USRE24899E - Oil-containrab - Google Patents

Oil-containrab Download PDF

Info

Publication number
USRE24899E
USRE24899E US24899DE USRE24899E US RE24899 E USRE24899 E US RE24899E US 24899D E US24899D E US 24899DE US RE24899 E USRE24899 E US RE24899E
Authority
US
United States
Prior art keywords
oil
capsules
colloid
water
gelatin
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
Application number
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.)
Publication date
Application granted granted Critical
Publication of USRE24899E publication Critical patent/USRE24899E/en
Expired legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41JTYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J13/00Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, specially adapted for supporting or handling copy material in short lengths, e.g. sheets
    • B41J13/10Sheet holders, retainers, movable guides, or stationary guides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules 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
    • A61K9/5089Processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/06Making microcapsules or microballoons by phase separation
    • B01J13/08Simple coacervation, i.e. addition of highly hydrophilic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/06Making microcapsules or microballoons by phase separation
    • B01J13/10Complex coacervation, i.e. interaction of oppositely charged particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124Duplicating 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
    • B41M5/165Duplicating 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
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S101/00Printing
    • Y10S101/29Printing involving a color-forming phenomenon
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984Microcapsule with fluid core [includes liposome]

Definitions

  • This :invention relates to oil-containing microscopic capsules .ofa'gelled hydrophilic coloid material and to -a-method of making them by salt-coacervation.
  • the microscopic oil-impermeable capsules made in an aqueous medium, are .several microns in diameter, and :each contains, as a .central nucleus, oil surrounded by .a relatively and uniformly thick encapsulating wall of the;gelled colloid material. If the capsules are dispersedsin a -great deal of water they may exist individually, but if the free water is removed thecapsules tend to agglomerate like bunchesof grapes until'the mass becomes adherent and more or less solid.
  • the colloid encapsulating material is rendered impermeable, as far as the .oil is concerned, so that it cannot escape until the capsule is ruptured. In this way the oil is contained protected against-environmental and otherdeleterious influences.
  • the capsules may be treated asisolid material even though more than 50% of the weight of the mass may be oil .in liquid form. If desired, the capsules may be hardened and rendered insoluble so that the free water may be .drivenofibyheat, the dried material being immune to the destructive influence of'water and other equivalent solvents.
  • oils which may be used in the process are the watervimmiscible oils which are inert as to the encapsulating material and which may tbe emulsified with an aqueous sol of the particular hydrophilic gellable colloid used.
  • oils include the mineral oils such as petroleum fractions; animal oils such as sperm .oil; fish oils such .as halibut liver oil; vegetable oils such as cotton .seed oil, corn oil, castor oil, and coconut oil; essential oils from plants, and synthetic oils such as methyl salicylate and chlorinated diphenyl.
  • gellable hydrophilic colloid materials may be mentionedgelatin and agar-agar.
  • the oil that is usedto form the droplets which are surrounded by the encapsulating material, may be dissolved various selected materials, or dispersed solid materiaL-ofcolloidal size, such added substances, of course, being inert to the other ingredient materials.
  • dispersed solid materiaL-ofcolloidal size such added substances, of course, being inert to the other ingredient materials.
  • dyes such as are used in making inks, solid chemical reactant substances which will be described, medicines, perfumes, and. other materials which it is desired to have protected from the environment or which it is desired to have isolated for other reasons.
  • substances which maybe dissolved in the oil may be mentioned oil- Reissuecl Nov. 29, 19.60
  • a paper coating composition which forms a transfer film.
  • Theoil in the microscopic capsules so used would be of itself or contain a marking material which would be transferred to an underlying sheet by printing or marking pressures that rupture the capsules of the overlying transfer film, to cause said marks on the underlying sheet.
  • Transfer films of rupturable type which contain oily droplets of marking fluid are disclosed in United States Patent No. 2,548,366, whichissued on the applicaiton ofBarrett K. Green, this applicant, and Robert W. Sandberg, but such disclosed films are not composed of capsules.
  • Transfer films such as disclosed in said patent consistof a continuous film phase of gelled hydrophilic colloid material having fluid droplets of oil dispersed therethrough.
  • the aforesaid continuous film afiords someuopportunity for escape of the fluid droplets because of the sponge-like texture of the colloid gel film surrounding the voids which hold the oil.
  • Cracks in the films of the type disclosed in said patent will run right across the voids which 'hold the oil, releasing the oil. Such cracks may be caused by folding or rough handling of the material, or may be caused by unusualenvironmental conditions.
  • the product of this invention makes transfer films superior to thosedisclosed in said patent, int-hat cracks in the film formed by the capsular material of this invention do not runacross the capsules, but around them, so that the oil is deleased by random cracks pro- .duced in'the film.
  • the pore size of the hydroiphilic colloid encapsulating film may be reduced during gelatin-n and drying to render the encapsulating film impermeable to theoil inside, as will be explained.
  • EBacaus-e all .films of gelled hydrophilic colloid material aretoa degree molecularly porous because of the nature of .gel structures, the capsules will be-more or less porous according to the control exercised in forming :them. If the gelation step is performed rapidly the pore vsize'will .be small and the capsules will retain, by sieve action, .oils having relatively small molecules. If the gelation step is performed slowly the pore structure of the encapsulating material will be coarser.
  • the hardening step is carried out in a high pH environment, as will be described, which makes the capsules'harder, more heat resistant, and insoluble in water. If the capsules are used to hold marking fluids, small pores are desired, whereas if the capsules are to be used for other purposes where slow releaseof theoil from the capsules is desired, larger pores would be preferred.
  • the process is flexible to achieve either condition.
  • the capsules are to be dried, they may be dried in an oven and the resulting agglomerate material ground and washed to remove the oil which escaped during grinding, to form apparently dry granules or, if desired, the fluid-dispersed capsules may be spray dried, in which event no comminution or washing is necessary.
  • the capsules containing the fluid oil are handled and stored in the same manner as other dry materials are handled and stored.
  • Another further object of the invention is to provide such oil-containing capsules in which the encapsulating material has been hardened.
  • Fig. 1 is a reproduction of a micro-photograph of the capsules dispersed in a great amount of water, the magnification being about 800 diameters.
  • Fig. 2 is a block diagram showing the steps followed in making the gelled and hardened colloid capsules, this figure showing the process in general Without the specific recitation of ingredients and amounts of ingredients.
  • Fig. 3 shows the method in more specific form, with gelatin and trichlorodiphenyl as the ingredients, and with sodium sulphate as the salt.
  • Fig. 4 is a tertiary diagram showing the coacervation region of a sol of gelatin in water, using sodium sulphate as the salt.
  • FIG. 5 is a ternary diagram showing the coacervation region of a sol of gelatin in water, using ammonium sulphate as the salt.
  • the process in general, includes the first step of forming an emulsion of oil and a gellable colloid aqueous sol. This is made by dispersing the colloid in water, adding the oil and forming an emulsion by stirring.
  • a coacervate is formed by the addition of a proper amount of an aqueous solution of a suitable coacervating salt.
  • the foregoing steps are performed at a temperature above the melting point of the colloid sol.
  • the colloid is gelled by pouring the coacervate mixture into a cool solution of the same salt which was used for the coacervation, causing the colloid deposited around the individual oil droplets to gel.
  • This gelled colloid capsular mass is washed with water and filtered to remove the salt. If it is desired to harden and make the capsular material hard and insoluble, the filter cake is treated with a solution of formaldehyde. According to what use is to be made of the finished material, the free water is adjusted to the desired concentration, or the free water is removed entirely.
  • the preferred form of the invention utilizes gelatin, preferably high quality pigskin gelatin which has its iso-electric point at pH8.
  • gelatin preferably high quality pigskin gelatin which has its iso-electric point at pH8.
  • the preferred oil used is trichlorodiphenyl which is relatively non-volatile, inert, and which can be ob tained in a colorless and pure form.
  • a colorless color-reactant such as the crystal violet lactone which is, as specified in the patent to which reference has been made, 3,3 bisCp-dimethylaminophenyl) 6-dimethylamino phthalide.
  • the described phthalide compound has a white crystalline structure and, when dissolved to the extent of about 3%, by weight, in the trichlorodiphenyl and placed in contact with a sheet of paper sensitized with attapulgite, will turn to a dark blue color similar to crystal violet.
  • the capsules When fluid-dispersed capsular material containing this oil is applied to a sheet and dried to form a transfer film, the capsules may be ruptured locally at points of printing and marking pressures to release the oil which will thereupon come in contact with the sensitized undersheet, as mentioned in said patent.
  • the coacervation then is induced by adding, slowly and uniformly, four-tenths of a gallon of 20%, by weight, of sodium sulphate in water.
  • the gelatin molecules are deposited uniformly about each oil droplet as a nucleus. The uniform addition of this material is accomplished by continuous agitation.
  • the heated coacervate mixture is poured into 10 gallons of 7%, by Weight, of sodium sulphate in Water at 19 centigrade, with agitation. At this point the encapsulation of the oil with gelled hydrophilic material has taken place and the further steps are to put it in condition for use as is intended.
  • the material is filtered and washed with water, the temperature being kept below the melting point of the gelatin, to remove the salt. If desired, the filtered material is hardened by combining it with 2 gallons of a 37% solution of formaldehyde in water. This hardened mass then is filtered and washed to remove the residual formaldehyde.
  • the resulting filter cake is adjusted to the proper water content by the addition of water or the removal thereof, by ordinary means such as centrifuging or spray drying, and the material is ready for use. If this material is intended for paper coating composition it is kept in aqueous suspension and applied directly to the paper which is then dried leaving the capsules adherent to the paper and to each other in a film.
  • Fig. 5 shows the results of testing various amounts of the same gelatin with an ammonium sulphate solution.
  • the salt attracts water away from the colloid material causing the colloid material to separate or unmix, forming, in the vessel in which this step is taken, after they are allowed to separate by gravity, a colloidrich fluid in the bottom and a layer extremely poor in colloid material on top.
  • a particular sol is made of the pigskin gelatin and various solutions of sodium sulphate in water are added thereto. Referring to Fig. 4, with a starting point of any place on line 23, that is to say any sol of gelatin and water having less than 20% gelatin content, by weight, the aqueous sodium sulphate solution is added. For instance, if a 10% gelatin in water sol is used, the starting point would be 24 (Fig. 4) on line 23.
  • a 17 /2% sol of gelatin in water, represented by point 29, is treated with a l2 /z% solution of sodium sulphate in water as represented by point 30.
  • this sodium sulphate solution is added to the aqueous gelatin sol, the addition takes the mixture along the line 31 toward point 30, the clouding effect of coacervation becoming apparent at point 32.
  • the contour of line 28 may be ascertained and the ranges within which coacervation occurs by the addition of sodium sulphate solution to the gelatin sol may be ascertained.
  • the region to the right of line 28 is the coacervate region of the mixture but the addition of salt solution should not be carried far past the line 28 in actual practice, the more salt solution added the more aggregation occurring until a lumpy mass is formed.
  • the line 33 of Fig. 5 may be determined by the use of ammonium sulphate solution.
  • ammonium sulphate solution is not as efiicient in action as the sodium sulphate solution and the same dilferences occur with other salts.
  • Useful salts for coacervation may be made from the cations Na K Rb Cs NH Li and the anions S04 citrate tartrate acetate Cl such being arranged in the order of their eifectiveness in this process.
  • the size of the pores in the encapsulated material may be controlled during the gelling process.
  • the gelation of the gelatin was accomplished by pouring the coacervated mixture, amounting to about a gallon and a half, into gallons of relatively cool water-l9 centigrade. This causes rapid cooling and rapid gelation of the gelatin, resulting in a pore size so small that the encapsulated trichlorodiphenyl cannot escape through the capsule walls.
  • paper which had been coated with a film of the capsular material containing 3,3 bis (p-dimethylaminophenyl) 6-dirnethylamino phthalide in the oil droplets was similarly treated in the Soxhlet extractor. Upon removal and drying, it was used as a transfer sheet by placing it over a paper coated with attapulgite clay. It made marks on the clay-coated sheet when subjected to printing and writing pressures, that were as good as those made with an amount of unprotected oil equal to that in the paper. Whereas the unprotected 6 oil evaporated one day, there was no evidence of any loss of oil from the paper, even though left in the oven for over days at the same temperature.
  • the method of making oil-containing microscopic capsules of gellable hydrophilic colloid material including the steps of making an aqueous sol of a gellable hydrophilic colloid material; emulsifying therein an oil; adding and stirring into the emulsion a previously determined aqueous coacervate salt soluiton, of such concentration and in such amount as to bring the emulsion into the coacervate region defined by the occurrence of a clouding effect when the aqueous salt solution is added to the colloid solution in the absence of oil, all of the fore going steps being carried out at a temperature above the gelation point of the colloid material, whereby the colloid material deposits around each oil droplet by coacervate forces, encapsulating each of them; and gelling the colloid material by cooling.
  • Oil-containing microscopic capsules made according to the method of claim 2.
  • Oil-containing microscopic capsules made according to the method of claim 3.
  • Oil-containing microscopic capsules made according to the method of claim 4.
  • Oil-containing microscopic capsules made according to the method of claim 5.
  • Oil-containing microscopic capsules made according to the method of claim 6.
  • Oil-containing microscopic capsules made according to the method of claim 7.
  • the method of making oil-containing microscopic capsules of gellable hydrophilic colloid material including the steps of forming an emulsion of oil and an aqueous sol of gellable hydrophilic colloid material, then changing the condition of the resultant oil-containing sol to increase interaction between colloid molecules of said sol and bring said sol into the coacervate region wherein said colloid material contracts as a colloid-rich coacervate, the said region being defined by the occurrence of a clouding efiect when the condition of the same c olloid sol is changed in the some way in the absence 0 oil, all of the foregoing steps being carried out at a temperature above the gelation point of the colloid material, whereby coacervate colloid material deposits around each oil droplet encapsulating each of them, and gelling the encapsulating colloid material by cooling.
  • Oil-containing microscopic capsules made according to the method of claim 15.
  • Oil-containing,microscopic capsules made accord- 12,730,457 ing to the method of claim 17. 2,800,457

