SE190178C1

SE190178C1 -

Info

Publication number: SE190178C1
Authority: SE
Publication date: 1964-01-01

Description

Uppfinnare: I A Herbig och J F Hanny Prioritet begard (ran den 5 septenzber 1961 (USA) Foreliggande uppfinning avser ett forfarande for framstallning av myeket sma kapslar, sarskin kapslar med karnor av ett med olja oblandbart material, som omges av somlosa vaggar av ett i varme smaltbart, vaxartat material. Inventors: IA Herbig and JF Hanny Priority Required (as of September 5, 1961 (USA) The present invention relates to a process for the manufacture of very small capsules, sarskin capsules with cores of an oil-immiscible material, which are surrounded by somlosa rocks of one in heat fusible, waxy material.

Forfarandet genomfdres i ett varmt oljeartat medium, i vilket ett vaxartat vaggbildande material, antingen osmalt eller i forvag smalt, och karnmaterial infOres for bildning av ett trefassystem dar oljemediet utgor den kontinuerliga fasen och det vaxartade vaggbildande materialet och karnmaterialen utgUr tva dispersa laser. Systemet Mies omrifirt, sa att det av varmet smaltande vaxet sonderslas till srna. partiklar, som tacker partiklarna av karnmaterialet under bildning av kapslar med vaggar av flytande vax. Darefter kyles systemet under fortsatt omroring for stelning av vaggarna till fast tillstand for fardigbildning av kapslarna, som darefter tillvaratas och anvands pa onskat satt. The process is carried out in a hot oily medium in which a waxy rock-forming material, either unmalted or pre-narrowed, and core material is introduced to form a three-phase system where the oil medium constitutes the continuous phase and the waxy rock-forming material and the core materials constitute two dispersed lasers. The Mies system has been redesigned, so that the wax melting by the heat is separated to the south. particles, which thank the particles of the core material during the formation of capsules with rocks of liquid wax. The system is then cooled with continued agitation to solidify the cradles to a solid state for completion of the capsules, which are then recovered and used as desired.

Sadana kapslar kan anvandas individuellt for att skydda karnmaterialet mot olika mintier, for att verka som bestandsdel av en blandning av kapslar med olika karnmaterial med fiirmaga att reagera med varandra vid beroring, nar kapselvaggarna brister, for att astadkomma skenbart torra vatskor, nar karnorna är flytande, for att astadkomma smakmaskering for lakemedel och for manga andra andamal, som kommer att framga av det foljande. Such capsules can be used individually to protect the core material from various minties, to act as a constituent of a mixture of capsules with different core materials with the ability to react with each other when touched, when the capsule walls rupture, to produce seemingly dry liquids when the kernels are liquid , to provide taste masking for drugs and for many other purposes, which will be apparent from the following.

Dessa kapslar kan ha en storlek rnellan 11u och 1000 ,t6 och darover, beroende pa det for anvandning i kapslarna valda karnmaterialet. Vid anvandning av fasta karnmaterial kan stone dimensioner uppnas. These capsules can have a size of 11u and 1000, t6 and above, depending on the core material selected for use in the capsules. When using solid core materials, stone dimensions can be achieved.

De enda villkoren vid valet av materialet Or att de maste vara inbordes oblandbara, att de ej reagerar med varandra och att det vaxartade materialet Or fast vid rumstemperatur, har formaga att avsatta sig pa karnmaterialet, sasom de fiesta vaxartade flytande material gor, och smalter i det valda °nip. framstallningsmediet. Karnmaterialet kan vara flytande eller fast, eller besta av blandningar av flytande och fasta material. Det kan Oven besta av en suspension av fasta partiklar i en vatska. Om det vaxartade materialet smalter under 100° C, kan vatten inkapslas. The only conditions in the choice of the material Or that they must be in-mix immiscible, that they do not react with each other and that the waxy material Or solid at room temperature, have been able to settle on the core material, as most waxy liquid materials do, and melt in the selected nip. the production medium. The core material may be liquid or solid, or consist of mixtures of liquid and solid materials. It can also consist of a suspension of solid particles in a liquid. If the waxy material melts below 100 ° C, water can be encapsulated.

