorpLight polarization employing magnetically oriented ferrite suspensions
US3954666 *Jul 11, 1974May 4, 1976E. I. Du Pont De Nemours And CompanySemipermeable microcapsules containing heterogeneous catalysts and ferromagnetic materials
US3954678 *Jul 11, 1974May 4, 1976E. I. Du Pont De Nemours And CompanySemipermeable microcapsules containing a silica gel
US4099186 *Feb 25, 1977Jul 4, 1978E. I. Du Pont De Nemours And CompanyMagnetic printing process and apparatus
US4101435 *Jun 14, 1976Jul 18, 1978Meito Sangyo Kabushiki KaishaMagnetic iron oxide-dextran complex and process for its production
US4105572 *Mar 31, 1976Aug 8, 1978E. I. Du Pont De Nemours And CompanyDye and/or chemical treating agent
US4115534 *Jun 20, 1977Sep 19, 1978Minnesota Mining And Manufacturing CompanyComplexing radioactive material with magnetically responsive microparticles
US4117498 *Feb 25, 1977Sep 26, 1978E. I. Du Pont De Nemours And CompanyMagnetic printing process and apparatus
US4169804 *Jun 20, 1977Oct 2, 1979Minnesota Mining And Manufacturing CompanyMagnetically responsive composite microparticle
US4247406 *Apr 23, 1979Jan 27, 1981Widder Kenneth JIntravascularly-administrable, magnetically-localizable biodegradable carrier
US4331654 *Jun 13, 1980May 25, 1982Eli Lilly And CompanyDrug carrier formulation
US4732811 *Oct 22, 1986Mar 22, 1988Yeda Research And Development Company, Ltd.Agarose-polyaldehyde beads and their biological application affinity chromatography, hemoperfusion, cell separation, etc.
US4770183 *Jul 3, 1986Sep 13, 1988Advanced Magnetics IncorporatedIn vivo diagnosis, iron oxides coated with protein or carbohydrate
US5401516 *Apr 22, 1993Mar 28, 1995Emisphere Technologies, Inc.Encapsulation of biologically active materials, drug delivery, reaction with benzenesulfonyl chloride or benzoyl chloride
US5443841 *Jul 27, 1992Aug 22, 1995Emisphere Technologies, Inc.Proteinoid microspheres and methods for preparation and use thereof
US5447728 *Dec 16, 1993Sep 5, 1995Emisphere Technologies, Inc.A carrier comprising an acylated amino acid; lowering iron concentration in mammals
US5540939 *Apr 25, 1994Jul 30, 1996Emisphere Technologies, Inc.Encapsulating active materials
US5541155 *Apr 22, 1994Jul 30, 1996Emisphere Technologies, Inc.Acids and acid salts and their use in delivery systems
US5578323 *Jun 14, 1993Nov 26, 1996Emisphere Technologies, Inc.Proteinoid carriers and methods for preparation and use thereof
US5585725 *Apr 13, 1995Dec 17, 1996Associated Universities, Inc.Magnetic detection of underground pipe using timed-release marking droplets
US5601846 *May 9, 1995Feb 11, 1997Emisphere Technologies, Inc.Oligopeptide
US5629020 *Apr 22, 1994May 13, 1997Emisphere Technologies, Inc.Delivery of sensitive agents such as bioactive peptides
US5643957 *Oct 25, 1994Jul 1, 1997Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5650386 *Mar 31, 1995Jul 22, 1997Emisphere Technologies, Inc.Compositions for oral delivery of active agents
US5667806 *Jun 7, 1995Sep 16, 1997Emisphere Technologies, Inc.Spray drying method and apparatus
US5693338 *Sep 29, 1994Dec 2, 1997Emisphere Technologies, Inc.Delivery composition comprising active agent, diketopiperazine, enzyme inhibitor
US5709861 *Jan 13, 1995Jan 20, 1998Emisphere Technologies, Inc.Compositions for the delivery of antigens
US5714167 *Oct 25, 1994Feb 3, 1998Emisphere Technologies, Inc.Reversibly forming supramolecular complex of active agent with perturbant; drug delivery