Description

OIL-CONTAINING MICROSCOPIC CAPSULES AND METHOD OF MAKING THEM Original Filed June 30, 1953 4 Sheets-Sheet 1 NOV. 1960 B K GREEN I Re. 24, 899
FIG. I
MICROSCOPIC OIL" CONTAINING CAPSULES OF GELLED HYDROPHILIC COLLOID MATERIAL MAGNIFICATION 800 X GELATIN CAPSULES CONTAINING TRICHLORODIPHENYL DROPLETS, THE CAPSULES BEING SPARSELY DISPERSED IN WATER TO SHOW INDIVIDUALLY INVENTOR BARRETT K. GREEN Nov. 29, 1950 B. K. GREEN R OIL-CONTAINING MICROSCOPIC CAPSULES e z4899 AND METHOD OF MAKING THEM Original Filed June 30, 1953 4 Sheets-Sheet 2 FIG. 2
MAKE AN EMULSION OF OIL AND A GELLABLE COLLOID AQUEOUS SOL COACERVATE BY ADDITION OF AN AQUEOUS SALT SOLUTION STEPS ABOVE THIS LINE PREFORMED AT TEMPERATURE, ABOVE MELTING POINT OF THE COLLOID SOL GEL THE COLLOID BY POURING COACERVATE MIXTURE IN COOL SALT SOLUTION WASH WITH WATER AND FILTER TO REMOVE THE SALT HARDEN FILTER CAKE WITH SOLUTION OF FORMALDEHYDE IN WATER WASH WITH WATER AND FILTER TO REMOVE RESIDUAL FORMAL DEHYDE ADJUST WATER CONCENTRATION TO DESIRED AMOUNT INVENTOR BARRETT K. GREEN HIS ATTORNEYS Nov. 29, 1960 a. K. GREEN 24,399
' OIL-CONTAINING MICROSCOPIC CAPSULES AND METHOD OF MAKING THEM Original Filed June 30, 1953 4 Sheets-Sheet 3 FIG. 3
MAKE I GALLON OF AN OIL'IN'WATER EMULSION 0F 20 PARTS BY WEIGHT, 0F TRICHLORODIPHENYL AND I00 PARI'S,BY WEIGHT, OF A SOL OF 10%, av WEIGHT, OF GELATIN m WATER THE on. DROP SIZE OF WHICH IS 2-5 mcRdNs COACERVATE BY ADDING SLOWLY AND UNIFORMLY 4/IO GALLON OF 20%, BY WEIGHT, SODIUM SULPHATE IN WATER KEEP INGREDIENTS ABOVE THIS LINE AT 50C POUR THE RESULTING COACERVATE MIXTURE INTO IO GALLONS OF 7%, BY WEIGHT, OF SODIUM SULPHATE IN WATER AT I9C, TO GEL THE COLLOID FILTER AND WASH FILTER CAKE WITH WATER AT A TEMPERATURE BELOW THE MELTING POINT OF THE GELATIN, TO REMOVE THE SALT HARDEN WASHED FILTER CAKE MATERIAL WITH 2 GALLONS OF 37% SOLUTION OF FORMAL DEHYDE IN WATER FILTER AND WASH THE COACERVATE MATERIAL TO REMOVE THE RESIDUAL FORMALDEHYDE REMOVE RESIDUAL FLUID IF DESIRED I NVE NTOR BARRETT K. GREEN kew/0W Nov. 29, 1960 a GREEN Re. 24,899
K. OIL-CONTAINING MICROSCOPIC CAPSULES AND METHOD OF MAKING THEM Original Filed June 30, 1953 4 Sheets-Sheet 4 I00% WATER A ABOUT 50: 24 90% fee INVENTOR BARRETT K GREEN United States Patent OIL-CONTATNIN G MICROSCOPIC CAPSULES AND METHOD OF MAKING THEM Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specifi- Lcation; :matter printed in italics indicates the additions made .by 1 reissue.
This :invention relates to oil-containing microscopic capsules .ofa'gelled hydrophilic coloid material and to -a-method of making them by salt-coacervation.
The microscopic oil-impermeable capsules, made in an aqueous medium, are .several microns in diameter, and :each contains, as a .central nucleus, oil surrounded by .a relatively and uniformly thick encapsulating wall of the;gelled colloid material. If the capsules are dispersedsin a -great deal of water they may exist individually, but if the free water is removed thecapsules tend to agglomerate like bunchesof grapes until'the mass becomes adherent and more or less solid.
.BY the process steps to be described, the colloid encapsulating material is rendered impermeable, as far as the .oil is concerned, so that it cannot escape until the capsule is ruptured. In this way the oil is contained protected against-environmental and otherdeleterious influences. In the event the free water is removed, the capsules may be treated asisolid material even though more than 50% of the weight of the mass may be oil .in liquid form. If desired, the capsules may be hardened and rendered insoluble so that the free water may be .drivenofibyheat, the dried material being immune to the destructive influence of'water and other equivalent solvents.
The oils which may be used in the process are the watervimmiscible oils which are inert as to the encapsulating material and which may tbe emulsified with an aqueous sol of the particular hydrophilic gellable colloid used. Among such oils are the mineral oils such as petroleum fractions; animal oils such as sperm .oil; fish oils such .as halibut liver oil; vegetable oils such as cotton .seed oil, corn oil, castor oil, and coconut oil; essential oils from plants, and synthetic oils such as methyl salicylate and chlorinated diphenyl.
Among the gellable hydrophilic colloid materials may be mentionedgelatin and agar-agar.
In the oil, that is usedto form the droplets which are surrounded by the encapsulating material, may be dissolved various selected materials, or dispersed solid materiaL-ofcolloidal size, such added substances, of course, being inert to the other ingredient materials. Among suchfine'lyoivided solid substances may be mentioned dyes such as are used in making inks, solid chemical reactant substances which will be described, medicines, perfumes, and. other materials which it is desired to have protected from the environment or which it is desired to have isolated for other reasons. Among substances which maybe dissolved in the oil may be mentioned oil- Reissuecl Nov. 29, 19.60
soluble dyes, adhesives, oil-soluble vitamins, and the like.
Among the most important uses for such material in an aqueous dispersion is as a paper coating composition which forms a transfer film. Theoil in the microscopic capsules so used would be of itself or contain a marking material which would be transferred to an underlying sheet by printing or marking pressures that rupture the capsules of the overlying transfer film, to cause said marks on the underlying sheet. Transfer films of rupturable type which contain oily droplets of marking fluid are disclosed in United States Patent No. 2,548,366, whichissued on the applicaiton ofBarrett K. Green, this applicant, and Robert W. Sandberg, but such disclosed films are not composed of capsules. Transfer films such as disclosed in said patent consistof a continuous film phase of gelled hydrophilic colloid material having fluid droplets of oil dispersed therethrough. The aforesaid continuous film afiords someuopportunity for escape of the fluid droplets because of the sponge-like texture of the colloid gel film surrounding the voids which hold the oil. Cracks in the films of the type disclosed in said patent will run right across the voids which 'hold the oil, releasing the oil. Such cracks may be caused by folding or rough handling of the material, or may be caused by unusualenvironmental conditions.
The product of this invention makes transfer films superior to thosedisclosed in said patent, int-hat cracks in the film formed by the capsular material of this invention do not runacross the capsules, but around them, so that the oil is notreleased by random cracks pro- .duced in'the film. Moreover, the pore size of the hydroiphilic colloid encapsulating film may be reduced during gelatin-n and drying to render the encapsulating film impermeable to theoil inside, as will be explained.
EBacaus-e all .films of gelled hydrophilic colloid material ,aretoa degree molecularly porous because of the nature of .gel structures, the capsules will be-more or less porous according to the control exercised in forming :them. If the gelation step is performed rapidly the pore vsize'will .be small and the capsules will retain, by sieve action, .oils having relatively small molecules. If the gelation step is performed slowly the pore structure of the encapsulating material will be coarser. The hardening step is carried out in a high pH environment, as will be described, which makes the capsules'harder, more heat resistant, and insoluble in water. If the capsules are used to hold marking fluids, small pores are desired, whereas if the capsules are to be used for other purposes where slow releaseof theoil from the capsules is desired, larger pores would be preferred. The process is flexible to achieve either condition.
If the capsules are to be dried, they may be dried in an oven and the resulting agglomerate material ground and washed to remove the oil which escaped during grinding, to form apparently dry granules or, if desired, the fluid-dispersed capsules may be spray dried, in which event no comminution or washing is necessary. In the .dry granular form the capsules containing the fluid oil are handled and stored in the same manner as other dry materials are handled and stored.
Therefore, it is an object of this invention to provide microscopic capsules of a gelled hydrophilic colloid material each having a centraloilnucleus.
It is another object of the invention to provide such capsules dispersed in a fluid.
It is an alternative object to provide such capsules in outwardly dry form.
It is further an object of the invention to provide microscopic oil-containing capsules of hydrophilic gelled colloid material in which the pore size of the encapsulating material was controlled by the conditions of its manufacture.
Another further object of the invention is to provide such oil-containing capsules in which the encapsulating material has been hardened.
With further objects in view which will become apparent in the specification to follow, the invention includes the use of novel ingredients and processing steps, some of which are optional, described with reference to the drawings which accompany and form part of this specification.
Of the drawings:
Fig. 1 is a reproduction of a micro-photograph of the capsules dispersed in a great amount of water, the magnification being about 800 diameters.
Fig. 2 is a block diagram showing the steps followed in making the gelled and hardened colloid capsules, this figure showing the process in general Without the specific recitation of ingredients and amounts of ingredients.
Fig. 3 shows the method in more specific form, with gelatin and trichlorodiphenyl as the ingredients, and with sodium sulphate as the salt.
Fig. 4 is a tertiary diagram showing the coacervation region of a sol of gelatin in water, using sodium sulphate as the salt.
\Fig. 5 is a ternary diagram showing the coacervation region of a sol of gelatin in water, using ammonium sulphate as the salt.
Referring to Fig. 2, the process, in general, includes the first step of forming an emulsion of oil and a gellable colloid aqueous sol. This is made by dispersing the colloid in water, adding the oil and forming an emulsion by stirring. Next, after having determined the coacervate region of the sol, by making a diagram as shown in Figs. 3 and 4, as will be described, a coacervate is formed by the addition of a proper amount of an aqueous solution of a suitable coacervating salt. In order that the colloid will not gel prematurely the foregoing steps are performed at a temperature above the melting point of the colloid sol. Thereafter, the colloid is gelled by pouring the coacervate mixture into a cool solution of the same salt which was used for the coacervation, causing the colloid deposited around the individual oil droplets to gel. This gelled colloid capsular mass is washed with water and filtered to remove the salt. If it is desired to harden and make the capsular material hard and insoluble, the filter cake is treated with a solution of formaldehyde. According to what use is to be made of the finished material, the free water is adjusted to the desired concentration, or the free water is removed entirely.
The preferred form of the invention, shown step by step in Fig. 3, utilizes gelatin, preferably high quality pigskin gelatin which has its iso-electric point at pH8. Inasmuch as the finished encapsulated material will find an important use in the making of coating compositions which will form a transfer film on record material, such as paper, the preferred oil used is trichlorodiphenyl which is relatively non-volatile, inert, and which can be ob tained in a colorless and pure form. Into this trichlorodiphenyl may be dissolved a colorless color-reactant such as the crystal violet lactone which is, as specified in the patent to which reference has been made, 3,3 bisCp-dimethylaminophenyl) 6-dimethylamino phthalide. The described phthalide compound has a white crystalline structure and, when dissolved to the extent of about 3%, by weight, in the trichlorodiphenyl and placed in contact with a sheet of paper sensitized with attapulgite, will turn to a dark blue color similar to crystal violet. When fluid-dispersed capsular material containing this oil is applied to a sheet and dried to form a transfer film, the capsules may be ruptured locally at points of printing and marking pressures to release the oil which will thereupon come in contact with the sensitized undersheet, as mentioned in said patent. In making up the preferred material, one gallon of an oil-in-water emulsion of 20 parts, by weight, of trichlorodiphenyl containing the phthalide and 100 parts, by weight, of a sol of 10%, by weight, of pigskin gelatin in water, is prepared, the emulsifying continuing until the drop size of the oil is from 2 to 5 microns. This material is kept at 50 centigrade to prevent the gelatin from gelling. With the temperature of the ingredient still kept at 50, the coacervation then is induced by adding, slowly and uniformly, four-tenths of a gallon of 20%, by weight, of sodium sulphate in water. During coacervation, the gelatin molecules are deposited uniformly about each oil droplet as a nucleus. The uniform addition of this material is accomplished by continuous agitation.
To gel the coacervate, the heated coacervate mixture is poured into 10 gallons of 7%, by Weight, of sodium sulphate in Water at 19 centigrade, with agitation. At this point the encapsulation of the oil with gelled hydrophilic material has taken place and the further steps are to put it in condition for use as is intended. The material is filtered and washed with water, the temperature being kept below the melting point of the gelatin, to remove the salt. If desired, the filtered material is hardened by combining it with 2 gallons of a 37% solution of formaldehyde in water. This hardened mass then is filtered and washed to remove the residual formaldehyde. The resulting filter cake is adjusted to the proper water content by the addition of water or the removal thereof, by ordinary means such as centrifuging or spray drying, and the material is ready for use. If this material is intended for paper coating composition it is kept in aqueous suspension and applied directly to the paper which is then dried leaving the capsules adherent to the paper and to each other in a film.
In determining under what conditions with particular materials coacervation takes place, resort may be had to the formation of a ternary diagram resulting from a testing of various amounts of pigskin gelatin and sodium sulphate solution, whereas Fig. 5 shows the results of testing various amounts of the same gelatin with an ammonium sulphate solution. In the causation of coacervation by use of a salt, the salt attracts water away from the colloid material causing the colloid material to separate or unmix, forming, in the vessel in which this step is taken, after they are allowed to separate by gravity, a colloidrich fluid in the bottom and a layer extremely poor in colloid material on top. The tests which are made to determine the coacervate region as far as amounts of material are concerned can be done with the colloid sol and the salt solution without the oil. Inasmuch as it is impractical to work with solutions of gelatin in which there is less than water, because of viscosity, the diagrams of Figs. 4 and 5 deal in that portion of the tenary scale above 80% water. The line 20 in Fig. 4 and the line 21 in Fig. 5 represent 80% water, the horizontal lines being indexed with the intermediate percentages of water. C0- acervation is noticed by a clouding effect appearing in the sol which transmits less light than normal. This may be noted by passing a beam of light through the sol as the salt solution is added and estimating by eye the change towards a cloudiness, or an electric photometer may be used. A particular sol is made of the pigskin gelatin and various solutions of sodium sulphate in water are added thereto. Referring to Fig. 4, with a starting point of any place on line 23, that is to say any sol of gelatin and water having less than 20% gelatin content, by weight, the aqueous sodium sulphate solution is added. For instance, if a 10% gelatin in water sol is used, the starting point would be 24 (Fig. 4) on line 23. If now a 15% solution of sodium sulphate in water, as would be plotted at point 25, is added slowly which would be plotted along the dotted line 26, at point 27 a clouding effect will be noticed which means that the gelatin in water S01 is changing so that the entire mass of gelatin in a liquid phase is contracted because of the increased interaction between the gelatin molecules. This clouding efi'ect, [first noticed at point 27, will continue as more of the sodium sulphate solution is added. During the experiinents to determine the coacervate line 28 by various experiments with different concentrations of sol and salt solution, the ingredients are kept at about 50 centigrade. As another example in determining the line 28 of Fig. 4, a 17 /2% sol of gelatin in water, represented by point 29, is treated with a l2 /z% solution of sodium sulphate in water as represented by point 30. As this sodium sulphate solution is added to the aqueous gelatin sol, the addition takes the mixture along the line 31 toward point 30, the clouding effect of coacervation becoming apparent at point 32. By making a number of such experimental additions of the sodium sulphate solution to various sol concentrations, the contour of line 28 may be ascertained and the ranges within which coacervation occurs by the addition of sodium sulphate solution to the gelatin sol may be ascertained. The region to the right of line 28 is the coacervate region of the mixture but the addition of salt solution should not be carried far past the line 28 in actual practice, the more salt solution added the more aggregation occurring until a lumpy mass is formed. In a similar manner the line 33 of Fig. 5 may be determined by the use of ammonium sulphate solution.
It will be evident that the ammonium sulphate solution is not as efiicient in action as the sodium sulphate solution and the same dilferences occur with other salts. Useful salts for coacervation may be made from the cations Na K Rb Cs NH Li and the anions S04 citrate tartrate acetate Cl such being arranged in the order of their eifectiveness in this process.
When oil droplets are present the gelatin still in the liquid phase starts to draw together entrapping the oil droplets by deposition of the sol material around them individually as nuclei, forming a strong shell-like wall, and upon gelation of the colloid material the capsules are complete.-
Reference has been made to the fact that the size of the pores in the encapsulated material may be controlled during the gelling process. The faster the gelation of the colloid the finer the pore size of the gelled structure will be, and vice versa. As was said with reference to Fig. 3, the gelation of the gelatin was accomplished by pouring the coacervated mixture, amounting to about a gallon and a half, into gallons of relatively cool water-l9 centigrade. This causes rapid cooling and rapid gelation of the gelatin, resulting in a pore size so small that the encapsulated trichlorodiphenyl cannot escape through the capsule walls. Less rapid cooling will result in pores of larger size and the oil used may gradually escape or not as is determined by the size of the pores in the encapsulating film and the size of the oil molecules. That capsules made in accordance with the process of Fig. 3 actually retain the trichlorodiphenyl oil has been proved in various Ways. Some of the dried capsular material was placed in a Soxhlet extractor with toluene and subjected to extraction for a week. The material was then removed and dried. Upon crushing the capsular material, oil was released. In another instance paper which had been coated with a film of the capsular material containing 3,3 bis (p-dimethylaminophenyl) 6-dirnethylamino phthalide in the oil droplets was similarly treated in the Soxhlet extractor. Upon removal and drying, it was used as a transfer sheet by placing it over a paper coated with attapulgite clay. It made marks on the clay-coated sheet when subjected to printing and writing pressures, that were as good as those made with an amount of unprotected oil equal to that in the paper. Whereas the unprotected 6 oil evaporated one day, there was no evidence of any loss of oil from the paper, even though left in the oven for over days at the same temperature.
While the invention, including the ingredients and steps, has been fully outlined in the foregoing specification, the steps are capable of some modification in regard to temperature and amounts of ingredients used, and the ingredients themselves, of course, may be changed, as indicated earlier in the specification.
What is claimed is:
l. The method of making oil-containing microscopic capsules of gellable hydrophilic colloid material, including the steps of making an aqueous sol of a gellable hydrophilic colloid material; emulsifying therein an oil; adding and stirring into the emulsion a previously determined aqueous coacervate salt soluiton, of such concentration and in such amount as to bring the emulsion into the coacervate region defined by the occurrence of a clouding effect when the aqueous salt solution is added to the colloid solution in the absence of oil, all of the fore going steps being carried out at a temperature above the gelation point of the colloid material, whereby the colloid material deposits around each oil droplet by coacervate forces, encapsulating each of them; and gelling the colloid material by cooling.
2. The method of claim 1 in which the colloid used is gelatin.
3. The method of claim 1 in which the salt is sodium sulphate.
4. The method of claim '1 in which the colloid material is gelatin and the salt is sodium sulphate.
5. The method of claim 1 in which the salt is ammonium sulphate.
6. The method of claim 1 in which the colloid material is gelatin and the salt ammonium sulphate.
7. The method of claim 1 in which the steps before gelation are carried out above the gelation point of the colloid and the pore size of the capsular material around the oil droplets is made small by the rapid cooling of the coacervate material to cause rapid gelation of the colloid.
8. Oil-containing microscopic capsules made according to the method of claim 1..
9. Oil-containing microscopic capsules made according to the method of claim 2.
l0. Oil-containing microscopic capsules made according to the method of claim 3.
11. Oil-containing microscopic capsules made according to the method of claim 4.
12. Oil-containing microscopic capsules made according to the method of claim 5.
13. Oil-containing microscopic capsules made according to the method of claim 6.
14. Oil-containing microscopic capsules made according to the method of claim 7.
15. The method of making oil-containing microscopic capsules of gellable hydrophilic colloid material, including the steps of forming an emulsion of oil and an aqueous sol of gellable hydrophilic colloid material, then changing the condition of the resultant oil-containing sol to increase interaction between colloid molecules of said sol and bring said sol into the coacervate region wherein said colloid material contracts as a colloid-rich coacervate, the said region being defined by the occurrence of a clouding efiect when the condition of the same c olloid sol is changed in the some way in the absence 0 oil, all of the foregoing steps being carried out at a temperature above the gelation point of the colloid material, whereby coacervate colloid material deposits around each oil droplet encapsulating each of them, and gelling the encapsulating colloid material by cooling.
16. Oil-containing microscopic capsules made according to the method of claim 15.
17. The method of claim 15, in which said cooling is with agitation.
18. Oil-containing,microscopic capsules made accord- 12,730,457 ing to the method of claim 17. 2,800,457
References Cited in the file of this patent or the original patent 5 514 047 UNITED STATES PATENTS 454,3 5
2,183,053 Taylor Dec. 12, 1939 2,410,110 Taylor Oct. 26, 1946 2,714,375 Sandberg June 21, 1955 '8 Green et al. Jan. 10, 1956 Green et a1. July 23, 1957 FOREIGN PATENTS Great Britain Oct. 30, 1939 Germany Jan. 6, 1928 OTHER REFERENCES Emulsion Technology (1946,) pages 26, 68, 69.
US24899D 1953-06-30 Oil-containrab Expired USRE24899E (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US365106A US2800458A (en) 1953-06-30 1953-06-30 Oil-containing microscopic capsules and method of making them

Publications (1)

Publication Number Publication Date
USRE24899E true USRE24899E (en) 1960-11-29

Family

ID=23437495

Family Applications (2)

Application Number Title Priority Date Filing Date
US24899D Expired USRE24899E (en) 1953-06-30 Oil-containrab
US365106A Expired - Lifetime US2800458A (en) 1953-06-30 1953-06-30 Oil-containing microscopic capsules and method of making them

Family Applications After (1)

Application Number Title Priority Date Filing Date
US365106A Expired - Lifetime US2800458A (en) 1953-06-30 1953-06-30 Oil-containing microscopic capsules and method of making them

Country Status (7)

Country Link
US (2) US2800458A (en)
BE (3) BE530008A (en)
CH (3) CH334334A (en)
DE (2) DE1010822B (en)
FR (3) FR1165805A (en)
GB (4) GB751600A (en)
NL (3) NL95043C (en)

Cited By (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3092553A (en) * 1959-01-30 1963-06-04 Jr Carl E Fisher Pharmaceutical preparations and method and apparatus for making same
US3238103A (en) * 1961-04-26 1966-03-01 Clarence A Vogenthaler Therapeutic composition and method of making it
US3455848A (en) * 1964-05-05 1969-07-15 Ncr Co Polyurethane foam-producing compositions comprising microencapsulated particles and a method of making foams therefrom
US3460972A (en) * 1965-09-29 1969-08-12 Battelle Development Corp Liquid encapsulation
US3469439A (en) * 1968-02-21 1969-09-30 Sanford B Roberts Means for measuring distributed forces using microcapsules
US4428869A (en) 1981-08-20 1984-01-31 International Flavors & Fragrances Inc. Cologne consisting of microcapsule suspension
US4471880A (en) 1983-10-03 1984-09-18 Rubbermaid Incorporated Center press outer seal bowl lid
US4599271A (en) 1983-06-09 1986-07-08 Moore Business Forms, Inc. Microencapsulation of polyisocyanates by interchange of multiple
US4927802A (en) 1988-12-09 1990-05-22 Ppg Industries, Inc. Pressure-sensitive multi-part record unit
US5035896A (en) * 1988-06-15 1991-07-30 Warner-Lambert Company Water insoluble drugs coated by coacervated fish gelatin
US5447728A (en) * 1992-06-15 1995-09-05 Emisphere Technologies, Inc. Desferrioxamine oral delivery system
US5540939A (en) 1992-12-21 1996-07-30 Emisphere Technologies, Inc. Modified hydrolyzed vegetable protein microspheres and methods for preparation and use thereof
US5541155A (en) 1994-04-22 1996-07-30 Emisphere Technologies, Inc. Acids and acid salts and their use in delivery systems
US5578323A (en) * 1992-06-15 1996-11-26 Emisphere Technologies, Inc. Proteinoid carriers and methods for preparation and use thereof
US5601846A (en) * 1992-06-15 1997-02-11 Emisphere Technologies, Inc. Proteinoid microspheres and methods for preparation and use thereof
US5603952A (en) * 1994-12-30 1997-02-18 Tastemaker Method of encapsulating food or flavor particles using warm water fish gelatin, and capsules produced therefrom
US5616315A (en) * 1994-10-13 1997-04-01 Gillette Canada Inc. Particles including degradable material and anti-microbial agent
US5629020A (en) * 1994-04-22 1997-05-13 Emisphere Technologies, Inc. Modified amino acids for drug delivery
US5643957A (en) * 1993-04-22 1997-07-01 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5650386A (en) 1995-03-31 1997-07-22 Emisphere Technologies, Inc. Compositions for oral delivery of active agents
US5660817A (en) 1994-11-09 1997-08-26 Gillette Canada, Inc. Desensitizing teeth with degradable particles
US5667806A (en) 1995-06-07 1997-09-16 Emisphere Technologies, Inc. Spray drying method and apparatus
US5693338A (en) 1994-09-29 1997-12-02 Emisphere Technologies, Inc. Diketopiperazine-based delivery systems
US5709861A (en) * 1993-04-22 1998-01-20 Emisphere Technologies, Inc. Compositions for the delivery of antigens
US5714167A (en) * 1992-06-15 1998-02-03 Emisphere Technologies, Inc. Active agent transport systems
US5750147A (en) 1995-06-07 1998-05-12 Emisphere Technologies, Inc. Method of solubilizing and encapsulating itraconazole
US5766633A (en) 1993-04-22 1998-06-16 Emisphere Technologies, Inc. Oral drug delivery compositions and methods
US5792451A (en) * 1994-03-02 1998-08-11 Emisphere Technologies, Inc. Oral drug delivery compositions and methods
US5804688A (en) * 1997-02-07 1998-09-08 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5811127A (en) * 1992-06-15 1998-09-22 Emisphere Technologies, Inc. Desferrioxamine oral delivery system
US5820881A (en) * 1995-04-28 1998-10-13 Emisphere Technologies, Inc. Microspheres of diamide-dicarboxylic acids
US5824345A (en) * 1995-06-07 1998-10-20 Emisphere Technologies, Inc. Fragrances and flavorants
US5863944A (en) 1997-04-30 1999-01-26 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5866536A (en) * 1995-03-31 1999-02-02 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5876710A (en) * 1997-02-07 1999-03-02 Emisphere Technologies Inc. Compounds and compositions for delivering active agents
US5879681A (en) * 1997-02-07 1999-03-09 Emisphere Technolgies Inc. Compounds and compositions for delivering active agents
US5939381A (en) 1997-02-07 1999-08-17 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5958457A (en) * 1993-04-22 1999-09-28 Emisphere Technologies, Inc. Compositions for the delivery of antigens
US5962710A (en) 1997-05-09 1999-10-05 Emisphere Technologies, Inc. Method of preparing salicyloylamino acids
US5965121A (en) 1995-03-31 1999-10-12 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5989539A (en) 1995-03-31 1999-11-23 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5990166A (en) 1997-02-07 1999-11-23 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6051258A (en) 1995-06-07 2000-04-18 Emisphere Technologies, Inc. Proteinoid emulsions and methods for preparation and use thereof
US6060513A (en) 1997-02-07 2000-05-09 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6071510A (en) 1995-03-31 2000-06-06 Emisphere Technologies, Inc. Modified amino acids and compositions comprising the same for delivering active agents
US6084112A (en) 1995-09-11 2000-07-04 Emisphere Technologies, Inc. Method for preparing ω-aminoalkanoic acid derivatives from cycloalkanones
US6090958A (en) 1995-03-31 2000-07-18 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6099856A (en) * 1992-06-15 2000-08-08 Emisphere Technologies, Inc. Active agent transport systems
US6103378A (en) 1998-11-23 2000-08-15 The Mead Company Capsules having discrete solvent/color former and diluent capsule encapsulated phases
US6221367B1 (en) 1992-06-15 2001-04-24 Emisphere Technologies, Inc. Active agent transport systems
US6242495B1 (en) 1997-02-07 2001-06-05 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6331318B1 (en) 1994-09-30 2001-12-18 Emisphere Technologies Inc. Carbon-substituted diketopiperazine delivery systems
US6346242B1 (en) 1995-03-31 2002-02-12 Emishpere Technologies, Inc. Compounds and compositions for delivering active agents
US6375872B1 (en) 1992-11-17 2002-04-23 Moore Business Forms Microencapsulated adhesive
US6375983B1 (en) 1996-06-14 2002-04-23 Emisphere Technologies, Inc. Microencapsulated fragrances and method for preparation
US6475542B1 (en) * 1996-01-08 2002-11-05 Ajinomoto Co., Inc. Edible microcapsule and food containing the same
US20050075420A1 (en) * 2003-10-06 2005-04-07 Terry Stovold Invisible ink
US20050165131A1 (en) * 2003-10-06 2005-07-28 Terry Stovold Invisible ink
US20080113862A1 (en) * 2003-10-06 2008-05-15 Nocopi Technologies, Inc. Invisible Ink And Scratch Pad
US7417022B2 (en) 1996-03-29 2008-08-26 Mhr Institutional Partners Iia Lp Compounds and compositions for delivering active agents
US7553872B2 (en) 1997-02-07 2009-06-30 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US8927026B2 (en) 2011-04-07 2015-01-06 The Procter & Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules
US8980292B2 (en) 2011-04-07 2015-03-17 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
US9162085B2 (en) 2011-04-07 2015-10-20 The Procter & Gamble Company Personal cleansing compositions with increased deposition of polyacrylate microcapsules
US9186642B2 (en) 2010-04-28 2015-11-17 The Procter & Gamble Company Delivery particle
US9993793B2 (en) 2010-04-28 2018-06-12 The Procter & Gamble Company Delivery particles

Families Citing this family (348)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2929736A (en) * 1957-07-25 1960-03-22 Ncr Co Heat and pressure responsive record material
US3016308A (en) * 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US3080250A (en) * 1958-03-13 1963-03-05 Xerox Corp Self-tackifying xerographic toner
US3080251A (en) * 1958-03-13 1963-03-05 Xerox Corp Method of xerographic development
US3080318A (en) * 1958-03-13 1963-03-05 Xerox Corp Three-component xerographic toner
US2968066A (en) * 1958-04-03 1961-01-17 Dow Chemical Co Formation of solid beads by congelation of suspended liquid droplets
NL283761A (en) * 1958-06-04
US2969331A (en) * 1958-06-04 1961-01-24 Ncr Co Process of making dual-walled oil containing capsules
US3042616A (en) * 1958-08-26 1962-07-03 Ibm Process of preparing magnetic ink
NL106610C (en) * 1958-10-23
US2980941A (en) * 1958-12-08 1961-04-25 Ncr Co Cleaning sheet
US3096189A (en) * 1958-12-10 1963-07-02 Allied Chemical Comporation Duplicating sheet and colored coating compositions therefor
GB929408A (en) * 1958-12-22 1963-06-19 Upjohn Co Encapsulated emulsions and processes for their preparation
GB929402A (en) * 1958-12-22 1963-06-19 Upjohn Co Encapsulated emulsions and processes for their preparation
GB929401A (en) * 1958-12-22 1963-06-19 Upjohn Co Encapsulated emulsions and processes for their preparation
GB929227A (en) * 1958-12-22 1963-06-19 Upjohn Co Encapsulated emulsions and processes for their preparation
US3069370A (en) * 1958-12-22 1962-12-18 Upjohn Co Coacervation process for encapsulation of lipophilic materials
GB911483A (en) * 1958-12-22 1962-11-28 Upjohn Co Encapsulated emulsions and processes for their preparation
GB929470A (en) * 1958-12-22 1963-06-26 Upjohn Co Encapsulated emulsions and processes for their preparation
US3265629A (en) * 1958-12-22 1966-08-09 Ncr Co Coating by phase separation
NL104256C (en) * 1958-12-22
US3265630A (en) * 1958-12-22 1966-08-09 Ncr Co Encapsulating lipophilic material by coacervation
GB929403A (en) * 1958-12-22 1963-06-19 Upjohn Co Encapsulated emulsions and processes for their preparation
US3242051A (en) * 1958-12-22 1966-03-22 Ncr Co Coating by phase separation
US3054751A (en) * 1958-12-30 1962-09-18 Ibm Magnetic lithographic inks
NL246985A (en) * 1958-12-31
BE585460A (en) * 1959-01-02 1900-01-01
DE1119302B (en) * 1959-07-11 1961-12-14 Gerhard Ritzerfeld Process for the production of impressions of printing forms with an ink supply of triphenylmethane dyes
US3092463A (en) * 1959-11-02 1963-06-04 Miles Lab Stable blood detecting composition
US3085015A (en) * 1959-11-27 1963-04-09 Lever Brothers Ltd Process for making oil containing compositions
US3137631A (en) * 1959-12-01 1964-06-16 Faberge Inc Encapsulation in natural products
US3173878A (en) * 1960-02-26 1965-03-16 Ibm Process of making microcapsules
IT631615A (en) * 1960-02-26
US3415758A (en) * 1960-03-09 1968-12-10 Ncr Co Process of forming minute capsules en masse
NL262194A (en) * 1960-03-10 1900-01-01
US3129103A (en) * 1960-05-16 1964-04-14 Ncr Co Ink coating for pressure sensitive transfer record sheet
US3201353A (en) * 1960-06-14 1965-08-17 American Agricultural Chem Co Micro-inclusions and method of making same
NL268635A (en) * 1960-08-26 1900-01-01
NL271010A (en) * 1960-11-04
US3405070A (en) * 1961-01-30 1968-10-08 Ibm Process for preparation of microcapsules
US3159585A (en) * 1961-04-12 1964-12-01 Nat Starch Chem Corp Method of encapsulating water insoluble oils and product thereof
NL277911A (en) * 1961-05-04
DE1181934B (en) * 1961-08-25 1964-11-19 Siemens Ag Fault recorder for deletable storage of events
NL129277C (en) * 1961-09-14
NL288245A (en) * 1962-01-29
BE627711A (en) * 1962-01-29
BE628650A (en) * 1962-02-20
US3369900A (en) * 1963-03-25 1968-02-20 Polaroid Corp Microscopic capsules and method of making the same
DE1255081B (en) * 1963-06-10 1967-11-30 Roha Werk Walter Buehner & Co Transfer of oily substances into capsules by spray-drying oil-in-water emulsions
US3305382A (en) * 1964-01-02 1967-02-21 Ibm Pressure sensitive transfer sheet
US3357354A (en) * 1965-09-03 1967-12-12 Xerox Corp Reproduction method
US3396117A (en) * 1965-09-07 1968-08-06 Amp Inc Encapsulation technique
US3396116A (en) * 1965-09-07 1968-08-06 Amp Inc Encapsulation technique
US3505428A (en) * 1966-01-03 1970-04-07 Inmont Corp Curable normally stable compositions containing cross linking agent in capsule form
GB1136099A (en) * 1966-01-27 1968-12-11 Ncr Co Liquid-containing pressure- or heat-sensitive dry sheet material
US3447945A (en) * 1966-04-09 1969-06-03 Fuji Photo Film Co Ltd Process for the preparation of pressure-sensitive copying papers
US3436355A (en) * 1966-04-18 1969-04-01 Ncr Co Process for making capsules and method of making premix used therein
US3539465A (en) * 1968-10-08 1970-11-10 Ncr Co Encapsulation of hydrophilic liquid-in-oil emulsions
US3549555A (en) * 1968-10-08 1970-12-22 Ncr Co Encapsulation of lipophilic liquid-in-hydrophilic liquid emulsions
BE744162A (en) * 1969-01-16 1970-06-15 Fuji Photo Film Co Ltd ENCAPSULATION PROCESS
US3872024A (en) * 1970-05-27 1975-03-18 Ncr Co Encapsulation process by simple coacervation using inorganic polymers
US3769066A (en) * 1971-06-22 1973-10-30 Ncr Co Replacement of capsule contents
US3922373A (en) * 1973-03-26 1975-11-25 Capsulated Systems Inc Solid microglobules containing dispersed materials
JPS5748780B2 (en) * 1975-01-10 1982-10-18
DE2708977A1 (en) * 1977-03-02 1978-09-07 Basf Ag FUNGICIDE
US4228216A (en) * 1978-06-05 1980-10-14 The Mead Corporation Production of radiation curable microcapsular coating compositions, pressure-sensitive transfer paper and its production
JPS5489819A (en) * 1977-12-27 1979-07-17 Fuji Photo Film Co Ltd Production of pressure sensitive copying sheet
DE2830539A1 (en) * 1978-07-12 1980-01-24 Basf Ag METHOD FOR CURING MICROCAPSULES
JPS5538826A (en) * 1978-09-11 1980-03-18 Fuji Photo Film Co Ltd Color-developing ink
IT1194595B (en) * 1979-11-29 1988-09-22 Montedison Spa SOLID FORMULATIONS CONTAINING FERORMONES
IT1129711B (en) * 1980-01-23 1986-06-11 Montedison Spa SOLID FORMULATIONS CONTAINING FERORMONES
IT1148784B (en) * 1980-04-09 1986-12-03 Eurand Spa PROCEDURE FOR THE PREPARATION OF MICRO CAPSULES IN A LIQUID VEHICLE
JPS5719662A (en) * 1980-07-09 1982-02-01 Fuji Photo Film Co Ltd Preparation of microcapsule reagent for immune reaction
US4324767A (en) * 1980-08-04 1982-04-13 Occidental Research Corporation Separation process utilizing microcapsules
DD160393A3 (en) * 1980-11-14 1983-07-27 Horst Dautzenberg MICRO CAPSULES AND METHOD FOR THE PRODUCTION THEREOF
US4446032A (en) * 1981-08-20 1984-05-01 International Flavors & Fragrances Inc. Liquid or solid fabric softener composition comprising microencapsulated fragrance suspension and process for preparing same
US4464271A (en) * 1981-08-20 1984-08-07 International Flavors & Fragrances Inc. Liquid or solid fabric softener composition comprising microencapsulated fragrance suspension and process for preparing same
US4956300A (en) * 1982-01-05 1990-09-11 Helena Laboratories Corporation Aid for determining the presence of occult blood, method of making the aid, and method of using the aid
JPS59120654A (en) * 1982-12-27 1984-07-12 Shin Nisso Kako Co Ltd Fluoran compound
JPS59197463A (en) * 1983-04-26 1984-11-09 Shin Nisso Kako Co Ltd Fluoran compound
DE3337387A1 (en) * 1983-10-14 1985-04-25 Basf Ag, 6700 Ludwigshafen NEW FLUORANE AND THEIR USE
US5702913A (en) * 1983-12-21 1997-12-30 Helena Laboratories Corporation Chromgen-reagent test system
US5273888A (en) * 1984-01-16 1993-12-28 Helena Laboratories Corporation Chemical test kit and method for determining the presence of blood in a specimen and for verifying the effectiveness of the chemicals
US4696863A (en) * 1984-08-28 1987-09-29 Mitsubishi Paper Mills, Ltd. Biocapsule
DE3507173A1 (en) 1985-03-01 1986-09-04 Basf Ag, 6700 Ludwigshafen COLOR IMAGE MIXTURES AND PRESSURE SENSITIVE RECORD MATERIAL CONTAINING THESE MIXTURES
US4657582A (en) * 1985-05-30 1987-04-14 Pennwalt Corporation Polyhydroxy polymer delivery systems
AU593305B2 (en) 1985-11-21 1990-02-08 Fuji Photo Film Co., Ltd. Light-sensitive material employing microcapsules containing polymerisable compound and silver halide, and light-sensitive material employing the same
EP0232512B1 (en) * 1985-12-13 1992-04-08 E.I. Du Pont De Nemours And Company Encapsulated pigment in silver halide wash-off film
US6231873B1 (en) 1986-01-10 2001-05-15 Shiseido Company, Ltd Cosmetic containing fine soft microcapsules
JPH0619570B2 (en) 1986-02-07 1994-03-16 富士写真フイルム株式会社 Photosensitive material
DE3605552A1 (en) * 1986-02-21 1987-08-27 Bayer Ag HIGHLY CONCENTRATED, STABLE SOLUTIONS OF COLOR IMAGES
JPS63159489A (en) * 1986-12-23 1988-07-02 Shin Etsu Chem Co Ltd Gel composition
FR2641467B2 (en) * 1987-06-15 1991-04-26 Chicouri Marcel NOVEL LAXATIVE COMPOSITIONS AND PROCESS FOR OBTAINING THEM
US5081040A (en) * 1987-06-29 1992-01-14 Helena Laboratories Corporation Composition and kit for testing for occult blood in human and animal excretions, fluids, or tissue matrixes
JPH0641227B2 (en) * 1987-07-15 1994-06-01 富士写真フイルム株式会社 Recording material
FR2618334B1 (en) * 1987-07-22 1990-12-14 Somalead Sa LAXATIVE PHARMACEUTICAL PRODUCT
DE3724757A1 (en) * 1987-07-25 1989-02-09 Basf Ag BENZOPYRAN DERIVATIVES
EP0322669B1 (en) * 1987-12-18 1993-08-11 Fuji Photo Film Co., Ltd. Dry liquid analysis element
CA2009047C (en) * 1989-02-27 1999-06-08 Daniel Wayne Michael Microcapsules containing hydrophobic liquid core
US4946624A (en) * 1989-02-27 1990-08-07 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
US5196167A (en) * 1989-04-04 1993-03-23 Helena Laboratories Corporation Fecal occult blood test product with positive and negative controls
US5217874A (en) * 1989-04-04 1993-06-08 Helena Laboratories Corporation Fecal occult blood test product with positive and negative controls
US4961871A (en) * 1989-11-14 1990-10-09 The Procter & Gamble Company Powdered abrasive cleansers with encapsulated perfume
EP0449537B1 (en) * 1990-03-27 1996-03-06 The Wiggins Teape Group Limited Pressure-sensitive copying paper
DE4010641C2 (en) * 1990-04-03 1997-05-22 Bayer Ag Color former mixture for pressure and heat sensitive recording systems
KR930006431B1 (en) * 1990-10-11 1993-07-16 재단법인 한국화학연구소 Microcapsulation of drugs
US5084433A (en) * 1990-11-21 1992-01-28 Minnesota Mining And Manufacturing Company Carbonless paper printable in electrophotographic copiers
GB9110608D0 (en) * 1991-05-16 1991-07-03 Wiggins Teape Group Ltd Colour developer composition
US5516621A (en) * 1992-04-09 1996-05-14 Brother Kogyo Kabushiki Kaisha Photosensitive microcapsule having increased photosensitive sensitivity
US5302486A (en) * 1992-04-17 1994-04-12 Xerox Corporation Encapsulated toner process utilizing phase separation
US5922652A (en) 1992-05-05 1999-07-13 Procter & Gamble Microencapsulated oil field chemicals
US5305053A (en) * 1992-05-14 1994-04-19 Brother Kogyo Kabushiki Kaisha Image forming apparatus
DE69321765T3 (en) * 1992-06-04 2006-08-24 Arjo Wiggins Ltd., Basingstoke Pressure-sensitive recording material
US5334094A (en) * 1992-09-21 1994-08-02 Minnesota Mining And Manufacturing Company Carbonless pad assembly
GB9221621D0 (en) * 1992-10-15 1992-11-25 Wiggins Teape Group Ltd Solvents for use in pressure-sensitive record material
US5378413A (en) * 1993-01-21 1995-01-03 The United States Of America As Represented By The Secretary Of The Navy Process for preparing microcapsules having gelatin walls crosslinked with quinone
GB9313790D0 (en) * 1993-07-03 1993-08-18 Wiggins Teape Group The Ltd Pressure-sensitive copying material
JP3362745B2 (en) * 1993-07-28 2003-01-07 ブラザー工業株式会社 Photosensitive microcapsule type toner
US5552149A (en) * 1993-10-12 1996-09-03 Lignotech Usa, Inc. Method for microencapsulation of agriculturally active substances
CN1103540C (en) * 1993-11-15 2003-03-26 泽尼卡有限公司 Microcapsules containing suspensions of biologically active compound
US5846554A (en) * 1993-11-15 1998-12-08 Zeneca Limited Microcapsules containing suspensions of biologically active compounds and ultraviolet protectant
IL108835A (en) * 1994-03-03 1997-08-14 Ben Researchiversity Of The Ne Microencapsulated composition containing chlorpyrifos or endosulfan
US6531156B1 (en) 1994-04-15 2003-03-11 Temple University Aqueous solven encapsulation method, apparatus and microcapsules
US5449399A (en) 1994-06-07 1995-09-12 Minnesota Mining And Manufacturing Company Blendable writing instrument
US5529772A (en) * 1994-06-09 1996-06-25 Lignotech, Usa, Inc. Method for producing improved biological pesticides
GB9414637D0 (en) * 1994-07-20 1994-09-07 Wiggins Teape Group The Limite Presure-sensitive copying material
US5993842A (en) * 1994-12-12 1999-11-30 Zeneca Limited Microcapsules containing suspensions of biologically active compounds
JPH08206489A (en) * 1995-02-09 1996-08-13 Brother Ind Ltd Photo-curing composition and photosensitive capsule
GB9522233D0 (en) * 1995-10-31 1996-01-03 Wiggins Teape Group The Limite Pressure-sensitive copying paper
US5670145A (en) * 1996-01-30 1997-09-23 Troy Biosciences, Inc. Biologically active system for dispersion of pheromones
JPH09218514A (en) * 1996-02-09 1997-08-19 Brother Ind Ltd Photosetting composition and photosensitive capsule
JPH09274315A (en) * 1996-04-09 1997-10-21 Brother Ind Ltd Photosensitive recording medium
DE19634393A1 (en) * 1996-08-26 1998-03-05 Bayer Ag Process for the preparation of crosslinked polymers
US5961967A (en) * 1996-09-06 1999-10-05 3M Innovative Properties Company Multiphase candle containing locally enriched regions of deliverable actives
US6039901A (en) 1997-01-31 2000-03-21 Givaudan Roure Flavors Corporation Enzymatically protein encapsulating oil particles by complex coacervation
US5827913A (en) * 1997-02-05 1998-10-27 H.B. Fuller Licensing & Financing, Inc. Hot melt adhesive comprising an encapsulated ingredient
JPH10254130A (en) * 1997-03-11 1998-09-25 Brother Ind Ltd Photosensitive recording medium
JPH10319584A (en) * 1997-05-21 1998-12-04 Brother Ind Ltd Photosensitive recording material using microcapsules
US6106875A (en) * 1997-10-08 2000-08-22 Givaudan Roure (International) Sa Method of encapsulating flavors and fragrances by controlled water transport into microcapsules
US6045835A (en) * 1997-10-08 2000-04-04 Givaudan Roure (International) Sa Method of encapsulating flavors and fragrances by controlled water transport into microcapsules
JP4085449B2 (en) * 1997-10-09 2008-05-14 ブラザー工業株式会社 Electrophoretic display device, microcapsule and medium
JPH11184084A (en) 1997-12-22 1999-07-09 Brother Ind Ltd Quick hardening photosensitive composition and recording sheet
JPH11202484A (en) 1998-01-16 1999-07-30 Brother Ind Ltd Image forming medium
DE19911484B4 (en) * 1998-03-16 2008-04-03 Ricoh Co., Ltd. Material for indicating the history of the temperature, method for producing the same and method using the same
ES2339835T3 (en) 1998-09-04 2010-05-25 Chemipro Kasei Kaisha, Ltd. COLOR REVELATOR COMPOUND AND RECORDING MATERIAL.
JP4061734B2 (en) 1998-09-30 2008-03-19 ブラザー工業株式会社 Display medium display method and display device
DE19917300A1 (en) * 1999-04-16 2000-10-19 Drom Fragrances Int Kg Perfume application
US6866906B2 (en) * 2000-01-26 2005-03-15 International Paper Company Cut resistant paper and paper articles and method for making same
AU2002243599A1 (en) 2001-01-22 2002-07-30 Unified Environmental Services Group Production and use of biosolid granules
ATE454827T1 (en) * 2001-11-15 2010-01-15 San Ei Gen Ffi Inc MICRO CAPSULES AND ORAL PREPARATIONS CONTAINING SAME
US6974592B2 (en) * 2002-04-11 2005-12-13 Ocean Nutrition Canada Limited Encapsulated agglomeration of microcapsules and method for the preparation thereof
US20030216488A1 (en) 2002-04-18 2003-11-20 The Procter & Gamble Company Compositions comprising a dispersant and microcapsules containing an active material
AR040093A1 (en) * 2002-05-21 2005-03-16 Procter & Gamble CLEANING COMPOSITION THAT INCLUDES SUSPENDED PEARLS
US20030224030A1 (en) 2002-05-23 2003-12-04 Hirotaka Uchiyama Methods and articles for reducing airborne particulates
US20040032036A1 (en) * 2002-08-19 2004-02-19 Anandaraman Subramaniam Process for the preparation of flavor or fragrance microcapsules
US7473467B2 (en) * 2002-09-03 2009-01-06 Firmenich Sa Preparation of microcapsules
CN1703555B (en) 2002-09-13 2011-09-14 国际纸业公司 Paper with improved stiffness and bulk and method for making same
EP1402790A3 (en) * 2002-09-27 2004-05-06 Nestec S.A. Interface stabilisation of a product with 2 or more phases with a protein-polysaccharide complex
JP4833553B2 (en) * 2002-11-04 2011-12-07 オーシャン・ニュートリション・カナダ・リミテッド Microcapsules having a plurality of shells and methods for their preparation
US7108190B2 (en) * 2003-02-28 2006-09-19 Appleton Papers Inc. Token array and method employing authentication tokens bearing scent formulation information
EP1459887A3 (en) 2003-03-20 2005-03-16 Fuji Photo Film Co., Ltd. Image forming method and image exposure apparatus
US7282321B2 (en) 2003-03-26 2007-10-16 Fujifilm Corporation Lithographic printing method and presensitized plate
US20040251309A1 (en) * 2003-06-10 2004-12-16 Appleton Papers Inc. Token bearing magnetc image information in registration with visible image information
JP2005028774A (en) 2003-07-07 2005-02-03 Fuji Photo Film Co Ltd Original plate for planographic printing plate, and planographic printing method
JP2005059446A (en) 2003-08-15 2005-03-10 Fuji Photo Film Co Ltd Original printing plate for lithographic printing plate and method for lithographic printing
US7531365B2 (en) * 2004-01-08 2009-05-12 International Flavors & Fragrances Inc. Analysis of the headspace proximate a substrate surface containing fragrance-containing microcapsules
US20050153239A1 (en) 2004-01-09 2005-07-14 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor and lithographic printing method using the same
EP1733016B1 (en) 2004-04-09 2012-02-01 Unilever N.V. Granulate for use in a cleaning product and process for its manufacture
EP2246741A1 (en) 2004-05-19 2010-11-03 Fujifilm Corporation Image recording method
EP2618215B1 (en) 2004-05-31 2017-07-05 Fujifilm Corporation Method for producing a lithographic printing plate
JP2006021396A (en) 2004-07-07 2006-01-26 Fuji Photo Film Co Ltd Original lithographic printing plate and lithographic printing method
ATE398298T1 (en) 2004-07-20 2008-07-15 Fujifilm Corp IMAGE-PRODUCING MATERIAL
US7425406B2 (en) 2004-07-27 2008-09-16 Fujifilm Corporation Lithographic printing plate precursor and lithographic printing method
US20060032390A1 (en) 2004-07-30 2006-02-16 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor and lithographic printing method
US7745090B2 (en) 2004-08-24 2010-06-29 Fujifilm Corporation Production method of lithographic printing plate, lithographic printing plate precursor and lithographic printing method
JP2006062188A (en) 2004-08-26 2006-03-09 Fuji Photo Film Co Ltd Color image forming material and original plate of lithographic printing plate
JP2006068963A (en) 2004-08-31 2006-03-16 Fuji Photo Film Co Ltd Polymerizable composition, hydrophilic film using this composition and original lithographic printing plate
US7462437B2 (en) 2004-08-31 2008-12-09 Fujifilm Corporation Presensitized lithographic plate comprising support and hydrophilic image-recording layer
US20060150846A1 (en) 2004-12-13 2006-07-13 Fuji Photo Film Co. Ltd Lithographic printing method
JP2006181838A (en) 2004-12-27 2006-07-13 Fuji Photo Film Co Ltd Original plate of lithographic printing plate
US8034450B2 (en) * 2005-01-21 2011-10-11 Ocean Nutrition Canada Limited Microcapsules and emulsions containing low bloom gelatin and methods of making and using thereof
EP1685957B1 (en) 2005-01-26 2013-12-11 FUJIFILM Corporation Packaged body of lithographic printing plate precursors
WO2006091645A2 (en) 2005-02-23 2006-08-31 Blue Water Investments Manufacturing of bioorganic-augmented high nitrogen-containing inorganic fertilizer
EP1696268B1 (en) 2005-02-28 2016-11-09 FUJIFILM Corporation Lithographic printing plate precursor
US8192519B2 (en) * 2005-03-09 2012-06-05 Vitag Corporation Beneficiated, heat-dried biosolid pellets
JP5302670B2 (en) 2005-03-11 2013-10-02 インターナショナル・ペーパー・カンパニー Compositions containing expandable microspheres and ionic compounds, and methods for making and using these compositions
EP1705241B1 (en) 2005-03-23 2008-08-13 Unilever N.V. Detergent compositions in tablet form
WO2006104623A2 (en) 2005-03-25 2006-10-05 Appleton Papers Inc. Adhesively securable stock packaging materials
JP2006272782A (en) 2005-03-29 2006-10-12 Fuji Photo Film Co Ltd Planographic printing plate
US9968120B2 (en) 2006-05-17 2018-05-15 Dsm Nutritional Products Ag Homogenized formulations containing microcapsules and methods of making and using thereof
EP1746152A1 (en) 2005-07-20 2007-01-24 Unilever N.V. Detergent compositions
JP4792326B2 (en) 2005-07-25 2011-10-12 富士フイルム株式会社 Planographic printing plate preparation method and planographic printing plate precursor
JP4815270B2 (en) 2005-08-18 2011-11-16 富士フイルム株式会社 Method and apparatus for producing a lithographic printing plate
JP4759343B2 (en) 2005-08-19 2011-08-31 富士フイルム株式会社 Planographic printing plate precursor and planographic printing method
CA2622881C (en) 2005-09-15 2015-01-27 Vitag Llc Organic containing sludge to fertilizer alkaline conversion process
GB0524659D0 (en) 2005-12-02 2006-01-11 Unilever Plc Improvements relating to fabric treatment compositions
US9695092B2 (en) 2006-02-23 2017-07-04 Anuvia Plant Nutrients Corporation Process for treating sludge and manufacturing bioorganically-augmented high nitrogen-containing inorganic fertilizer
US20070197670A1 (en) * 2006-02-23 2007-08-23 International Business Machines Corporation Rigidized compliant foam and method for implementing a rigidized compliant foam
EP1836897A1 (en) * 2006-03-22 2007-09-26 Nestec S.A. A solid product comprising oil-droplets
EP2040682B1 (en) * 2006-06-05 2017-07-26 DSM Nutritional Products AG Microcapsules with improved shells
JP2007328172A (en) * 2006-06-08 2007-12-20 Fuji Xerox Co Ltd Image forming apparatus and image forming method
JP4730235B2 (en) * 2006-07-13 2011-07-20 富士ゼロックス株式会社 Image forming apparatus
JP5185126B2 (en) 2006-09-29 2013-04-17 日本製紙株式会社 Thermal recording material
US7935201B2 (en) * 2006-11-29 2011-05-03 Wausau Paper Mills, Llc Non-slip masking product, and methods
US8771924B2 (en) 2006-12-26 2014-07-08 Fujifilm Corporation Polymerizable composition, lithographic printing plate precursor and lithographic printing method
JP4945432B2 (en) 2006-12-28 2012-06-06 富士フイルム株式会社 Preparation method of lithographic printing plate
CN101641087B (en) * 2007-01-10 2013-08-21 加拿大海洋营养食品有限公司 Vegetarian microcapsules
EP2447779A1 (en) 2007-01-17 2012-05-02 Fujifilm Corporation Method for preparation of lithographic printing plate
JP4881756B2 (en) 2007-02-06 2012-02-22 富士フイルム株式会社 Photosensitive composition, lithographic printing plate precursor, lithographic printing method, and novel cyanine dye
CA2678548C (en) * 2007-02-16 2013-04-23 Vitag Corporation Process for treating sludge and manufacturing bioorganically-augmented high nitrogen-containing inorganic fertilizer
JP2008230028A (en) 2007-03-20 2008-10-02 Fujifilm Corp On-machine developable original plate of lithographic printing plate
JP2008230024A (en) 2007-03-20 2008-10-02 Fujifilm Corp Lithographic printing plate precursor and method of preparing lithographic printing plate
EP1972440B1 (en) 2007-03-23 2010-06-23 FUJIFILM Corporation Negative lithographic printing plate precursor and lithographic printing method using the same
EP1974914B1 (en) 2007-03-29 2014-02-26 FUJIFILM Corporation Method of preparing lithographic printing plate
EP1975710B1 (en) 2007-03-30 2013-10-23 FUJIFILM Corporation Plate-making method of lithographic printing plate precursor
EP1975706A3 (en) 2007-03-30 2010-03-03 FUJIFILM Corporation Lithographic printing plate precursor
JP5046744B2 (en) 2007-05-18 2012-10-10 富士フイルム株式会社 Planographic printing plate precursor and printing method using the same
BRPI0811425A2 (en) * 2007-05-21 2014-11-04 Firmenich & Cie BIG COACERVED CAPSULES
EP2006738B1 (en) 2007-06-21 2017-09-06 Fujifilm Corporation Lithographic printing plate precursor
US8426102B2 (en) 2007-06-22 2013-04-23 Fujifilm Corporation Lithographic printing plate precursor and plate making method
DE602008002963D1 (en) 2007-07-02 2010-11-25 Fujifilm Corp Planographic printing plate precursor and planographic printing method with it
JP2009069761A (en) 2007-09-18 2009-04-02 Fujifilm Corp Plate making method for planographic printing plate
US20090078918A1 (en) * 2007-09-25 2009-03-26 Cary Michael Huettner Methods and Structures With Fire Retardant Spheres for Implementing Enhanced Fire Protection
JP5244518B2 (en) 2007-09-28 2013-07-24 富士フイルム株式会社 Planographic printing plate precursor and lithographic printing plate preparation method
JP5002399B2 (en) 2007-09-28 2012-08-15 富士フイルム株式会社 Processing method of lithographic printing plate precursor
JP5055077B2 (en) 2007-09-28 2012-10-24 富士フイルム株式会社 Image forming method and planographic printing plate precursor
EP2042311A1 (en) 2007-09-28 2009-04-01 FUJIFILM Corporation Lithographic printing plate precursor, method of preparing lithographic printing plate and lithographic printing method
JP5322537B2 (en) 2007-10-29 2013-10-23 富士フイルム株式会社 Planographic printing plate precursor
EP2070510A1 (en) * 2007-12-10 2009-06-17 Takasago International Corporation Personal cleansing system
JP2009139852A (en) 2007-12-10 2009-06-25 Fujifilm Corp Method of preparing lithographic printing plate and lithographic printing plate precursor
JP5231189B2 (en) 2008-01-09 2013-07-10 ローム アンド ハース カンパニー Method for producing uniformly sized polymer beads
JP2009186997A (en) 2008-01-11 2009-08-20 Fujifilm Corp Lithographic printing plate precursor, method of preparing lithographic printing plate and lithographic printing method
JP5155677B2 (en) 2008-01-22 2013-03-06 富士フイルム株式会社 Planographic printing plate precursor and its plate making method
JP2009184188A (en) 2008-02-05 2009-08-20 Fujifilm Corp Lithographic printing original plate and printing method
JP5150287B2 (en) 2008-02-06 2013-02-20 富士フイルム株式会社 Preparation method of lithographic printing plate and lithographic printing plate precursor
JP5175582B2 (en) 2008-03-10 2013-04-03 富士フイルム株式会社 Preparation method of lithographic printing plate
JP2009214428A (en) 2008-03-11 2009-09-24 Fujifilm Corp Original plate of lithographic printing plate and lithographic printing method
JP2009236942A (en) 2008-03-25 2009-10-15 Fujifilm Corp Planographic printing plate precursor and plate making method of the same
US7923197B2 (en) 2008-03-25 2011-04-12 Fujifilm Corporation Lithographic printing plate precursor
JP5422146B2 (en) 2008-03-25 2014-02-19 富士フイルム株式会社 Processing solution for preparing a lithographic printing plate and processing method of a lithographic printing plate precursor
JP5020871B2 (en) 2008-03-25 2012-09-05 富士フイルム株式会社 Planographic printing plate manufacturing method
EP2259137B1 (en) 2008-03-27 2016-08-31 FUJIFILM Corporation Method for producing a of lithographic printing plate
JP5183268B2 (en) 2008-03-27 2013-04-17 富士フイルム株式会社 Planographic printing plate precursor
EP2105298B1 (en) 2008-03-28 2014-03-19 FUJIFILM Corporation Negative-working lithographic printing plate precursor and method of lithographic printing using same
JP2009244421A (en) 2008-03-28 2009-10-22 Fujifilm Corp Plate-making method of lithographic printing plate
JP4914864B2 (en) 2008-03-31 2012-04-11 富士フイルム株式会社 Preparation method of lithographic printing plate
EP2110261B1 (en) 2008-04-18 2018-03-28 FUJIFILM Corporation Aluminum alloy plate for lithographic printing plate, ligthographic printing plate support, presensitized plate, method of manufacturing aluminum alloy plate for lithographic printing plate and method of manufacturing lithographic printing plate support
US8067089B2 (en) * 2008-05-01 2011-11-29 Appleton Papers Inc. Cationic microcapsule particles
US8071214B2 (en) * 2008-05-01 2011-12-06 Appleton Papers Inc. Particle with selected permeance wall
US20090274906A1 (en) * 2008-05-01 2009-11-05 Appleton Papers Inc. Particle with low permeance wall
JP5296434B2 (en) 2008-07-16 2013-09-25 富士フイルム株式会社 Master for lithographic printing plate
CN102137878B (en) 2008-08-28 2014-06-18 国际纸业公司 Expandable microspheres and methods of making and using the same
JP5444933B2 (en) 2008-08-29 2014-03-19 富士フイルム株式会社 Negative-type planographic printing plate precursor and planographic printing method using the same
JP5364513B2 (en) 2008-09-12 2013-12-11 富士フイルム株式会社 Developer for lithographic printing plate precursor and method for producing lithographic printing plate
JP5466462B2 (en) 2008-09-18 2014-04-09 富士フイルム株式会社 Planographic printing plate precursor, method for producing a planographic printing plate, and planographic printing plate
JP5408942B2 (en) 2008-09-22 2014-02-05 富士フイルム株式会社 Planographic printing plate precursor and plate making method
JP2010097175A (en) 2008-09-22 2010-04-30 Fujifilm Corp Method of preparing lithographic printing plate and lithographic printing plate precursor
JP5449898B2 (en) 2008-09-22 2014-03-19 富士フイルム株式会社 Planographic printing plate precursor and printing method using the same
EP2330464A4 (en) 2008-09-24 2012-03-14 Fujifilm Corp Process for producing lithographic printing plate
EP2168767A1 (en) 2008-09-24 2010-03-31 Fujifilm Corporation Method of preparing lithographic printing plate
JP5433351B2 (en) 2008-09-25 2014-03-05 富士フイルム株式会社 Planographic printing plate precursor and lithographic printing plate manufacturing method
JP2010102322A (en) 2008-09-26 2010-05-06 Fujifilm Corp Method for making lithographic printing plate
ES2385762T3 (en) 2008-09-30 2012-07-31 The Procter & Gamble Company Composition comprising microcapsules
JP5140540B2 (en) 2008-09-30 2013-02-06 富士フイルム株式会社 Preparation of lithographic printing plate precursor and lithographic printing plate
JP5660268B2 (en) 2008-09-30 2015-01-28 富士フイルム株式会社 Planographic printing plate precursor, lithographic printing plate making method and polymerizable monomer
US7915215B2 (en) 2008-10-17 2011-03-29 Appleton Papers Inc. Fragrance-delivery composition comprising boron and persulfate ion-crosslinked polyvinyl alcohol microcapsules and method of use thereof
US20120021358A1 (en) 2008-11-26 2012-01-26 Fujifilm Corporation Process for making lithographic printing plate, developer for lithographic printing plate precursor, and replenisher for lithographic printing plate precursor development
CN101844061B (en) * 2009-03-25 2013-03-27 中国科学院大连化学物理研究所 Method for preparing microcapsules using starch sodium octenyl succinate(SSOS) as wall material
US8455098B2 (en) * 2009-04-07 2013-06-04 Appleton Papers Inc. Encapsulated solid hydrophilic particles
US20120213764A1 (en) 2009-09-25 2012-08-23 B.R.A.I.N. Biotechnology Research And Information Network Ag Novel method for the production of a antimicrobial peptide
EP2336286A1 (en) 2009-12-18 2011-06-22 The Procter & Gamble Company Composition comprising microcapsules
EP2336285B1 (en) 2009-12-18 2013-09-04 The Procter & Gamble Company Composition comprising microcapsules
WO2011084141A2 (en) * 2009-12-21 2011-07-14 Appleton Papers Inc. Hydrophilic liquid encapsulates
ES2741133T3 (en) 2009-12-30 2020-02-10 Anuvia Plant Nutrients Holdings Llc High value fertilizer bioorganically increased
JP5537980B2 (en) 2010-02-12 2014-07-02 富士フイルム株式会社 Planographic printing plate precursor and plate making method
US9743688B2 (en) 2010-03-26 2017-08-29 Philip Morris Usa Inc. Emulsion/colloid mediated flavor encapsulation and delivery with tobacco-derived lipids
BR112012024804B1 (en) 2010-03-30 2020-12-15 Unilever N.V PROCESS FOR THE INCORPORATION OF MICROCASULES WITH ANIONIC LOAD IN A STRUCTURED CONCENTRATED LIQUID DETERGENT
EP2553072B1 (en) 2010-04-01 2015-05-06 Unilever PLC Structuring detergent liquids with hydrogenated castor oil
US20110269657A1 (en) 2010-04-28 2011-11-03 Jiten Odhavji Dihora Delivery particles
CN102985054B (en) 2010-06-30 2015-11-25 弗门尼舍有限公司 Solid core core coacervated capsules
US8936030B2 (en) 2011-03-25 2015-01-20 Katherine Rose Kovarik Nail polish remover method and device
EP2495300A1 (en) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuring detergent liquids with hydrogenated castor oil
CN104245631A (en) 2011-03-28 2014-12-24 维塔格控股有限责任公司 High value organic-enhanced inorganic fertilizers
JP5989102B2 (en) 2011-06-07 2016-09-07 フイルメニツヒ ソシエテ アノニムFirmenich Sa Core-shell capsule
US20120095605A1 (en) 2011-09-17 2012-04-19 Tran Bao Q Smart building systems and methods
US8359750B2 (en) 2011-12-28 2013-01-29 Tran Bao Q Smart building systems and methods
CN104245910B (en) 2012-04-23 2017-02-15 荷兰联合利华有限公司 Externally structured aqueous isotropic liquid detergent compositions
CN104364362A (en) 2012-04-23 2015-02-18 荷兰联合利华有限公司 Externally structured aqueous isotropic liquid laundry detergent compositions
EP2841551B1 (en) 2012-04-23 2015-12-09 Unilever Plc. Externally structured aqueous isotropic liquid detergent compositions
US10092023B2 (en) 2012-05-24 2018-10-09 Firmenich Sa Hybrid coacervate capsules
TWI500701B (en) 2012-10-08 2015-09-21 Rohm & Haas Curing of aromatic carbodiimides
AU2013351426B2 (en) 2012-11-29 2015-11-26 Unilever Plc Polymer structured aqueous detergent compositions
WO2014176306A1 (en) 2013-04-23 2014-10-30 Montecito Bio Sciences Ltd Flow through testing system with pressure indicator
US8951708B2 (en) 2013-06-05 2015-02-10 Xerox Corporation Method of making toners
US20150099412A1 (en) * 2013-10-09 2015-04-09 Shurtape Technologies, Llc Fragrance adhesive tape
EP2926659A1 (en) 2014-04-04 2015-10-07 LANXESS Deutschland GmbH Biocidal agent
BR112016024695A2 (en) 2014-04-22 2017-08-15 Procter & Gamble release system for applying hair treatment comprising a composition
US9579673B2 (en) 2014-06-09 2017-02-28 The Procter & Gamble Company Flushing dispensers for delivering a consistent consumer experience
CN106457273B (en) 2014-06-09 2019-05-07 宝洁公司 For delivering the flushing distributor of consistent consumer experience
BR112016028703A2 (en) 2014-06-09 2017-08-22 Procter & Gamble flush dispensers for a consistent consumer experience
WO2015191494A1 (en) 2014-06-09 2015-12-17 The Procter & Gamble Company Dispensers for delivering a consistent consumer experience
EP3151977B1 (en) 2014-06-09 2018-07-25 The Procter and Gamble Company Flushing dispensers for delivering a consistent consumer experience
CN106659280A (en) 2014-06-09 2017-05-10 宝洁公司 Articles providing long lasting fragrances
US9839930B2 (en) 2015-06-09 2017-12-12 The Procter & Gamble Company Flushing dispensers for delivering a consistent consumer experience
US9925550B2 (en) 2014-06-09 2018-03-27 The Procter & Gamble Company Articles providing long lasting fragrances
US9579677B2 (en) 2014-06-09 2017-02-28 The Procter & Gamble Company Flushing dispensers for delivering a consistent consumer experience
US9550200B2 (en) 2014-06-09 2017-01-24 The Procter & Gamble Company Dispensers for delivering a consistent consumer experience
BR112016028697A2 (en) 2014-06-09 2017-08-22 Procter & Gamble articles that provide long lasting fragrances
US9902861B2 (en) 2014-06-21 2018-02-27 Klt Technologies Single color reversible temperature indicator
CA3099534C (en) 2014-06-30 2023-01-03 The Procter & Gamble Company Antiperspirant products with improved longevity of fragrance
WO2016003948A1 (en) 2014-06-30 2016-01-07 The Procter & Gamble Company Personal care compositions and methods
CN107148263B (en) 2014-11-10 2021-07-06 宝洁公司 Personal care compositions
US9951294B2 (en) 2014-12-16 2018-04-24 Noxell Corporation Coated microcapsules
CN107249545B (en) 2014-12-16 2021-05-25 诺赛尔股份有限公司 Composition providing delayed release of active substances
WO2016100479A1 (en) 2014-12-16 2016-06-23 The Procter & Gamble Company Coated microcapsules
WO2016100499A1 (en) 2014-12-16 2016-06-23 The Procter & Gamble Company Coated microcapsules
CN106999896B (en) 2014-12-16 2020-10-30 诺赛尔股份有限公司 Coated microcapsules
CN107206343B (en) 2015-02-06 2021-02-05 弗门尼舍有限公司 Microcapsules imparting strong vanilla odor notes
MX2017011309A (en) 2015-03-03 2018-01-23 Procter & Gamble Hair conditioning compositions with microcapsules.
MX2017011308A (en) 2015-03-03 2018-04-11 Procter & Gamble Hair conditioning compositions with microcapsules.
EP3302782A4 (en) 2015-06-05 2019-01-09 Anuvia Plant Nutrients Holdings, LLC High value organic containing fertilizers and methods of manufacture
CN107847768A (en) 2015-06-30 2018-03-27 宝洁公司 For the method for the composition for preparing multiple colonies comprising microcapsules
WO2017004339A1 (en) 2015-06-30 2017-01-05 The Procter & Gamble Company Composition comprising multiple populations of microcapsules comprising perfume
US11820960B2 (en) 2015-06-30 2023-11-21 The Procter & Gamble Company Compositions containing multiple populations of microcapsules
WO2017044083A1 (en) 2015-09-09 2017-03-16 The Procter & Gamble Company Dispensers for dispensing microcapsules
WO2017044085A1 (en) 2015-09-09 2017-03-16 The Procter & Gamble Company Dispensers for dispensing microcapsules
EP3359296A1 (en) 2015-09-09 2018-08-15 The Procter and Gamble Company Dispensers for dispensing microcapsules
WO2017044086A1 (en) 2015-09-09 2017-03-16 The Procter & Gamble Company Dispensers for microcapsules
WO2017044087A1 (en) 2015-09-09 2017-03-16 The Procter & Gamble Company Dispensers for dispensing microcapsules
WO2017074997A1 (en) 2015-10-27 2017-05-04 Encapsys, Llc Encapsulation
US10292915B2 (en) 2016-01-06 2019-05-21 The Procter & Gamble Company Antiperspirant compositions
EP3408363A1 (en) 2016-01-26 2018-12-05 The Procter and Gamble Company Treatment compositions
CN108884420B (en) 2016-04-18 2021-12-31 蒙诺苏尔有限公司 Perfume microcapsules and related films and detergent compositions
WO2018030431A1 (en) 2016-08-09 2018-02-15 Takasago International Corporation Solid composition comprising free and encapsulated fragrances
EP3535621A1 (en) 2016-11-03 2019-09-11 3M Innovative Properties Company Compositions including a photolatent amine, camphorquinone, and a coumarin and related methods
CA3042864A1 (en) 2016-11-03 2018-05-11 3M Innovative Properties Company Composition including a polythiol, a polyepoxide, a photolatent base, and an amine and methods relating to the composition
CA3051268C (en) 2016-11-21 2022-11-29 Bell Flavors & Fragrances, Inc. Malodor counteractant composition and methods
WO2018210524A1 (en) 2017-05-15 2018-11-22 Unilever Plc Composition
WO2018210700A1 (en) 2017-05-15 2018-11-22 Unilever Plc Composition
WO2018210523A1 (en) 2017-05-15 2018-11-22 Unilever Plc Composition
WO2018210522A1 (en) 2017-05-15 2018-11-22 Unilever Plc Composition
US10870609B2 (en) 2018-08-16 2020-12-22 Anuvia Plant Nutrients Corporation Reactive inorganic coatings for agricultural fertilizers
WO2020079556A1 (en) 2018-10-15 2020-04-23 3M Innovative Properties Company Composition including a polythiol, a polyepoxide, an amine catalyst, and a conductive filler and methods relating to the composition
EP3883999A1 (en) 2018-11-19 2021-09-29 3M Innovative Properties Company Composition including a polythiol, a polyepoxide, a polymeric catalyst, and a conductive filler and methods relating to the composition
CN112770713A (en) 2019-01-11 2021-05-07 恩盖普有限公司 Incorporation of chitosan into microcapsule walls
ES2948614T3 (en) 2020-04-21 2023-09-14 Takasago Perfumery Co Ltd Encapsulated fragrance composition
EP3900697B1 (en) 2020-04-21 2023-03-15 Takasago International Corporation Fragrance composition
EP4175758A1 (en) 2020-07-06 2023-05-10 Coty Inc. Dual reservoir spray dispenser

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE454386C (en) * 1924-05-27 1928-01-06 Chemische Produkte Vormals H S Process for the production of pharmaceutical and dietetic preparations in spherical form
US2183053A (en) * 1936-12-03 1939-12-12 Atlantic Coast Fisheries Co Vitamin preparation and method of making same
DE837853C (en) * 1937-05-12 1952-05-02 Ncr Co Pressure sensitive recording material
GB514047A (en) * 1938-03-25 1939-10-30 Ernest Edmund Wells Improvements in and relating to processes for manufacturing insulated products in the form of powder
US2410110A (en) * 1943-01-14 1946-10-29 Brewer & Company Inc Method of making tablets
BE485589A (en) * 1944-01-31
US2548365A (en) * 1948-07-13 1951-04-10 Ncr Co Process for making pressure sensitive record materials

Cited By (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3092553A (en) * 1959-01-30 1963-06-04 Jr Carl E Fisher Pharmaceutical preparations and method and apparatus for making same
US3238103A (en) * 1961-04-26 1966-03-01 Clarence A Vogenthaler Therapeutic composition and method of making it
US3455848A (en) * 1964-05-05 1969-07-15 Ncr Co Polyurethane foam-producing compositions comprising microencapsulated particles and a method of making foams therefrom
US3460972A (en) * 1965-09-29 1969-08-12 Battelle Development Corp Liquid encapsulation
US3469439A (en) * 1968-02-21 1969-09-30 Sanford B Roberts Means for measuring distributed forces using microcapsules
US4428869A (en) 1981-08-20 1984-01-31 International Flavors & Fragrances Inc. Cologne consisting of microcapsule suspension
US4599271A (en) 1983-06-09 1986-07-08 Moore Business Forms, Inc. Microencapsulation of polyisocyanates by interchange of multiple
US4471880A (en) 1983-10-03 1984-09-18 Rubbermaid Incorporated Center press outer seal bowl lid
US5035896A (en) * 1988-06-15 1991-07-30 Warner-Lambert Company Water insoluble drugs coated by coacervated fish gelatin
US4927802A (en) 1988-12-09 1990-05-22 Ppg Industries, Inc. Pressure-sensitive multi-part record unit
US5811127A (en) * 1992-06-15 1998-09-22 Emisphere Technologies, Inc. Desferrioxamine oral delivery system
US5840340A (en) * 1992-06-15 1998-11-24 Emisphere Technologies, Inc. Proteinoid carriers and methods for preparation and use thereof
US5714167A (en) * 1992-06-15 1998-02-03 Emisphere Technologies, Inc. Active agent transport systems
US5578323A (en) * 1992-06-15 1996-11-26 Emisphere Technologies, Inc. Proteinoid carriers and methods for preparation and use thereof
US5601846A (en) * 1992-06-15 1997-02-11 Emisphere Technologies, Inc. Proteinoid microspheres and methods for preparation and use thereof
US6071538A (en) * 1992-06-15 2000-06-06 Emisphere Technologies, Inc. Oral delivery composition comprising supramolecular complex
US6099856A (en) * 1992-06-15 2000-08-08 Emisphere Technologies, Inc. Active agent transport systems
US6348207B1 (en) 1992-06-15 2002-02-19 Emisiphere Technologies, Inc. Orally deliverable supramolecular complex
US6221367B1 (en) 1992-06-15 2001-04-24 Emisphere Technologies, Inc. Active agent transport systems
US6413550B1 (en) 1992-06-15 2002-07-02 Emisphere Technologies, Inc. Proteinoid carriers and methods for preparation and use thereof
US6245359B1 (en) 1992-06-15 2001-06-12 Emisphere Technologies, Inc. Active agent transport systems
US5447728A (en) * 1992-06-15 1995-09-05 Emisphere Technologies, Inc. Desferrioxamine oral delivery system
US6375872B1 (en) 1992-11-17 2002-04-23 Moore Business Forms Microencapsulated adhesive
US5540939A (en) 1992-12-21 1996-07-30 Emisphere Technologies, Inc. Modified hydrolyzed vegetable protein microspheres and methods for preparation and use thereof
US5972387A (en) 1992-12-21 1999-10-26 Emisphere Technologies, Inc. Modified hydrolyzed vegetable protein microspheres and methods for preparation and use thereof
US5766633A (en) 1993-04-22 1998-06-16 Emisphere Technologies, Inc. Oral drug delivery compositions and methods
US5643957A (en) * 1993-04-22 1997-07-01 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5709861A (en) * 1993-04-22 1998-01-20 Emisphere Technologies, Inc. Compositions for the delivery of antigens
US5958457A (en) * 1993-04-22 1999-09-28 Emisphere Technologies, Inc. Compositions for the delivery of antigens
US5955503A (en) * 1993-04-22 1999-09-21 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6100298A (en) * 1993-04-22 2000-08-08 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5792451A (en) * 1994-03-02 1998-08-11 Emisphere Technologies, Inc. Oral drug delivery compositions and methods
US5935601A (en) * 1994-04-22 1999-08-10 Emisphere Technologies, Inc. Modified amino acids for drug delivery
US5629020A (en) * 1994-04-22 1997-05-13 Emisphere Technologies, Inc. Modified amino acids for drug delivery
US6180140B1 (en) 1994-04-22 2001-01-30 Emisphere Technologies, Inc. Modified amino acids for drug delivery
US5541155A (en) 1994-04-22 1996-07-30 Emisphere Technologies, Inc. Acids and acid salts and their use in delivery systems
US5976569A (en) 1994-09-29 1999-11-02 Emisphere Technologies, Inc. Diketopiperazine-based delivery systems
US5693338A (en) 1994-09-29 1997-12-02 Emisphere Technologies, Inc. Diketopiperazine-based delivery systems
US6331318B1 (en) 1994-09-30 2001-12-18 Emisphere Technologies Inc. Carbon-substituted diketopiperazine delivery systems
US5616315A (en) * 1994-10-13 1997-04-01 Gillette Canada Inc. Particles including degradable material and anti-microbial agent
US5660817A (en) 1994-11-09 1997-08-26 Gillette Canada, Inc. Desensitizing teeth with degradable particles
US5741479A (en) 1994-11-09 1998-04-21 Gillette Canada Inc. Desensitizing teeth with degradable particles
US5603952A (en) * 1994-12-30 1997-02-18 Tastemaker Method of encapsulating food or flavor particles using warm water fish gelatin, and capsules produced therefrom
US5965121A (en) 1995-03-31 1999-10-12 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6090958A (en) 1995-03-31 2000-07-18 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6428780B2 (en) 1995-03-31 2002-08-06 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5989539A (en) 1995-03-31 1999-11-23 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5650386A (en) 1995-03-31 1997-07-22 Emisphere Technologies, Inc. Compositions for oral delivery of active agents
US6346242B1 (en) 1995-03-31 2002-02-12 Emishpere Technologies, Inc. Compounds and compositions for delivering active agents
US6071510A (en) 1995-03-31 2000-06-06 Emisphere Technologies, Inc. Modified amino acids and compositions comprising the same for delivering active agents
US5866536A (en) * 1995-03-31 1999-02-02 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5820881A (en) * 1995-04-28 1998-10-13 Emisphere Technologies, Inc. Microspheres of diamide-dicarboxylic acids
US6100285A (en) 1995-06-07 2000-08-08 Emisphere Technologies, Inc. Method of solubilizing itraconazole
US6051258A (en) 1995-06-07 2000-04-18 Emisphere Technologies, Inc. Proteinoid emulsions and methods for preparation and use thereof
US6461545B1 (en) 1995-06-07 2002-10-08 Emisphere Technologies, Inc. Method of solubilizing and encapsulating itraconazole
US5824345A (en) * 1995-06-07 1998-10-20 Emisphere Technologies, Inc. Fragrances and flavorants
US5667806A (en) 1995-06-07 1997-09-16 Emisphere Technologies, Inc. Spray drying method and apparatus
US5750147A (en) 1995-06-07 1998-05-12 Emisphere Technologies, Inc. Method of solubilizing and encapsulating itraconazole
US6084112A (en) 1995-09-11 2000-07-04 Emisphere Technologies, Inc. Method for preparing ω-aminoalkanoic acid derivatives from cycloalkanones
US6592916B2 (en) 1996-01-08 2003-07-15 Ajinomoto Co., Inc. Edible microcapsule and food containing the same
US6475542B1 (en) * 1996-01-08 2002-11-05 Ajinomoto Co., Inc. Edible microcapsule and food containing the same
US7417022B2 (en) 1996-03-29 2008-08-26 Mhr Institutional Partners Iia Lp Compounds and compositions for delivering active agents
US6375983B1 (en) 1996-06-14 2002-04-23 Emisphere Technologies, Inc. Microencapsulated fragrances and method for preparation
US5939381A (en) 1997-02-07 1999-08-17 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6313088B1 (en) 1997-02-07 2001-11-06 Emisphere Technologies, Inc. 8-[(2-hydroxy-4-methoxy benzoyl) amino]-octanoic acid compositions for delivering active agents
US6060513A (en) 1997-02-07 2000-05-09 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US6242495B1 (en) 1997-02-07 2001-06-05 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5990166A (en) 1997-02-07 1999-11-23 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5879681A (en) * 1997-02-07 1999-03-09 Emisphere Technolgies Inc. Compounds and compositions for delivering active agents
US5876710A (en) * 1997-02-07 1999-03-02 Emisphere Technologies Inc. Compounds and compositions for delivering active agents
US7553872B2 (en) 1997-02-07 2009-06-30 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5804688A (en) * 1997-02-07 1998-09-08 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5863944A (en) 1997-04-30 1999-01-26 Emisphere Technologies, Inc. Compounds and compositions for delivering active agents
US5962710A (en) 1997-05-09 1999-10-05 Emisphere Technologies, Inc. Method of preparing salicyloylamino acids
US6103378A (en) 1998-11-23 2000-08-15 The Mead Company Capsules having discrete solvent/color former and diluent capsule encapsulated phases
US20050165131A1 (en) * 2003-10-06 2005-07-28 Terry Stovold Invisible ink
US20080113862A1 (en) * 2003-10-06 2008-05-15 Nocopi Technologies, Inc. Invisible Ink And Scratch Pad
US20050075420A1 (en) * 2003-10-06 2005-04-07 Terry Stovold Invisible ink
US8053494B2 (en) 2003-10-06 2011-11-08 Nocopi Technologies, Inc. Invisible ink and scratch pad
US9186642B2 (en) 2010-04-28 2015-11-17 The Procter & Gamble Company Delivery particle
US9993793B2 (en) 2010-04-28 2018-06-12 The Procter & Gamble Company Delivery particles
US11096875B2 (en) 2010-04-28 2021-08-24 The Procter & Gamble Company Delivery particle
US8927026B2 (en) 2011-04-07 2015-01-06 The Procter & Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules
US8980292B2 (en) 2011-04-07 2015-03-17 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
US9162085B2 (en) 2011-04-07 2015-10-20 The Procter & Gamble Company Personal cleansing compositions with increased deposition of polyacrylate microcapsules
US9561169B2 (en) 2011-04-07 2017-02-07 The Procter & Gamble Company Conditioner compositions with increased deposition of polyacrylate microcapsules
US10143632B2 (en) 2011-04-07 2018-12-04 The Procter And Gamble Company Shampoo compositions with increased deposition of polyacrylate microcapsules

Also Published As

Publication number Publication date
CH327303A (en) 1958-01-31
BE530009A (en)
CH334334A (en) 1958-11-30
NL95045C (en)
GB759800A (en) 1956-10-24
NL95043C (en)
DE1017905B (en) 1957-10-17
GB873943A (en) 1961-08-02
FR1114851A (en) 1956-04-17
BE530008A (en)
BE530010A (en)
DE1010822B (en) 1957-06-19
US2800458A (en) 1957-07-23
CH330500A (en) 1958-06-15
FR1165805A (en) 1958-10-29
NL95044C (en)
FR1114850A (en) 1956-04-17
GB751600A (en) 1956-06-27
GB750972A (en) 1956-06-20

Similar Documents

Publication Publication Date Title
USRE24899E (en) Oil-containrab
US2800457A (en) Oil-containing microscopic capsules and method of making them
US3190837A (en) Making individual capsules by dual deposition
US2712507A (en) Pressure sensitive record material
US3856699A (en) Process for producing capsules having walls of a waxy material
US3418250A (en) Microcapsules, process for their formation and transfer sheet record material coated therewith
US2969331A (en) Process of making dual-walled oil containing capsules
US2711375A (en) Pressure sensitive manifold sheet
US3041289A (en) Method of making walled clusters of capsules
US3341466A (en) Process for making capsules
US2980941A (en) Cleaning sheet
US3516943A (en) Replacement of capsule contents by diffusion
US3179600A (en) Minute color-forming capsules and record material provided with such
US3697437A (en) Encapsulation process by complex coacervation using inorganic polyphosphates and organic hydrophilic polymeric material
US2730457A (en) Pressure responsive record materials
US3888689A (en) Aqueous printing ink containing perfume-containing microcapsules
JPS5812055B2 (en) Method for curing capsules containing hydrophobic oil droplets
US3533958A (en) Process for making minute capsules
DE1142154B (en) Process for the production of microscopic capsules containing OE1 inside
US3897361A (en) Process for producing microcapsules
DE1096038B (en) Process for the production of capsules containing oil
DE1912323B2 (en) METHOD OF MANUFACTURING MICROCAPSULES
US4171981A (en) Process for the production of hot melt coating compositions containing microcapsules
US3565819A (en) Process of producing microcapsules
US3804775A (en) Method of preparing microcapsules