Det Egger mom ramen for uppfinningen att astadkomma system, i vilka flera an ett slag av karnmaterial anvands, vilka kan ha olika sammansattning eller fysikaliskt tillstand. Karnmaterialet kan inforas i systemet antingen som ett finfordelat fast amne eller i form av en vatska, som finfordelas till den onskade droppstorleken genom en for detta andamal 1Nmpligt reglerad ,omroring. Karnmaterialet kan vara fast vid rumstemperatur och flytande vid vaxets smalttemperatur. Ordningsfonden vid materialens infOring i karlet spelar ej nagon storre roll. Salunda kan Karnmaterialet sattas till det oljiga framstallningsmediet som redan innehaller vaxet; vaxet sattas till det oljiga framstallningsmediet, som redan innehaller karnmaterialet; en suspension av det oljiga framstallningsmediet och vaxet sattas till en dispersion av det oljiga mediet och karnmatedalet; en uppslamning av smalt vax och karnmaterial sattas till det oljiga mediet; eller det oljiga mediet sattas till vaxet och karnmaterialet. It is within the scope of the invention to provide systems in which several types of core material are used, which may have different composition or physical state. The core material can be introduced into the system either as a finely divided solid or in the form of a liquid, which is finely divided into the desired droplet size by a stirring, which is conveniently controlled for this purpose. The core material can be solid at room temperature and liquid at the melting temperature of the wax. The order fund for the introduction of the materials into the vessel does not play a major role. Thus, the seed material can be added to the oily preparation medium which already contains the wax; the wax is added to the oily preparation medium, which already contains the core material; a suspension of the oily preparation medium and the wax is added to a dispersion of the oily medium and the core material; a slurry of narrow wax and core material is added to the oily medium; or the oily medium is added to the wax and the core material.

Om bestandsdelarna Or kalla, nar de tillsattes tillsammans, kan de vid en senare tidpunkt varmas till framstallningstemperatur. Blandningen av bestandsdelarna kan lagras kallt for senare anvandning, under forutsattning att materialen ej paverkas genom aldring eller langvarig bertiring med varandra eller med omgivningen. Den atmosfariska omgivningen kan utestangas 2— genom blandningens inldggning pa burk for framtida bruk. - De dispergerade materialen far ej overhopas i framstallningsmediet till ett stadium, dar agglomerering intrader. Det har visat sig, att det foretradesvis bOr finnas minst 5 ggr sâ. stor volym av det oljiga framstallningsmediet som volymen dispergerat material, Viktforhfillandet mellan kdrnmaterial och vaxartat material kan variera mellan 1: 10 och 10: 1. If the constituents Or are cold when added together, they can be heated to production temperature at a later time. The mixture of the constituents can be stored cold for later use, provided that the materials are not affected by aging or prolonged contact with each other or with the environment. The atmospheric environment can be excluded by canning the mixture for future use. - The dispersed materials must not accumulate in the production medium until a stage where agglomeration enters. It has been found that there should preferably be at least 5 times as many. large volume of the oily preparation medium as the volume of dispersed material. The weight difference between core material and waxy material can vary between 1:10 and 10: 1.

Foremal for uppfinningen är sdlunda ett fOrfarande att framstalla sind kapslar, inneslutande ett flytande ochfeller fast kdrnmaterial, vilket forfarande kUnnetecknas genom atgarderna att dstadkomma ett up-pvarmt och omrort trefassystem, bestaende av en kontinuerlig fas av ett i huvudsak inert, oljeartat medium, som innehaller tva. diskontinuerliga faser, av vilka den ena bestar av ett kdrnmaterial och den andra av ett vaxartat, vaggbildande material, varvid materialen ej har formaga att reagera med varandra och det vaxartade materialet dr flytande i det vdrinda systemet men fast vid rumstemperatur och liar fOrmaga att avsatta sig vid kontakt med varje partikel av karnmaterialet och bilda flytande vaggar ddromkring; samt att under fortsatt °mitring kyla systemet, tills de flytande, vaxartade kapselvaggarna stelnat. The object of the invention is thus a process for producing its capsules, including a liquid and solid core material, which process is characterized by the steps of providing a heated and stirred three-phase system, consisting of a continuous phase of a substantially inert, oily medium, as two. discontinuous phases, one of which consists of a core material and the other of a waxy, rock-forming material, the materials not being able to react with each other and the waxy material being liquid in the air system but solid at room temperature and capable of settling upon contact with each particle of the core material and forming liquid rocks around it; and during continued metering, cooling the system until the liquid, waxy capsule walls solidify.