US5750147 *Jun 7, 1995May 12, 1998Emisphere Technologies, Inc.Fungicides for oral administration
US5766633 *Apr 22, 1994Jun 16, 1998Emisphere Technologies, Inc.Modified amino acid carrier, bioactive peptides
US5792451 *Mar 2, 1994Aug 11, 1998Emisphere Technologies, Inc.Oral drug delivery compositions and methods
US5804688 *Feb 7, 1997Sep 8, 1998Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5811127 *Oct 24, 1994Sep 22, 1998Emisphere Technologies, Inc.Desferrioxamine oral delivery system
US5820881 *Apr 28, 1995Oct 13, 1998Emisphere Technologies, Inc.Microspheres of diamide-dicarboxylic acids
US5824345 *Jun 7, 1995Oct 20, 1998Emisphere Technologies, Inc.Microsphere comprising active agent, proteinoid, modified hydrolyzed vegetable protein
US5840340 *Aug 30, 1996Nov 24, 1998Emisphere Technologies, Inc.Oligopeptides with fragrance, cosmetics and dye
US5863944 *Apr 30, 1997Jan 26, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5866536 *Feb 6, 1997Feb 2, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5876710 *Feb 7, 1997Mar 2, 1999Emisphere Technologies Inc.Drug delivery; using a brominated benzamide compound
US5879681 *Feb 7, 1997Mar 9, 1999Emisphere Technolgies Inc.Compounds and compositions for delivering active agents
US5939381 *Feb 7, 1997Aug 17, 1999Emisphere Technologies, Inc.4-(4-(phenoxyacetyl)aminophenyl)butyric acid as a carrier for drug delivery
US5955503 *Feb 6, 1997Sep 21, 1999Emisphere Technologies, Inc.Modified amino acid compounds useful as carriers in the delivery of biologically active agents such as, for example, bioactive peptides and the like
US5958457 *May 10, 1995Sep 28, 1999Emisphere Technologies, Inc.Compositions for the delivery of antigens
US5962710 *May 9, 1997Oct 5, 1999Emisphere Technologies, Inc.Reacting an oligosalicylate and an amino acid
US5965121 *Feb 6, 1997Oct 12, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5972387 *Nov 21, 1994Oct 26, 1999Emisphere Technologies, Inc.Modified hydrolyzed vegetable protein microspheres and methods for preparation and use thereof
US5976569 *Apr 29, 1997Nov 2, 1999Emisphere Technologies, Inc.Diketopiperazine-based delivery systems
US5989539 *Feb 6, 1997Nov 23, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5990166 *Feb 7, 1997Nov 23, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US6001347 *Feb 6, 1997Dec 14, 1999Emisphere Technologies, Inc.Organic acid compound of given structure having an aromatic amide group, a methoxy group in the ortho position on the aromatic ring, and a lipophilic chain terminated with a carboxylic acid is useful as a nontoxic carrier
US6051258 *Jun 7, 1995Apr 18, 2000Emisphere Technologies, Inc.Proteinoid emulsions and methods for preparation and use thereof
US6060513 *Feb 7, 1997May 9, 2000Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US6071510 *Apr 23, 1997Jun 6, 2000Emisphere Technologies, Inc.Modified amino acids and compositions comprising the same for delivering active agents
US6071538 *Sep 30, 1997Jun 6, 2000Emisphere Technologies, Inc.Oral delivery composition comprising supramolecular complex
US6084112 *Sep 10, 1996Jul 4, 2000Emisphere Technologies, Inc.Method for preparing ω-aminoalkanoic acid derivatives from cycloalkanones
US6090958 *Feb 7, 1997Jul 18, 2000Emisphere Technologies, Inc.N-(8-carboxyoctyl)-o-hydroxybenzamide and salts