En fOredragen utforingsform av forfarandet enligt uppfinningen skall nn beskrivas med exempel. I 500 g silikonolja (i del foljande kallad forming III) med en viskositet av 475-525 cSt vid 25° C dispergeras 5 g polyeten med en skarp smaltpunkt av c:a 130° C, en densitet av 0,920,95 och en molekylvikt av c:a 2500, varvid oljans temperatur halles Over polyetenets smdltpunkt och systemet halles omrort, tills det smalta polyetcnets droppstorlek nâr c:a 100 u. I detta system infores vid vilken tidpunkt som heist under de foregdende operationerna partiklar av ammoniumnitrat med en kornstorlek av 2ft. Det flytande polyetenet avatter sig p partiklarna och bildar flytande vaxartade vdggar daromkring. For stelning av vdggarna far systemet under fortsatt omroring svalna till rumstemperatur. De fardiga kapslarna kan darefter avlagsnas Iran det oljiga mediet genom brukliga metoder, sasom dekantering, filtrering, centrifugering och liknande, eller kan ocksa anvandas i det medium i vilket de framstallts. A preferred embodiment of the method according to the invention will now be described by way of example. In 500 g of silicone oil (hereinafter referred to as forming III) having a viscosity of 475-525 cSt at 25 ° C, 5 g of polyethylene having a sharp melting point of about 130 ° C, a density of 0.920.95 and a molecular weight of about 2500, the temperature of the oil being kept above the melting point of the polyethylene and the system being stirred until the droplet size of the narrow polyethylene reaches about 100 u. . The liquid polyethylene settles on the particles and forms liquid waxy walls around it. For solidification of the walls, the system is allowed to cool to room temperature during continued stirring. The finished capsules can then be removed from the oily medium by conventional methods, such as decantation, filtration, centrifugation and the like, or can also be used in the medium in which they are made.

Typiska vaxartade material Or polyetener med skarp smaltpunkt och deras med alkylgrupper med rak eller grenad kolkedja substituerade derivat, vilka Or fasta vid rumstemperatur (° C). Andra anvdndbara material Or karnaubavax, spermaceti och ett stort flertal syntetiska och naturliga vaxer, foretrddesvis med skarpa smaltpunkter. Bland mineralvaxerna kan sarskilt ndmnas mikrokristallint vax. Blandningar av vaxer kan anvandas. Andra f Or forfarandet ldmpade vaxer Or bivax, kanelillavax, paraffinvax, montanvax, japanvax och liknande. Typical waxy materials Or sharp melting point polyethylenes and their straight or branched carbon chain alkyl groups substituted derivatives which are solid at room temperature (° C). Other useful materials Or carnauba wax, spermaceti and a large number of synthetic and natural waxes, preferably with sharp melting points. Among the mineral waxes, microcrystalline wax can be especially mentioned. Mixtures of waxes can be used. Other f Orced procedure waxed bees Or beeswax, cinnamon wax, paraffin wax, montan wax, japan wax and the like.

Bland oljeartade framstallningsmedier som visat sig mest lampliga kan namnas I. ett flytande polysiloxan med formeln — *CH, 1 (CHO- Si-0— —Si(CH,), CH,n med en sonderdelningstemperatur av 250-300° C; foreningen I, i vilkert 25 % av *CHrsubstituenterna Or ersatta av fenylgrupper, varvid en sadam forening har en sonderdelningstemperatur av 350-400° C; foreningen I, i vilken 100 % av *CHrsubstituenterna Or ersatta med fenylgrupper, varvid en sadan forening har en sonderdelningstemperatur av 450-500° C; tributylamin (C4H9)3N, i vilken valet ersatts av fluor, vilken forening liar en kokpunkt av 170-180° C, och isomerer dray; en isomerblandning av en cyklisk perfluoreter (C8F160) med ett kokpunktsintervall av 100-1° C. Among the oily production media which have proved to be most suitable are I. a liquid polysiloxane of the formula - * CH, 1 (CHO-Si-O-—Si (CH 2), CH I, in which 25% of the * CH 2 substituents Or are replaced by phenyl groups, wherein such compound has a probe division temperature of 350-400 ° C, the compound I, in which 100% of the * CH 2 substituents Or are replaced by phenyl groups, wherein such a compound has a probe division temperature of 450-500 ° C; tributylamine (C4H9) 3N, in which the choice is replaced by fluorine, which compound has a boiling point of 170-180 ° C, and isomers dry; an isomeric mixture of a cyclic perfluoroether (C8F160) with a boiling point range of 100 -1 ° C.

Alla dessa foreningar atom foreningarna I, II och III Or fluorsubstituerade, och samtliga av dem Or praktiskt taget inerta gentemot vilket vaxartat material som heist eller vilket karnmaterial som heist, som det Or onskvart att inkapsla. Detta utesluter ej anyandningen av oljeartade medier med en viss reaktionsformaga, om de anvands tillsammans med vaxartade vaggmaterial och karnmaterial, som ej har formaga att reagera darmed, och uppfinningen far ej anses begransad till kiseloljor eller fluorerade oljeartade material. For speciella temperaturbetingelser kan alltefter behov blandningar av de oljeartade materialen anyandas. All of these compounds are compounds I, II and III or fluorosubstituted, and all of them are practically inert to which waxy material heist or which core material heist, which it is desirable to encapsulate. This does not preclude the use of oily media with a certain reactive form, if they are used together with waxy rock materials and core materials which are not capable of reacting therewith, and the invention may not be considered limited to silicon oils or fluorinated oily materials. For special temperature conditions, mixtures of the oily materials may be used as needed.

I det foljande anges ett antal kemiskt kombinerbara, inbordes oblandbara material, som visat sig vara sdrdeles ldmpliga kombinationer for uppfinningens syften. The following are a number of chemically compatible, in-mix materials which have been found to be particularly suitable combinations for the purposes of the invention.