US6099856 *Dec 10, 1996Aug 8, 2000Emisphere Technologies, Inc.Increased bioavailable
US6100285 *Nov 11, 1997Aug 8, 2000Emisphere Technologies, Inc.Method of solubilizing itraconazole
US6100298 *Feb 6, 1997Aug 8, 2000Emisphere Technologies, Inc.Mixture of drug and n-(4-(carboxypropyl)phenyl-4-phenyl-butyramide for improved oral drug delivery
US6180140Jun 2, 1995Jan 30, 2001Emisphere Technologies, Inc.Modified amino acids for drug delivery
US6221367Sep 29, 1997Apr 24, 2001Emisphere Technologies, Inc.Exposing a biologically active agent to a complexing perturbant to reversibly transform the biologically active agent to the intermediate state and to form a transportable supramolecular complex
US6242495Jun 16, 2000Jun 5, 2001Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US6245359Sep 30, 1997Jun 12, 2001Emisphere Technologies, Inc.Active agent transport systems
US6313088Feb 7, 1997Nov 6, 2001Emisphere Technologies, Inc.Carriers used to deliver various active agents through various biological, chemical, and physical barriers
US6331318Sep 30, 1994Dec 18, 2001Emisphere Technologies Inc.Carbon-substituted diketopiperazine delivery systems
US6346242Feb 8, 2000Feb 12, 2002Emishpere Technologies, Inc.Compounds and compositions for delivering active agents
US6348207Sep 30, 1997Feb 19, 2002Emisiphere Technologies, Inc.Exposing biologically active agent to complexing perturbant to reversibly transform biologically active agent to intermediate state and form orally deliverable supramolecular complex, orally administering complex to subject
US6375983Jun 12, 1997Apr 23, 2002Emisphere Technologies, Inc.Microencapsulated fragrances and method for preparation
US6413550Nov 23, 1998Jul 2, 2002Emisphere Technologies, Inc.Proteinoid carriers and methods for preparation and use thereof
US6428780May 5, 1999Aug 6, 2002Emisphere Technologies, Inc.Modified amino acid
US6461545Jan 6, 2000Oct 8, 2002Emisphere Technologies, Inc.Method of solubilizing and encapsulating itraconazole
US7249604 *May 10, 2002Jul 31, 2007Vasmo, Inc.Medical devices for occlusion of blood flow
US7417022Apr 11, 2005Aug 26, 2008Mhr Institutional Partners Iia LpAmino acid for deliverying active materials; bioavailability
US7553872Feb 13, 2006Jun 30, 2009Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US7968117Apr 9, 2008Jun 28, 2011The United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationExternally triggered microcapsules
US8686154Jun 10, 2009Apr 1, 2014Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
USRE35862 *Aug 14, 1987Jul 28, 1998Emisphere Technologies, Inc.Delivery systems for pharmacological agents encapsulated with proteinoids
DE2602176A1 *Jan 21, 1976Aug 4, 1977Omnitechnic GmbhMetallverbindungen enthaltende mikrokapseln, insbesondere als haerter fuer polymerisationen und als vulkanisations-hilfsmittel sowie verfahren zur herstellung solcher mikrokapseln
EP0000667A1 *Jul 28, 1978Feb 7, 1979Northwestern UniversityIntravascularly-administrable, magnetically-localizable biodegradable carrier and process for its preparation
Classifications
U.S. Classification252/62.53, 324/214, 101/DIG.370, 428/407, 346/135.1, 346/74.6
International ClassificationH01F1/44, G03G19/00, G03G9/083, G03G9/093, B41M5/165, B01J13/10
Cooperative ClassificationB41M5/165, G03G9/0833, H01F1/44, B01J13/10, G03G19/00, G03G9/0839, Y10S101/37, G03G9/093
European ClassificationG03G9/083T, G03G9/093, H01F1/44, B41M5/165, G03G9/083B4, G03G19/00, B01J13/10