MrnmaterialVaggmaterial Magnesiumhydrid Polyeten Ammoniumnitrat Polyeten KaliumdikromatPolyeten Ammoniumdikromat Polyeten AcetylsalicylsyraPolyeten d-Propoxyfenhydro- Polyeten klorid (Mercks In- dex, 7 th Ed, p. 862) KinidinglukonatParaffin Kadmiumb oratPolyeten AcetylsalicylsyraTristearin AcetylsalicylsyraDiglycerid Ammoniumdikromat Tristearin d-Propoxyfen-hydro- Tristearin klorid Natriumbikarb onat Paraffin Natriumbikarbonat Tristearin Tenn (II) fluoridTristearin Tenn (II) fluoridParaffin Tenn (II) fluoridPolyeten Framstall- ningsmedium I, II, III I, II, HI, IV I, II, HI, IV I, II, III, IV I, II, III, IV I, II, III, IV IV I, II, III, IV IV IV IV IV IV IV IV IV IV — —3 KarnmaterialVaggmaterial Bitoluylen-4,4-Japanvax diisocyanat Toluen-diisocyanat Paraffin Toluen-diisocyanat Polyeten Difenylmetan-4,4-Paraffin diisocyanat Difenylmetan-4,4-Paraffin + diisocyanat5 % Vinylplast AmmoniumnitratPolyeten (MetaIlpar- tiklar) Difenylmetan-4,4- Japanvax diisocyanat Difenylmetan-4,4-Ceritavax diisocyanat Natriumdiklorocy- Polyeten anurat Kaliumdiklorocy-Polyeten anurat Klorerat trinatrium- Polyeten fosf at JasmedelPolyeten DietylentriaminParaffin + 20% vinylplast De i denna lista angivna materialen utgor endast exempel, och listan far darfor inte anses innebara nagon begransning av uppfinningen. Polyetenerna har en rnolekylvikt av mellan 2500 och 12000. Den i listan forekommande hanvisningen till metallpartiklar avser inforingen av sadana i form av pulver i mediet efter det att de flytande vaggarna av vaxartat material bildats. Sadant material fastnar i vaggarna och kvarhalles dãr efter vaggarnas kylning och stelning. Aluminiumpulver är ett typiskt exempel, men vilket dispergerbart pulver som heist av joke reaktionsbendgen natur kan avsattas i kapselvaggarna, medan dessa fortfarande befinner sig i flytande tillstand. Andra exempel fir kolloidal kiseldkodd, ferromagnetisk jdrnoxid, jdrnpulver och liknande. De pulvri serade materialen kan verka som isolatorer, elektriska eller elektrostatiska material, pulvriserade kemikalier med fOrmaga att reagera med kapselinnehallet etc. Den anvanda vinylplasten var en sampolymer av eten och vinylacetat. MrnmaterialVaggmaterial magnesium hydride Polyethylene Polyethylene KaliumdikromatPolyeten Ammonium Ammonium Aspirin Polyethylene Polyethylene Polyethylene Propoxyfenhydro- d-chloride (Merck In- dex, 7 th Ed, p. 862) KinidinglukonatParaffin Kadmiumb oratPolyeten AcetylsalicylsyraTristearin AcetylsalicylsyraDiglycerid Tristearin Ammonium d-Propoxyphene-hexahydro- Tristearin chloride Natriumbikarb paraffin sulfonate Sodium bicarbonate Tristearin Tenn (II) fluorideTristearin Tin (II) fluorideParaffin Tin (II) fluoridePolyethylene Preparation medium I, II, III I, II, HI, IV I, II, HI, IV I, II, III, IV I, II, III, IV I, II, III, IV IV I, II, III, IV IV IV IV IV IV IV IV IV IV IV - —3 Core materialWall material Bitoluylene-4,4-Japan wax diisocyanate Toluene diisocyanate Paraffin Toluene diisocyanate Polyethylene Diphenylmethane-4,4- Paraffin diisocyanate Diphenylmethane-4,4-Paraffin + diisocyanate 5% Vinyl plastic Ammonium nitrate Polyethylene (Metal particles) Diphenylmethane-4,4-Japan wax diisocyanate Diphenylmethane-4,4-Ceritavax dii socyanate Sodium dichlorocy- Polyethylene anurate Potassium dichlorocy-Polyethylene anurate Chlorinated trisodium- Polyethylene phosphate at DetergentPolyethylene DiethylenetriamineParaffin + 20% vinyl plastic The materials listed in this list are examples only, and the list should therefore not be construed as limiting the invention. The polyethylenes have a molecular weight of between 2500 and 12000. The male reference to metal particles in the list refers to the introduction of such in the form of powder into the medium after the liquid cradles of waxy material have been formed. Such material gets stuck in the cradles and is retained there after the cradles have cooled and solidified. Aluminum powder is a typical example, but any dispersible powder heist of the joke reaction bend nature can be deposited in the capsule walls, while these are still in a liquid state. Other examples are colloidal silica, ferromagnetic iron oxide, iron powder and the like. The powdered materials can act as insulators, electrical or electrostatic materials, powdered chemicals capable of reacting with the capsule contents, etc. The vinyl plastic used was a copolymer of ethylene and vinyl acetate.

Det är tydligt, att de enligt det beskrivna forfarandet framstallda kapslarna kan anvandas som karnor for avsattning av ett yttre skikt av ett annat material med vaxliknande egenskaper, eller av hydrofoba eller hydrofila polymerer, som anbringas enligt kanda forfaranden. It is clear that the capsules produced according to the described process can be used as cores for depositing an outer layer of another material with wax-like properties, or of hydrophobic or hydrophilic polymers, which are applied according to known methods.

Claims

Patent claim:

Process for the production of small capsules, enclosing a liquid and / or solid core material, characterized by the steps of providing a heated and stirred three-phase system, consisting of a continuous phase of a substantially inert oily medium, containing two discontinuous lasers, of which one is a core material and the other a waxy, rock-forming material, the materials not having the ability to react with each other and the waxy material being liquid in the heated system but fixed at room temperature and having the shape of a floating rock deposited with each core particle. ; and while continuing to stir, cooling the system, until the liquid, waxy capsule walls solidify.

Method according to claim 1, characterized in that the weight ratio between Urn material and waxy material varies between 1:10 and 10: 1.

A method according to claim 1 or 2, characterized in that a joke reactive powdered material is added to the system, after the liquid waxy rocks are formed. Request publications: