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Publication numberUS3016308 A
Publication typeGrant
Publication dateJan 9, 1962
Filing dateAug 6, 1957
Priority dateAug 6, 1957
Publication numberUS 3016308 A, US 3016308A, US-A-3016308, US3016308 A, US3016308A
InventorsMacaulay Norman
Original AssigneeMoore Business Forms Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US 3016308 A
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Description  (OCR text may contain errors)

Jan. 9, 1962 N. MA ULAY 3,016,303

RECORDING PAPER COATED w MICROSCOPIC CAPSULES OF COLORING MATERIAL, CAPSULES AND METHOD 0 AK Flled Aug. 6, 1957 Sh s-Sheet 1 MAGNIFIED CROSS-SECTION 0F DISCRETE CAPSULE ACCORDING TO THE INVENTION FIG.2

I MAGNIFIED C SS-SECTION O CLUSTER OF DISCRET APSULES AC DING TO THE INVENTION Jan. 9, 1962 N. MACAULAY 3,016,308

RECORDING PAPER COATED WITH MICROSCOPIC CAPSULES OF COLORING MATERIAL. CAPSULES AND METHOD OF MAKING Flled Aug. 6, 1957 2 Sheets-Sheet 2 FIG.3

PHOTOMICROGRAPH MAGNIFIED L000 TIMES OF DISCRETE CAPSULES ACCORDING TO THE INVENTION FIG.4

PHOTOMICROGRAPH MAGNIFIED I,OOO TIMES OF DISCRETE CAPSULES ACCORDING TO THE INVENTION 1 ate rates This invention relates to a novel product comprising a substantially dry free-flowing powder of microscopic discrete capsules, to the process of producing said product, and to a pressure-sensitive record or copying material having a transfer coating of said microscopic discrete capsules on at least a portion of one surface thereof. The discrete capsules which make up the free-flowing powder of the invention possess a shell or wall containing therein a marking fluid.

Present pressure-sensitive copying systems are primarily of two types. One such system employs as a coating 2. mixture consisting of waxes, oils, carbon black and fillers which are applied to a sheet surface as a hot melt. This type of coating, which is typified by ordinary carbon paper, provides a mark under pressure by transfer at the areas of pressure of a complete mass of coating containing the carbon black or other pigment. This waxy mixture is relatively soft and of low tensile strength and is, therefore, not resistant to scufl or offset. The mark obtained on the copy sheet is also prone to smudge and offset onto bands and clothing.

A second type of pressure sensitive copying system employs, on one side of a sheet, a continuous coating containing marking fluid inclusions. This type of system illustrates previous efforts employing minute droplets of a marking fluid in a transfer coating to be used with record material, particularly with record material in manifold form. Typical of this type of product are the record or copying materials disclosed in British Patent 392,220 and US. Patents Nos. 2,374,862; 2,548,366 and 2,550,466. In accordance with these patents, the paper of the record material is coated on one surface with a continuous film containing minute droplets of an oily marking fluid. In this type of copying sheet, the marking fluid may be colored or it may be colorless but capable of forming a color by a chemical reaction with another chemical upon being brought into contact with each other. Under the pressure of writing or typing, the coating ruptures and the droplets of marking fluid exude on to the copy sheet to make a mark by direct coloration or color transfer or by forming a color by chemical reaction with a coreacting chemical on the adjacent surface of the copy sheet. The difliculty with products of this type is that the surface of the coated sheet is susceptible to scufling, abrasion and incidental rubbing which unavoidably causes rupture of the film, release of the marking fluid, and consequently smudge or offset or both. Also, on storage of the sheets, the coating material tends to dry out and crack, particularly when bended or folded, thus releasing the marking fluid through the resulting cracks to smudge oroffset an adjacent copy sheet or the hands or clothing. In the case of such coatings containing a colorless marking fluid, this difficulty arises only when the ruptured film is in contact with a copy sheet or other source of the coreacting chemical. But this is a very real disadvantage since such copying materials are not only used, but usually stored, in this condition.

Further work has been carried out in an attempt to overcome some of the objectionable features of the coatings employing fluid inclusions described hereinabove. An example of such work is described in Green Patentv No. 2,712,507. According to this patent a coating for pressure-sensitive copying materials is prepared in which the fluid inclusions of marking materials are produced having a wall about them which is somewhat more concentrated with respect to colloid solids than the remainder of the continuous dried coating on the surface of the paper. This product is predicated upon the theory that the walls about the fluid inclusions are tougher than the remainder of the colloid coating material, thus cracks which develop in the coating are said to be more prone to run between the fluid inclusions than through them and the leakage of marking fluid is said to be reduced. This type of coating requires that the walls of the fluid inclusions be of the same hydrophilic colloid material as the coating on the paper in which the fluid inclusions are dispersed, since the patent produces the fluid inclusions in the same aqueous system which is applied to paper and dried to form the continuous coating. This type of product suffers from several disadvantages. First of all, as stated above, it usually employs an aqueous coating system in which the hydrophilic colloid forming the walls about the fluid inclusions is the same as that of the continuous coating on the paper. This leads to lack of flexibility and versatility in control of the product and in coating operations. it requires that aqueous coating methods be employed. This is a serious disadvantage since aqueous coatings require that special grades of generally more expensive paper be employed and even then often results in buckling, distortion, warping of the paper since water tends to strike through or penetrate the paper. Additionally, aqueous coatings are generally not suitable for spot application or application to limited areas of one side of a sheet of paper. They are generally suitable only for application to the entire side of a sheet to produce a continuous coating.

The above disadvantages are particularly serious since in producing manifold business forms, the' coating of marking material is usually applied to the backs of the sheets of paper or web. Even when a colorless colorforming dye intermediate is employed as the marking material it is generally applied to the backs of the sheets so as to react with a coreactant or developing agent which is applied to the fronts of the sheets of a manifold when pressure is applied to the sheets. During the usual handling which such business forms must undergo in their assembly, cutting, perforation, etc., the coating on the backs of the sheets containing marking fluid is in contact with the fronts of the copy sheets, which may or may not have the developing agent. When the coating on the backs of the sheets is continuous, the passage of the sheets over mill rolls, punching of holes, perforation and guillotining of edges will produce smudging or oflset at areas of pressure. This undesirable smudging and offset can be minimized by spot coating the coating material on limited areas which are 'less subject to unavoidable mechanical pressure until actually used to produce copying.

It is an object of the present invention to provide a substantially dry free-flowing powder of microscopic discrete capsules of marking fluid which may be applied to paper and other web material to provide pressuresensitive materials which avoid the disadvantages of the prior art.

It is another object of this invention to provide a substantially dry free-flowing powder of microscopic discrete capsules of marking fluid which may be applied to paper in a variety of ways and which does not require an aqueous coating system in preparing a pressure-sensitive copying material from the capsules.

It is a further object of this invention to provide a process for producing the substantially dry free-flowing powder of microscopic discrete capsules having an outer shell of a material which is a non-ionizable water-soluble film-former or a hydrophobic water-insoluble film-former according to the invention.

It is an additional object of this invention to provide a superior pressure-sensitive copying or record material having the microscopic discrete capsules of marking fluid applied to at least a portion of one side of a sheet of paper or other web material.

It is also an object of this invention to provide a superior pressure-sensitive copying or record material having the microscopic discrete capsules of marking fluid applied to at least a portion of at least one side of a sheet of paper by means of a carrier or binder which is of a different material from that of the walls of the capsules.

The above enumerated objects, as well as other objects, together with the advantages of the invention, will be readily comprehended by persons skilled in the art upon reference to the following description, taken in conjunction with the annexed drawings.

In the drawings:

FIG. 1 is a greatly magnified cross-section of a discrete capsule making up the free-flowing powder according to the invention in which is the marking fluid and 11 is the wall of the capsule;

FIG. 2 is a greatly magnified cross-section of a cluster of discrete capsules which is frequently produced in accordance with this invention, in which the reference numerals have the same significance as in FIG. 1;

FIG. 3 is a photomicrograph magnified 1000 times of the discrete capsules of marking fluid making up the freeflowing powder of the invention; and

FIG. 4 is a photomicrograph magnified 1000 times of another sample of discrete capsules of marking fluid making up the free-flowing powder of the invention.

The free-flowing powder of microscopic discrete capsules of the invention containing a marking fluid comprises a capsule shell or film containing a marking fluid. In FIG. 1 of the drawings, the shell is indicated at 11 and the liquid inclusion of marking fluid is shown at 10. Frequently the discrete capsules are produced in the form of aggregates or clusters as shown in FIG. 2. While FIG. 2 illustrates a cluster of six discrete capsules, the number of capsules or spheres in a cluster is usually not so great. The shell or film of the capsules is of a nonpermeable nature and comprises a substance which is substantially insoluble in the liquid of the marking fluid. The capsule shell remains intact and retains the fluid within. Under substantial pressures, such as that of a pencil, pen or typewriter key, the shell will break and release the marking fluid which then marks or stains any receptive or copy material with which it comes in contact. The marking fluid may contain a colored substance which produces a direct transfer to a copy sheet or which may be an uncolored color-forming dye intermediate which reacts with a coreactant present on the copy sheet to produce a color transfer. When the microscopic discrete capsules of the invention are aflixed over at least a portion of a surface, such as a surface of a sheet of paper, the coated sheet then acts as a pressure-sensitive copying material at the coated area.

The size of the microscopic capsules is desirably such that they may be dispersed in any of the common media used as binders or coatings or other backing material for application to paper without producing a surface rough to the touch. These micro-capsules may be considered as being analogous to pigment particles and they can be dispersed in any binder/vehicle combination in a manner similar to ordinary pigments. Various binder systems may be employed such as aqueous binders, an organic solvent/binder system, a plastisol or organosol binder system, a hot melt coating system or an ink-type coating which may be set to the paper by absorption, oxidation, evaporation, heat or moisture.

The discrete microscopic capsules of the invention are desirably of from between. about 0.1 and 70 microns in diameter. More desirably, the diameter of the capsules is from about 0.5 to 20 microns. For preferred results, it has been found that a capsule diameter of between about 1 and 5 microns is most satisfactory. When the particle size exceeds 20 microns in diameter, a coating of the capsules on a paper surface may feel slightly rough to the touch. Below a diameter of one micron, the capsules are less sensitive to rupture when subjected to the pressure employed to produce copying through rupture of the capsule shell. Since it is desired to employ the microscopic capsules of the invention in pressure-sensitive copying systems which do not require the use of excessive pressures, it is desirable to provide capsules having a diameter of from about 1 to 5 microns. The microscopic capsules of the invention falling within the various particle size ranges described hereinabove exist as a free-flowing powder.

It has been found that one convenient shell thickness is approximately ,6 to A of the diameter of the capsules. When shell thicknesses substantially in excess of /3 of the diameter are produced, it has been found that the capsules are more diflicult to rupture and the ability to produce a copy is reduced. With shell thicknesses substantially less than of the diameter, it has been found that the capsules are more prone to rupture prematurely and thus smudge or offset in a normal handling and preparation of the paper product. As will be appreciated by those skilled in the art, the sensitivity to rupture under pressure is dependent upon the size of the capsule as well as the thickness of the wall, with the larger size capsules having greater tendency to rupture when subjected to pressure than the smaller size capsules. Generally speaking, it is desirable to employ as thin a capsule shell as is practical.

The microscopic capsules of the invention are produced by first providing a stable emulsion having as a continuous phase the film-former material which is capable of forming the shell of the capsule. The discontinuous phase of the emulsion shall constitute the marking fluid which comprises the pigment, colored dye or colorless color-forming dye intermediate suspended or dissolved in a non-volatile liquid. An essential characteristic of a film-forming substance is that it be substantially insoluble in the marking fluid. The emulsions are produced by placing the two mutually insoluble liquids in a blender or emulsifier and by agitation producing a stable emulsion with droplets of marking fluid of the desired particle size, preferably 1 to 5 microns in diameter. The resulting emulsion is then dried, preferably by spray drying, or the continuous film-forming material first condensed around the emulsified droplets by curing or other means and then spray dried. The resulting product is a dry free-flowing powder.

The discrete microscopic capsules may be prepared by several types of emulsification processes. For example, one process which produces microscopic capsules of approximately one micron diameter is as follows: About 20 parts by weight of a non-volatile liquid containing up to 25% by weight of a pigment, colored or colorless color-forming dye intermediate is emulsified into a solution containing from about 5 to 40 or 50 parts of a filmforming material by agitation in a high-speed blender. In other words, the liquid droplets shall preferably comprise between about 23% and by Weight of the capsules. When the particle size of the marking fluid is substantially uniform and of the desired diameter, the resulting emulsion is sprayed into a drying chamber or spray drier to evaporate the solvent of the film-forming material. Upon drying, the film-former produces a shell about the non-volatile marking fluid. The dry freeflowing powder so produced is collected by means of a cyclone chamber and, if necessary, washed with a solvent capable of removing any marking fluid which may exist on the shell of the capsule. After washing, the powder is air dried and stored ready for use.

Another capsule-forming process employing a hot melt procedure which might be employed is as follows: About 50 parts by weight of a non-volatile liquid containing up to about 25% by weight of a pigment, colored or colorless color-forming dye intermediate is emulsified into about 50 parts by weight of a molten 100% solids film-former composition. The emulsion is produced in a high-speed agitator as in the above procedure. When the particles of color-forming marking fluid are of satisfactory particles size, the resulting emulsion =is hot sprayed into a chilled chamber and the resulting solidified free-flowing powder of discrete microscopic capsules is collected.

A third process for producing the microscopic capsules in accordance with the invention employs plastisol or organosol sphere formation. The general procedure is as follows: Up to about 50 parts by weight of a nonvolatile liquid containing up to about 25% by weight of pigment or colored or colorless color-forming ,dye intermediate is emulsified into 50 parts by weight of a dispersion of a polymeric material in a plasticizer. The dispersion employed may contain up to about 30% of a volatile diluent. The emulsion is produced by a highspeed agitator, as in the foregoing procedures, and is sprayed into a hot air chamber or spray drier where the individual particles produced are heated to a temperature such that the resin-plasticizer, film-forming combination mutually dissolves and cures to provide a rigid shell around the marking fluid particles. This resulting powder is then collected.

The shell 11 of the microscopic capsules of the invention is produced from a film-former which may be organic or inorganic in nature, capable of providing interactive forces such as are capable of producing a network in the form of a continuous dry film or shell. The film-former must be substantially insoluble in the marking fluid employed, and when the shell is produced it must not permit permeation of the marking fluid. The shell formed may be hard and brittle or, if desired, made soft and flexible by the incorporation of a plasticizer. The film-forming materials may be either of the nonionizable Water-soluble type or the hydropholic waterinsoluble (organic solvent-soluble) type. Among the filmformers which may be employed to produce the shell of the capsules are the following: acrylate and methacrylate resins, such as polymethylmethacrylate and po-lyacrylic acid; alkyd resins, such as those produced from esters of ethylene glycol and terephthalic acid; animal glues; casein; cellulose derivatives, such as hydroethyl cellulose, carboxymethyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate and nitrocellulose; a conmarone-indene resin; furan resins, such as those of furfuraldehyde and acetophenone', petroleum hydrocarbon polymer resins, such as the Piccopale resins; isobutylene resins, such as polyisobutylene; isocyanate resins, such as polymers of polyesters and tolylene diisocyanate; melamine resins, such as melamine-formaldehyde; phe' nolic resins, such as phenol-formaldehyde resins, etc.; polyamide resins, such as alkoxy substituted nylon; rubbers, both natural and synthetic, GR-S, etc.; shellac; styrene resins, such as polystyrene, styrene-divinyl-benzene and styrene-divinyl sulfide; terpene resins, such as polyterpene; urea resins, such as urea-formaldehyde resins and urea-acetaldehyde resins; vinyl resins, such as polyvinyl chloride and polyvinyl acetate; vinylidene resins, such as vinylidine chloride-vinyl chloride (Saran); natural and synthetic waxes, such as par-afi'in and candelilla wax; and zein. Additionally, inorganic filmformers, such as sodium silicate, may be employed, although this film-former is less desirable because it is more difficult to emulsify.

The film-formers may be used alone or in combinations, where compatible, or with various plasticizers and modifying agents which impart improved characteristics, such as flexibility, scuff resistance, solvent impermeability, or,

in the case of water soluble film-formers, agents which cause water impermeability to the film-former. As an example of the latter type of material, formaldehyde may be employed to harden the shell of the capsule produced from a water-soluble film-former. A plasticizer may be one of many types of materials which modify a particular film or shell to give suitable elasticity, flexibility and toughness, etc. Among some of the satisfactory plasticizers which may be employed are: adipic acid esters, such as dioctyl adipate and dibutyl adipate; biphenyl derivatives, such as chlorinated biphenyl; glycol derivatives, such as polyethylene glycol of molecular weight of 200 to 20,000, polypropylene glycols, ethylene glycol dibutyrate and ethyl phthalyl ethyl glycolate; hydrocarbons, such as the polyaromatic hydrocarbon oils; acid esters and ethers, such as butyl or isooctyl esters and glycol ethers of lauric, oleic, citric, abietic, adipic, azelaic, benzoic, palmitic, phosphoric acids, etc.; phthalic acid derivatives, such as dimethyl-, diethyl-, dibutyl-phthalates; polyesters, such as Flexol R2H of Carbide and Carbon Co.; sulphonic acid derivatives, such as n-ethyl-, 0-, p-toluene-sulphonamides; tall oil derivatives, such as the methyl esters of tall oil, etc.

The marking fluid may comprise any liquid, whether organic or inorganic which will provide a suspending or dissolving medium for the pigment, or colored or colorless color-forming dye intermediates. Desirably, the fluid medium within the capsule shell shall have a low volatility, i.e., wherein less than about 10% of the liquid evaporates through the shell wall over a period of several years of normal storage. Fluids having vapor pressure of less than 0.01 mm. of mercury at 25 C. are particularly satisfactory in this respect. Additionally, the fluid shall desirably have a low freezing point, i.e., a freezing point of less than 0 F., preferably as low as -30 F. Also, the fluid shall desirably have a high boiling point which will provide reduced volatility at temperatures of use. Fluids having boiling points in excess of 100 C. are usually suitable in this respect. An additional important property of the fluid is that it have a flash point above the temperature of proposed use. above 100 C. are generally satisfactory. As those skilled in the art will appreciate, the product will be more useful, permanent and safe with liquids having higher boiling points and flash points and lower volatility and freezing points. Of course, the fluid must not dissolve the filmformer or shell of the capsules. Among the satisfactory fluids which may be employed are those listed below in Table 1:

TABLE 1 V.P., mm. Freezing Boiling Flash Compound Hg. Point, Point. Point,

at 20 0. C. O. at 760 F.

mm. Hg.

100 Sec. mineral oil polyethylene glycol (mol.

wt. 400) 4-8 435 diethylene glycol. 0. 01 8. 0 245. 8 290 dipropylene glycol 0.01 231. 8 280 thiodiethylene glycol.-. 0. 0]. --l0. 0 282.0 320 pentanediol-1,5 0. 01 15. 6 242. 5 265 monoamylnaphthalene O. 01 279 255 dibutyl maleate 0. 01 280. 6 285 (ii (2-ethy1 hexyl) maleate 0. 01 -60 209 (10 365 mm. ethoxytriglycol 0. -18. 7 255. 8 275 dioctyl phthalate 1.3 (200 -46 231 (5 425 0.) mm.) chlorinated biphenyl (Arochlor 1248 Monsanto) 7 340 379 methyl phthalyl-ethyl glycollate 0. 01 35 189 (5mm) 374 dibutyl phthalata -35 340 338 cottonseed oil 582 rapeseed oil 10 530 As will be appreciated, the free-flowing powders in accordance with this invention permit extreme flexibility in the choice of film-formers and marking fluids.

The marking fluid may contain a colored pigment or Fluids having a flash point' dye or it may contain a colorless color-forming dye intermediate which will react with a coreactant when brought into contact with it to produce a colored finish. The line of demarcation between pigments and dyes is often difficult to delineate. As used herein, a pigment is considered to be a colored or color-forming substance which is insoluble in the fluid of the marking fluid. Examples of pigments which may be employed are: carbon blacks, iron blues, phthalocyanines, cadmium reds, ultramarine blues, phosphoand molybdotungstic acid laked colors. A dye or dye former is herein considered to be colored or colorforming compound soluble in the fluid of the marking fluid. Among the dyes and dye formers which may be employed are: triphenylmethane, e.g., malachite green and crystal violet, azo dyes, diazonium salts, indigoid dyes, phthalocyanine dyes, anthraquinone dyes, acridine dyes, azine dyes, oxazine dyes, thiazine dyes and thioindigoid dyes.

One type of colorless color-forming dye system which may be advantageously used in the products of the invention is that described in British Patent No. 757,136. In accordance with that patent a colorless color-forming dye intermediate, such as an ether of a triphenylmethane dye former is maintained in an alkaline condition by neutralizing the dye former with an alkaline substance, in which form the dye former is colorless, and then producing a color by bringing the alkaline colorless dyestutf into contact with an excess of an acid which converts the dye former into a colored product. Among the colorless ethers of triphenylmethane dyestuffs which may be employed are the butyl ethers of methyl violet 2B, methyl violet 10B, magenta, malachite green A. In accordance with one embodiment of the present invention the marking fluid of the microscopic capsules may contain the colorless color-forming dye intermediate along with a small amount of an alkaline substance such as sodium carbonate, potassium hydroxide, etc. These capsules are applied to one surface of sheets of paper. On the opposite side of some sheets of paper is placed suflicient acid which when brought into contact with marking fluid containing the colorless color-forming dye intermediate will neutralize the dye intermediate thereby producing a color. Among the acids which may be employed to coat the opposite surface of the sheets are tannic acid, gallic acid and stearic acid. Also one may employ an acidic clay such as attapulgite clay. As will be apparent to those skilled in the art from the teachings of this disclosure, it is possible to incorporate the acid into the marking fluid of the discrete capsules and to place the colorless colorforming dye intermediate on the opposite sides of the sheets of paper. In either instance when pressure is exerted through two or more sheets in a manifold, rupture of the capsules will produce intermixing of the reacting chemicals to produce a color or copy at the sites Where pressure is applied.

A coating of capsules and binder weighing 1 to 6 lbs., and preferably 2 lbs., per 500 sheets of 20"x 30" paper in which 50 to 95% of the weight of the coating consists of capsules has been found to be satisfactory.

Among the important advantages of the free-flowing capsule powders of the invention is the extreme flexibility and versatility in the manner in which they may be applied to web material, such as paper, to provide a pressure sensitive copying material having a coating of the rupturable capsules according to the invention which permits copying. What is also important is that the free-flowing capsule powders may be applied to a surface of a sheet of paper by means of a binder material which provides adhesion of the capsules to the paper surface, which binder is of a different material and different type of substance from that of the shells of the capsules. Also, binder coatings of various thickness may be employed, permitting precise control over the thickness of the coating on the paper. In essence the binder employed need serve only as an adhesive to hold the capsules to the paper. Only a small thin layer of binder is needed rather than a thick coating covering the capsules. Both aqueous binders and non-aqueous binders may be employed. Since non-aqueous binders may be used, it is not necessary to employ expensive papers thereby providing additional economies as well as a superior product. One of the particular advantages of the free-flowing powders of the invention is that it may be employed with a hot melt wax binder or dispersed in a printing ink vehicle. In the case of printing ink vehicles, the microscopic capsules may be dispersed in them and the resulting product reverse printed on a paper sheet at the same time as ordinary line printing is done. This is particularly satisfactory since it provides an excellent means of spot application whereby prescribed areas on the backs or fronts of the sheets of paper may be coated with capsules. This is one of the particular advantages of the present invention since it permits application of a transfer film or coating of capsules to only those areas of the paper where it is desired.

In order that the present invention may be better understood, the following examples of products prepared according to the invention are given for purposes of illustration. Although the number of film-formers, marking fluids, coloring and color-forming materials and binders is so great, and the number of combinations of materials suitable for making the capsules and record materials containing the capsules over an area thereof is vast, those skilled in the art will be able to readily practice the invention from reading the examples which illustrate the preparation of the products of the invention. Portions of components are given in terms of parts by weight, unless otherwise specified.

Example I This example describes the preparation of microscopic capsules prepared by spray drying an emulsion of mineral oil in aqueous hydroxyethylcellulose.

About 30 parts of second mineral oil containing 4.5 parts of Mogul A (Godfrey Cabot, Inc.) carbon black (high volatile contentlow oil absorption-336 Angstrom units mean diameter) was emulsified into 700 parts of a 10% aqueous solution of hydroxyethylcellulose (having a viscosity of 250-350 centipoises at 20 C. when in the form of a 5% aqueous solution). Emulsification was accomplished by agitating the 10% aqueous solution of hydroxyethylcellulose by itself in a Waring Blendor and then pouring in the oil solution slowly while agitation was continued. A fine particle size (one micron) stable emulsion was thus produced. The resulting emulsion was injected via a fine air feed nozzle into a heated spray drying chamber of a temperature of between about 225-265 F. and the dried product collected. On examination, microscopic capsules ranging from 1 to 10 microns were observed. The capsules exuded black oil when subjected to ordinary writing pressure.

Example II This example describes the preparation of microscopic capsules prepared by spray drying an emulsion of mineral oil in aqueous hydroxyethylcellulose.

About 17 parts of 100 second mineral oil containing 5% by weight of the butyl ether of malachite green A was emulsified into 3000 parts of a 5% aqueous solution of Cellosize WP-40 (hydroxyethylcellulose which when in the form of a 2% aqueous solution at 20 C. possesses a viscosity of 75 to centipoises). An emulsion was produced and then spray dried in accordance with the procedure of Example I. A free-flowing powder of microscopic capsules was obtained.

Example III This example describes the preparation of microscopic capsules containing a marking fluid containing a colorless color-forming dye intermediate.

About 4.5 parts of the butyl ether of methyl violet was dissolved in 180 parts of an equal part mixture of Arochlor 1254 (a chlorinated diphenyl having a Saybolt viscosity of 44-48 seconds at 210 F.), amyl diphenyl and amylnaphthalene. The resulting solution was colorless. This solution was emulsified into 600 parts of a 10% aqueous solution by hydroxyethylcellulose in accordance with the procedure of Example I and the resulting emulsion spray dried in accordance with Example I. A free-flowing powder of microscopic capsules having particle sizes from about 0.5 to 10 microns diameter was obtained.

When the capsules were subjected to pressure they exuded colorless marking fluid which produced a strong color when absorbed on a paper impregnated with a surface of attapulgite clay or a paper surface coated with tannic acid.

Example IV This example describes the preparation of microscopic capsules containing carbon black.

About 150 parts of a 10% Arochlor 1248 (a chlorinated diphenyl having a Saybolt viscosity of 36-37 seconds at 210 F.) and 90% 100 second mineral oil mixture containing 22.5 partsof carbon black was emulsified into 75 parts of an aqueous solution of water soluble urea-formaldehyde resin (Uformite 400-67% solids) and 2.5 parts of extra low viscosity (-25 centipoises in a 2% aqueous solution at 25 C.) carboxymethylcellulose in 175 parts of water. The emulsion was produced in accordance with the procedure of Example I and diluted with 600 parts of water, and while continuing the rapid agitation, sufiicient concentrated hydrochloric acid' was added to produce condensation and precipitation of the urea formaldehyde resin. The resulting mixture was agitated for another five minutes, filtered, and the filter cake washed with water and acetone and then agitated with toluene to remove any free oily liquid. The mixture was again filtered and the filter cake air dried and then subjected to further drying at 105 C. Under microscopic examination the resulting dry, free-flowing powder was found to consist of agglomerated microscopic capsules ranging in diameter from between about 4 to 50 microns. On applying pressure to these capsules, the Walls ruptured and black oil was exuded in copious quantities.

Example V This example describes the preparation of microscopic capsules prepared from an emulsion of mineral oil in cellulose acetate.

About 100 parts of 100 second mineral oil containing about 25% by weight of nigrosine dye was emulsified into a solution of 50 parts of cellulose acetate in 600 parts of acetone in accordance with the procedure of Example I. The resulting emulsion was sprayed through an aspirator into the air to evaporate the acetone and the resulting dry microscopic capsules collected. The capsules were of about 50 micron diameter particle size. When this free-flowing powder of capsules was subjected to writing pressure, the cellulose acetate shells of the capsules were ruptured and the oil containing the nigrosine exuded therefrom in copious quantities.

Example VI sules exuded the blue colored fluid when subjected; to pressure to give a blue mark on a receptive surface.

10 Example VII This example describes the preparation of capsules containing a colorless color-forming dye intermediate.

About 50 parts of second mineral oil containing about 2 parts of the butyl ether of malachite green A (Color Index No. 657) in the alkaline condition was emulsified into a solution of 40 parts of Zein and 1 part of sodium hydroxide in 200 parts of methanol. The emulsification was accomplished in accordance with the procedure of Example I. The resulting emulsion was spray dried by atomizing the emulsion into the air to provide rnicro-capsules ranging in size from about 1 to 60 microns. When the resulting capsules were coated' to a sheet of paper and the sheet of paper placed in contact with the surface of an adjacent sheet which was coated with tannic acid, and pressure applied to the sheets in the form of pencil writing, a strongly colored mark was produced on' the surface of the sheet containing the tannic acid.

Example VIII Microscopic capsules produced in accordance with Example III to the extent of 30 parts of free-flowing capsule powder was placed into 70 parts of a 5% solution of Du Pont isobutyl methacrylate in benzene. The resulting dispersion was applied to the backs of sheets of bond paper with a doctor blade and then subsequently air dried. The fronts of these sheets of paper had been sensitized with attapulgite clay. When a manifold of sheets were stacked one above the other, with the capsule coated surfaces adjacent to the clay sensitized surfaces and writing pressure applied, a copy was produced on the fronts sensitized with clay at the sites where pressure was applied.

Example IX Microscopic capsules produced in accordance with Example VII were placed in a flexographic vehicle (Bensing Bros. and Deeney D-536) (a water soluble protein dissolved in water) to the extent of 30 parts by weight of capsules and 70 parts of flexographic vehicle, to provide a printable ink which was applied to portions of a surface of sheets of paper by means of a gravure roll which printed the desired portion of the surface of the sheets of paper with the capsule coating. The coating dried on the paper promptly. When the resulting coated sheets were assembled with the coated portions facing adjacent sheets activated with attapulgite clay and writing pressure applied against the treated surface, a strong colored mark was produced.

Example X About 30 parts of capsules produced in accordance with Example I were mixed with 70 parts of a mixture of 6 parts of cellulose acetate and 64 parts of acetone. The resulting mixture was applied to one surface of sheets of paper by means of a doctor blade. The sheets were permitted to dry in the air. The surface of the sheets of paper coated with the capsules provided an excellent means of copying.

Example XI About 40 parts of paraflin wax having a melting point of 135 F. and 20 parts of FTC-200 petroleum wax (Fischer-Tropsch-l) were melted together at C. Into the resulting molten mixture were added about 5 parts of Alpex resin (a cyclized rubber resin) and 120 parts of Schenectady ST-5115 resin and the resulting clear melt reheated to 120 C. and maintained at this temperature. About parts of a solution of 5 parts of phenyl leuco auramine in 120 parts of butyl benzyl phthalate and 0.5 part of dimethylethanolamine, heated to 120 C. was added with rapid agitation to the foregoing melt in a Waring Blendor. The emulsion so formed was sprayed via a hot air stream C. temperature) inlet into a chilled atmosphere and the resulting spherical particles collected ranged in size from 1 to 60 microns. When subjected to writing pressures, these spheres ruptured and exuded the marking fluid which gave a strong blue coloration both on a paper sheet coated with attapulgite clay and on a paper sheet coated with citric acid.

12 As will be apparent from the foregoing examples various components of film-formers, plasticizers, marking fluids, dyes, pigments and binders may be employed. 5 Listed below in Table 2 are some of the components which may be employed.

TABLE 2 Binder Film Forming Resin or Polymer Plasticizer Resin Solvent or Fluid For Dye or Dye or Pigment Binder Solvent or Dispersion Medium Pigment Dispersion Medium Ce lulose acetate dibutyl-phthalate. acetone mineral oil oil soluble blue A carboxymethyl- Water.

(du Pont). cellulose. fiydr xyethylcellulose polylezhylene glywater rapeseed oil. carbon black nitrocellulose methanol.

co 00. Ze none water methanol mineral oil butyl ether of casein Wateralkali. crystal violet. yrenebutadiene copolymer do water chlorinated bimalachite green polyviuylchloride none.

phenyl. lactone. plastisol. Melamineformaldehyde do do amyl biphenyl phthalocyanine methylmethacryltoluene.

blue pigment. ate. Polyvillylchloride dioetyl adipate none polyethylene crystal violet nitrocellulose methanol glycol 400. carbiriol. toluene. y yl acetate-.. cottonseed il ultramarine blue lithovarnlsh none. yv pyrrolidone. amyluaphthalene. Hectograph hot melt resin"... D0.

White A du Pont. Petroleum resin paraffin wax none thirlidieti'hylerio methyl violet. starch water.

g yco Piccopale (Penna. Indus.

Chemical Co.) mineral oil Oyclized rubber do "Troi oir polyethylene Cadmium Red cellulose acetate-.- acetone- (Andersonglycol 400. Lithopone Eriehgrd Oil Dup Glidden.

orp. o yterpene resin. parafiin wax none glycerol pigment gelatin water. Piccolyte (Penn Chemc mineral oil Example XII An emulsion was prepared by homogenizing 100 parts of a 5050 mixture of polyethylene glycol 400 and ethoxytriglycol containing 7 parts of Spirit Hectograph Black A (a black pigment) (General Dyestutf Co.) into a molten mixture of 50 parts of parafiin wax and 45 parts of Piccopale 100 (a petroleum hydrocarbon resin). The resulting emulsion was sprayed into a chilled atmosphere and the solidified particles containing the colored fluid collected and stored. The spheres possessed a particle size of from 1 to 60 microns.

Example XIII About 50 parts of Geon 121 resin (polyvinyl chloride resin) was dispersed in 50 parts of dioctylphthalate as a plasticizer. Into this mixture was emulsified 50 parts of polyethylene glycol (mol. wt. 400) containing parts of carbon black. The resulting emulsion was sprayed into an air chamber at a temperature of 350 F. in order to fuse the resin and plasticizer about the fluid colored particles to form capsules containing marking fluid.

Example XIV About 50 parts of capsules prepared according to Example I were dispersed in 50 parts of Geon 121 resin and 50 parts of dioctylphthalate to provide a paste. The

resulting paste was printed onto paper and the coating cured by passing the coated paper over rollers at 350 F. An excellent copy sheet was produced.

It will be appreciated that if more than one copy is wanted it is possible to coat the capsules of the invention on at least a portion of one side of sheets of paper and, if necessary, a reactive coating on the other side, so that by placing a pile of such sheets one upon the other and pressing upon them with a pencil or subjecting them to the blow of a typewriter key, a suitable number of copies can be obtained depending upon the amount of pressure applied and the thickness of the paper.

The terms and expressions which have been employed are used as terms of description and not of limitation, and it is not intended, in the use of such terms and expressions, to exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.

What is claimed is:

1. A process for producing a free-flowing powder of microscopic discrete rupturable capsules comprising liquid droplets encapsulated within an outer rupturable shell of film-forming material, said encapsulating outer shell being formed directly by evaporation forces on the solvent of a film-former solution of a non-ionizable water-soluble film-former which comprises the continuous phase of suspended minute particles of an emulsion, the discontinuous phase of which emulsion comprises the liquid droplets and between about 23% and 80% by weight of the capsules, which process comprises producing an emulsion of the liquid droplets in a film-former solution in which the latter forms the continuous phase and is substantially insoluble in the liquid droplets, suspending minute particles of said emulsion in a gaseous atmosphere, and then subjecting said suspended emulsion particles to evaporation forces to produce said microscopic discrete capsules in the form of a free-flowing powder.

2. A process defined by claim 1, wherein the drying is accomplished by spray evaporation.

3. A process as defined by claim 1, wherein the resulting capsules which are produced have a diameter of between about 0.1 and microns.

4. A process for producing a free-flowing powder of microscopic discrete rupturable capsulescomprising'marking fluid droplets encapsulated within an outer rupturable shell of film-forming material, said encapsulating outer shell being formed directly by evaporation forces on the solvent of a film-former solution of a non-ionizable watersoluble film-former which comprises the continuous phase of suspended minute particles of an emulsion, the discontinuous phase of which emulsion comprises the marking fluid droplets and between about 23% and 80% by weight of the capsules, which process comprises producing an emulsion of the marking fluid in a film-former solution in which the latter forms the continuous'phase and is substantially insoluble in, the marking fluid, suspending minute particles of said emulsion in a gaseous atmosphere, and then subjecting said suspended minute emulsion particles to evaporation forces to produce said microscopic discrete capsules in the form of a free-flowing powder.

5. A process as defined by claim 4 wherein said marking fluid comprises a colored material.

6. A process for producing a free-flowing powder of microscopic discrete rupturable capsules comprising liquid droplets encapsulated within an outer rupturable shell of film-forming material, said encapsulating outer shell being formed from a hot molten non-aqueous film-former comprising the continuous phase of an emulsion, the discontinuous phase of which emulsion comprises liquid droplets comprising between about 23% and 80% by weight of the emulsion, which process comprises producing an emulsion of the liquid droplets in said hot molten nonaqueous film-former in which the latter forms the continuous phase and is substantially insoluble in the liquid droplets, suspending minute particles of said emulsion in a gaseous atmosphere, and cooling the suspended particles to solidify said film-former and produce microscopic discrete rupturable capsules in the form of a free-flowing powder.

7. A process as defined by claim 6, wherein the resulting capsules have a diameter between about 0.1 and 70 microns.

8. A process for producing a free-flowing powder of microscopic discrete rupturable capsules comprising liquid droplets encapsulated within an outer rupturable shell of film-forming material, said encapsulating outer shell consisting of a hydrophobic water-insoluble material pro duced by the chemical condensation of the reactive constituents of the film-former dissolved in aqueous solution, said solution comprising the continuous phase of an emulsion, the discontinuous phase of which emulsion comprises liquid droplets comprising between about 23% and 80% by weight of the capsules, which process comprises producing an emulsion of the liquid droplets in said aqueous solution of film-former constituents, causing said film-former constituents to undergo Chemical condensation about the liquid droplets, and thereby produce said microscopic discrete rupturable capsules in the form of a free-flowing powder.

9. A process for producing a free-flowing powder of microscopic discrete rupturable capsules comprising liquid droplets encapsulated within an outer rupturable shell of film-forming material, said encapsulating outer shell being formed of a plastisol film-former comprising the continuous phase of an emulsion, the discontinuous phase of which emulsion comprises liquid droplets comprising be tween about 23% and 80% by weight of the capsules, which process comprises producing an emulsion of the liquid droplets in said plastisol film-former in which the latter forms the continuous phase and is substantially insoluble in the liquid droplets, heating minute particles of said emulsion to thereby produce said microscopic discrete rupturable capsules in the form of a free-flowing powder.

10. A process for producing a free-flowing powder of microscopic discrete rupturable capsules comprising liquid droplets encapsulated within an outer rupturable shell of film-forming material, said encapsulating outer shell being formed directly by evaporation forces on the organic solvent of a film-former solution of a hydrophobic waterinsoluble film-former in an organic solvent which comprises the continuous phase' of suspended minute particles of an emulsion, the discontinuous phase of which emulsion comprises the liquid droplets, and between about 23% and by weight of the capsules, which process comprises producing an emulsion of the liquid droplets in the film-former solution in which the latter forms the continuous phase andis substantially insoluble in the liquid droplets, suspending minute particles of said emulsion in a gaseous atmosphere, and then subjecting said suspended emulsion particles to evaporation forces to produce said microscopic discrete capsules in the form of a free-flowing powder.

11. A free-fl0wing powder of microscopic discrete rupturable capsules having a particle size of between about 0.1 and 70 microns diameter, said capsules comp-rising liquid droplets encapsulated within an outer shell rupturable under pressure, said liquid droplets being substantially insoluble in and incapable of dissolving said outer shell and comprising between about 23% and 80% by weight of said capsules, said outer shell having a thickness comprising from about one-tenth to one-third of the capsule diameter and comprising a material selected from the class consisting of a non-ionizable water-soluble filmformer and a hydrophobic water-insoluble film-former.

12. A substantially dry free-flowing powder as defined by claim 11 wherein the capsules have a particle size of between about 1 and 20 microns diameter.

13. A substantially dry free-flowing powder as defined by claim 11 wherein the capsules have a particle size of between about 1 and 5 microns diameter.

14. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 11 wherein the outer shell material is a non-ionizable water-soluble film-former comprising a cellulosic material.

15. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 14 wherein the liquid droplets comprise a marking fluid.

16. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 11 wherein the shell material is a hydrophobic water-insoluble film-former comprising a chemical condensation polymer.

17. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 16 wherein the liquid droplets comprise a marking fluid.

18. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 11 wherein the shell material is a hydrophobic water-insoluble film-former comprising a vinyl polymer.

19. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 18 wherein the liquid droplets comprise a marking fluid.

20. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 11 wherein the shell material comprises a fusible wax material.

21. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 20 wherein the liquid droplets comprise a marking fluid.

22. A free-flowing powder of microscopic discrete rupturable capsules as defined by claim 11 wherein the liquid droplets comprise a marking fluid.

23. A record copying sheet having on at least a portion of one side thereof a coating of a free-flowing powder of microscopic discrete capsules comprising a rupturable shell containing therein a marking fluid capable of being liberated when the shells of said discrete capsules are ruptured upon being subjected to an external printing or marking pressure, said microscopic discrete capsules being those defined by claim 11.

24. A record copying sheet having on at least a portion of one side thereof a coating of microscopic discrete capsules comprising a rupturable shell containing therein a marking fluid capable of being liberated when the shells of said discrete capsules are ruptured upon being subjected to external pressure, said capsules being held to said sheet by a binder which is of a different substance from that forming the rupturable shell of said capsules, said microscopic discrete capsules being those defined by claim 11.

25. Paper having coated on at least a portion of a surface thereof microscopic discrete capsules comprising a rupturable shell containing therein a marking fluid capable of being liberated when the shells of said discrete capsules are ruptured upon being subjected to external pressure, said capsules being held to said sheet by a binder which is of a different substance from that forming the rupturable shell of said capsules, said microscopic discrete capsules being those defined by claim 11.

26. Paper as defined by claim 25 wherein the marking fluid comprises a colored transfer substance.

' ing a color when in the presence of an acidic substance.

29. Paper as defined by claim 25 wherein the capsules have a diameter of between about 0.1 and 70 microns.

References Cited in the file of this patent UNITED STATES PATENTS 2,650,895 Wallenmeyer Sept, 1, 1953 2,711,375 Sandberg June 21, 1955 2,712,507 Green July 5, 1955 2,777,798 Hochberg Jan. 15, 1957 2,800,457 Green July 23, 1957 2,800,458 Green July 23, 1957 UNITED STATES PATENT OFFICE CERTIFICATE, OF CORRECTION Patent No,, 3 016 368 January 9 1962 Norman Macaulay It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1 line 31 for ,"bands" read hands ---3 column 5 line 1O for "particles" read particle line 42,, for "'hydropholic" read hydrophobic column 'Z line 11, before "colored" insert a column 9 line 6 for "by" read of columns 11 and 12 TABLE 2"", the horizontal lines. beginning "Petroleum resin! and "Piccopale" should be presented as a single composition and not as two separate compositions as in the patent.

Signed and gsealed this 19th day of June 1962,

(SEAL) Attest ERNEST W. SWIDER v DAVID L. LADD Attesting Officer Commissioner of Patents UNITED STATES PATENT OFF-ICE CERTIFICATE, OF CORRECTION Patent Noe 3 O16 3O8 January 9 1962 NormanMacaulay It is hereby certified that error appears in the above numbered patant requiring correction and that the said Letters Patent should read as corrected below.

Column l line 31,, for -"bands" read hands column 5 line 10 for "particles" read particle line 42 for "hydropho1ic' read hydrophobic column '7 line 11,, before "coloned' insert a column 9 line 6 for "by" read of columns 11 and 12,, TABLE 2" the horizontal lines beginning "Petroleum resin"? and "Piccopale" should be presented as a single composition and not as two separate compositions as in the patent Signed and sea1ed this 19th day of June 1962.

(SEAL) Attest ERNEST w. SWIDER DAVID A D Attesting Officer Commissioner of Patents

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2650895 *Feb 24, 1947Sep 1, 1953Mead Johnson & CoSpray dried vitamin a and d emulsion
US2711375 *Feb 19, 1954Jun 21, 1955Ncr CoPressure sensitive manifold sheet
US2712507 *Jun 30, 1953Jul 5, 1955Ncr CoPressure sensitive record material
US2777798 *Feb 19, 1953Jan 15, 1957Nopco Chem CoStable fat-soluble vitamin-containing composition
US2800457 *Jun 30, 1953Jul 23, 1957Ncr CoOil-containing microscopic capsules and method of making them
US2800458 *Jun 30, 1953Jul 23, 1957Ncr CoOil-containing microscopic capsules and method of making them
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3079351 *Nov 26, 1958Feb 26, 1963Moore Business Forms IncCopying materials and emulsions
US3111407 *Feb 26, 1960Nov 19, 1963IbmMethods for making record materials
US3116206 *Dec 22, 1961Dec 31, 1963Ncr CoEncapsulation process and its product
US3130050 *Jan 18, 1960Apr 21, 1964Gen Aniline & Film CorpOil-dispersed dyes in photopolym-erization systems
US3132075 *Oct 17, 1960May 5, 1964Upjohn CoSolid medicinal dosage forms coated with hydroxyethylcellulose and hydrolyzed styrene-maleic anhydride copolymer
US3143436 *Oct 20, 1960Aug 4, 1964Us Rubber CoMethod of making breathable films and coated fabrics
US3161602 *Sep 5, 1961Dec 15, 1964Ncr CoProcess for making capsules
US3202510 *Jul 11, 1961Aug 24, 1965Frederick Post CoProduction of encapsulated light-sensitive diazotype compositions and coatings
US3202533 *Jul 24, 1962Aug 24, 1965IbmMethod of encapsulating liquids
US3208951 *Oct 30, 1961Sep 28, 1965Ht Res InstElectrostatic encapsulation
US3256090 *Mar 27, 1961Jun 14, 1966Polaroid CorpDiffusion transfer photographic package with pressure-rupturable capsule of edge-sealing adhesive
US3260620 *Oct 22, 1962Jul 12, 1966Monsanto Res CorpTape fed fuel cell
US3265630 *Dec 22, 1958Aug 9, 1966Ncr CoEncapsulating lipophilic material by coacervation
US3272629 *Jan 25, 1962Sep 13, 1966Nashua CorpPhotosensitive diazotype materials
US3276869 *May 9, 1961Oct 4, 1966Polaroid CorpCapsular product coated with silver halide and containing a color-providing substance
US3276876 *Mar 19, 1963Oct 4, 1966Gen Aniline & Film CorpPhotographic sheet material
US3281244 *Jan 24, 1963Oct 25, 1966Keuffel & Esser CoHeat-developable two-component diazotype reproduction material
US3305382 *Jan 2, 1964Feb 21, 1967IbmPressure sensitive transfer sheet
US3306748 *Mar 5, 1963Feb 28, 1967Chalkley LymanPhotosensitive system based on hydrophobic dye cyanides and polyvinylpyrrolidone
US3316119 *Nov 1, 1961Apr 25, 1967Litton Systems IncRecording member for visibly recording radio frequency microwaves
US3322556 *Dec 20, 1963May 30, 1967Keuffel & Esser CoMethod for preparing heat-developable two-component diazotype reproduction sheet
US3328257 *Feb 19, 1963Jun 27, 1967Gevaert Photo Prod NvPreparation of microcapsules
US3351531 *Aug 9, 1965Nov 7, 1967Beatrice Foods CoWheat gluten-encapsulated dried oilin-water dispersions of fat-soluble food, medicaments, flavoring agents or food coloring agents
US3357354 *Sep 3, 1965Dec 12, 1967Xerox CorpReproduction method
US3360371 *Dec 27, 1963Dec 26, 1967Keuffel & Esser CoHeat-developable two-component diazotype reproduction material
US3386824 *Mar 27, 1967Jun 4, 1968Chicago Aerial Ind IncPhotographic processing film laminate structure utilizing plastic microcapsules
US3389007 *Jul 17, 1963Jun 18, 1968Oda RyoheiRecord transfer sheet material, method of making and composition
US3391095 *Sep 20, 1965Jul 2, 1968Interchem CorpNormally stable curable epoxy resin composition containing encapsulated water insoluble amine curing agents
US3401123 *Apr 27, 1967Sep 10, 1968Ncr CoProcess for making case-hardened capsules and its capsule product
US3406137 *Apr 29, 1965Oct 15, 1968Xerox CorpImaging material
US3409461 *Nov 22, 1963Nov 5, 1968Kalle AgProcess for the manufacture of an encapsulated isocyanate
US3415186 *Feb 10, 1966Dec 10, 1968Xerox CorpDuplicating system
US3415758 *May 3, 1962Dec 10, 1968Ncr CoProcess of forming minute capsules en masse
US3418250 *Oct 23, 1965Dec 24, 1968Us Plywood Champ Papers IncMicrocapsules, process for their formation and transfer sheet record material coated therewith
US3418656 *Oct 23, 1965Dec 24, 1968Us Plywood Champ Papers IncMicrocapsules, process for their formation and transfer sheet record material coated therewith
US3421894 *Jan 13, 1966Jan 14, 1969Ncr CoRecording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US3427160 *Apr 26, 1966Feb 11, 1969Polaroid CorpCapsular products
US3432327 *Mar 8, 1965Mar 11, 1969Pilot Pen Co LtdPressure sensitive copying sheet and the production thereof
US3436234 *Apr 29, 1965Apr 1, 1969Xerox CorpDuplicating ink
US3446741 *Nov 14, 1963May 27, 1969Minnesota Mining & MfgInsulating device,composition,and method
US3454430 *Mar 29, 1966Jul 8, 1969Monsanto Res CorpTape feed for tape fuel cell and the method of operating a dry tape fuel cell
US3455390 *Dec 3, 1965Jul 15, 1969Union Oil CoLow fluid loss well treating composition and method
US3455838 *Apr 22, 1966Jul 15, 1969Nat Starch Chem CorpMethod of encapsulating water-insoluble substances and product thereof
US3461092 *Aug 23, 1965Aug 12, 1969Owens Illinois IncSolid particulate printing ink composition and process for producing same
US3463655 *Apr 5, 1967Aug 26, 1969Fuji Photo Film Co LtdPressure-sensitive copying paper
US3472675 *Dec 23, 1966Oct 14, 1969Ncr CoPressure-sensitive capsule-containing foraminated sheet material
US3486449 *Aug 26, 1966Dec 30, 1969Levine Alfred BProcess of repulsion printing employing a radiant energy field
US3486752 *Aug 28, 1967Dec 30, 1969Minnesota Mining & MfgTarget toy device
US3510435 *Nov 17, 1967May 5, 1970Ncr CoMethod of producing opaque encapsulated materials
US3516846 *Nov 18, 1969Jun 23, 1970Minnesota Mining & MfgMicrocapsule-containing paper
US3516941 *Jul 25, 1966Jun 23, 1970Minnesota Mining & MfgMicrocapsules and process of making
US3608488 *May 25, 1970Sep 28, 1971Levine Alfred BPrinting and reproducing process
US3615972 *Apr 28, 1967Oct 26, 1971Dow Chemical CoExpansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US3617334 *Nov 8, 1968Nov 2, 1971Ncr CoPressure-sensitive sheet material
US3639256 *May 27, 1970Feb 1, 1972Ncr CoEncapsulation process by complex coacervation using inorganic polymers
US3639257 *Jun 24, 1968Feb 1, 1972Pelikan Werke Wagner GuentherMicrocapsules as carriers for color reaction components in color reaction paper and process of making said microcapsules
US3691090 *Jan 13, 1970Sep 12, 1972Fuji Photo Film Co LtdEncapsulation method
US3720534 *May 25, 1970Mar 13, 1973Moore Business Forms IncPolymer gels and method of making same
US3763347 *Apr 13, 1972Oct 2, 1973Ncr CoVaporous lamp
US3769045 *Jun 22, 1971Oct 30, 1973Ncr CoProcess for producing liquid write crayon
US3819398 *Apr 28, 1972Jun 25, 1974Champion Int CorpProcess for production of pressure-sensitive copy sheet
US3836383 *Oct 27, 1971Sep 17, 1974Fuji Photo Film Co LtdPressure sensitive recording paper
US3852076 *Feb 22, 1972Dec 3, 1974Ryan JAqueous method of microencapsulation and capsules
US3852401 *Jun 27, 1972Dec 3, 1974Japan Exlan Co LtdMethod for producing artificial fibers containing microcapsules
US3865613 *Sep 11, 1972Feb 11, 1975Wiggins Teape Res DevPressure-sensitive copying systems
US3872023 *Apr 17, 1972Mar 18, 1975Basf AgMicrocapsules having walls made of copolymer of methylmethacrylate and acetylacetates of mono(meth) acrylates of aliphatic diols
US3872024 *May 27, 1970Mar 18, 1975Ncr CoEncapsulation process by simple coacervation using inorganic polymers
US3883298 *Nov 10, 1972May 13, 1975Platt GeraldEnergy responsive thread
US3888689 *Oct 1, 1971Jun 10, 1975Fuji Photo Film Co LtdAqueous printing ink containing perfume-containing microcapsules
US3896033 *Jul 3, 1972Jul 22, 1975Colgate Palmolive CoEncapsulated fabric softener
US3914511 *Oct 18, 1973Oct 21, 1975Champion Int CorpSpot printing of color-forming microcapsules and co-reactant therefor
US3919110 *Nov 8, 1972Nov 11, 1975Champion Int CorpColored organic synthetic pigments and method for producing same
US3939095 *Aug 8, 1973Feb 17, 1976Badische Anilin- & Soda-Fabrik AktiengesellschaftDye-containing microcapsules
US3968301 *Oct 29, 1974Jul 6, 1976Monsanto CompanyPressure-sensitive record material and dye solvents therefor
US3993831 *Apr 8, 1971Nov 23, 1976Champion International CorporationMicrocapsules, process for their formation and transfer sheet record material coated therewith
US4000087 *Jul 29, 1974Dec 28, 1976Moore Business Forms, Inc.Dye precursors in polyamide shells; incorporation of polystyrene or epoxy resins in the fill material
US4003589 *Oct 4, 1973Jan 18, 1977Kureha Kagaku Kogyo Kabushiki KaishaCarbonless copying paper
US4018688 *Jul 21, 1975Apr 19, 1977The Procter & Gamble CompanyCapsules, process of their preparation and fabric conditioning composition containing said capsules
US4039712 *Feb 24, 1972Aug 2, 1977Nippon Petrochemicals Company Ltd.Hydrogenated polycyclic aromatic hydrocarbons
US4050945 *Jul 8, 1974Sep 27, 1977Yoshio SuzukiMetallic compound reactant, chelating compound reactant, binder
US4054697 *Oct 28, 1975Oct 18, 1977Imperial Chemical Industries LimitedDecorative sheet material
US4055358 *Mar 15, 1976Oct 25, 1977Ciba-Geigy CorporationLeuco dyes
US4063754 *May 7, 1976Dec 20, 1977The Mead CorporationProcess for the production of pressure sensitive carbonless record sheets using novel hot melt systems and products thereof
US4070303 *Apr 26, 1976Jan 24, 1978Kureha Kagaku Kogyo Kabushiki KaishaAromatic hydrocarbon, aliphatic diester
US4087376 *Dec 30, 1976May 2, 1978Ncr CorporationCondensation polymerization
US4111874 *Oct 4, 1976Sep 5, 1978Canadian Patents And Development LimitedFatty acid soap, water, binder
US4137343 *Aug 29, 1977Jan 30, 1979The Mead CorporationProcess for producing pressure-sensitive carbonless transfer sheets
US4138362 *Jan 18, 1977Feb 6, 1979Champion International CorporationFormation of microcapsules by interfacial cross-linking, microcapsules produced, and microcapsular dispersion
US4139218 *Aug 29, 1977Feb 13, 1979The Mead CorporationNonaqueous, solvent-free hot melt adhesive suspension of microencapsulated chromogens, polarity
US4139392 *Aug 29, 1977Feb 13, 1979The Mead CorporationChromogenic hot melt coating compositions
US4143890 *Dec 6, 1976Mar 13, 1979The Mead CorporationPressure-sensitive carbonless transfer sheets using hot melt systems
US4162165 *Jun 16, 1977Jul 24, 1979The Mead CorporationHot melts, carbonless copying
US4171981 *Apr 29, 1977Oct 23, 1979The Mead CorporationProcess for the production of hot melt coating compositions containing microcapsules
US4187194 *Feb 7, 1974Feb 5, 1980Xerox CorporationEncapsulation process
US4191404 *Apr 7, 1978Mar 4, 1980The Mead CorporationProcess for producing a pressure-sensitive carbonless copy sheet using microcapsules formed in situ in a radiation curable binder
US4200667 *Apr 7, 1978Apr 29, 1980The Mead CorporationProcess for producing a pressure-sensitive carbonless copy sheet using microcapsules formed in situ in a radiation curable binder
US4201404 *May 17, 1978May 6, 1980Minnesota Mining And Manufacturing CompanyPressure-sensitive marking materials
US4208460 *Nov 21, 1977Jun 17, 1980Blockfabrik Lichtensteig, AGProcess for producing paper having a coating of pressure-sensitive transfer copying material
US4209188 *Apr 11, 1978Jun 24, 1980Moore Business Forms, Inc.Reacting a methoxylated epoxy compound with the outer surfaces of capsule walls
US4219439 *Mar 31, 1978Aug 26, 1980Kanzaki Paper Manufacturing Co., Ltd.Controlling aggregation by agitation of suspension during cooling process
US4221601 *Jan 6, 1977Sep 9, 1980Basf Farben & Fasern AgPackaged pigment pastes and process for coloring and toning water-diluted coating agents
US4235458 *Jan 8, 1979Nov 25, 1980The Mead CorporationProcess for the production of hot melt coating compositions containing microcapsules
US4264365 *Oct 1, 1979Apr 28, 1981The Mead CorporationProduction of pressure-sensitive carbonless record sheets using dioic acid hot melt systems and products thereof
US4327939 *Jun 16, 1980May 4, 1982Frye Copysystems, Inc.Chemical carbonless copy paper and image receptor medium therefor
US4339360 *Mar 11, 1980Jul 13, 1982Agency Of Industrial Science & TechnologyParticles of activated oxidized polysaccharide substance coated with inactive protective layer and method for manufacture thereof
US4371634 *Nov 16, 1981Feb 1, 1983Basf AktiengesellschaftMicrocapsule-containing wax composition
US4372581 *Oct 20, 1980Feb 8, 1983Hermann SchumacherMixture of alkanes and a cellulose derivative, hydrocarbon resin, melamine resin, phenolic resin, or styrene resin
US4396670 *Mar 24, 1981Aug 2, 1983The Wiggins Teape Group LimitedProcess for the production of microcapsules
US4399209 *Nov 12, 1981Aug 16, 1983The Mead CorporationTransfer imaging system
US4406816 *Sep 30, 1980Sep 27, 1983Basf AktiengesellschaftProcess for the preparation of microcapsules, and the microcapsules obtained thereby
US4440846 *Nov 12, 1981Apr 3, 1984Mead CorporationPhotocopy sheet employing encapsulated radiation sensitive composition and imaging process
US4487801 *Oct 11, 1983Dec 11, 1984Minnesota Mining And Manufacturing CompanyAdhesive with microcapsules which burst when layers separate
US4493869 *Oct 11, 1983Jan 15, 1985Minnesota Mining And Manufacturing CompanyFragrance-releasing microcapsules on a see-through substrate
US4495509 *Jun 9, 1983Jan 22, 1985Moore Business Forms, Inc.Continuous polymeric wall surrounding a colorless dye precursor
US4497887 *Jun 2, 1982Feb 5, 1985Ricoh Compay, Ltd.Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle
US4599271 *Sep 10, 1984Jul 8, 1986Moore Business Forms, Inc.Forming polymeric walls around organic droplets
US4606956 *Jun 7, 1985Aug 19, 1986Minnesota Mining And Manufacturing CompanyOn page fragrance sampling device
US4620726 *Dec 9, 1985Nov 4, 1986General Foods CorporationComputer-assisted laboratory notebook kit
US4626471 *Feb 25, 1985Dec 2, 1986Moore Business Forms, Inc.With polyfunctional amine curing agent
US4636818 *Jun 5, 1985Jan 13, 1987Moore Business Forms, Inc.Carbonless system including solvent-only microcapsules
US4640847 *Jan 11, 1985Feb 3, 1987Kureha Kagaku Kogyo Kabushiki KaishaDispersion of dye-containing microcapsules in wax; painting ink on part of paper
US4681806 *Feb 13, 1986Jul 21, 1987Minnesota Mining And Manufacturing CompanyPolyurea microspheres
US4692188 *Oct 15, 1985Sep 8, 1987Xerox CorporationPreparation of ink jet compositions
US4701397 *Feb 26, 1986Oct 20, 1987The Mead CorporationMethod for forming images on plain paper and an imaging sheet useful therein
US4729792 *May 22, 1986Mar 8, 1988The Standard Register CompanyDispersion, oils, curing agents, polysalt formation, polyamine, lipophilic, nonpolar
US4751165 *Apr 6, 1987Jun 14, 1988The Mead CorporationLess grainy; enhanced optical density
US4822416 *Sep 8, 1987Apr 18, 1989Nashua CorporationHigh solids content CB coating
US4822769 *Aug 20, 1987Apr 18, 1989Nashua CorporationHigh solids content coated back paper
US4859561 *Jul 14, 1987Aug 22, 1989The Mead CorporationDeveloper sheet useful in providing transparencies or reproductions having a controlled gloss finish
US4865943 *Aug 28, 1985Sep 12, 1989The Mead CorporationCoatings on a support
US4879174 *Jan 10, 1986Nov 7, 1989Minnesota Mining And Manufacturing CompanyDevice for exposing colorant to be transferred
US4879175 *Dec 11, 1985Nov 7, 1989Minnesota Mining And Manufacturing CompanyDevice for exposing colorant to be transferred
US4889877 *Jan 7, 1988Dec 26, 1989The Standard Register CompanyCarbonless copy paper
US4891245 *Mar 21, 1986Jan 2, 1990Koh-I-Noor Rapidograph, Inc.Electrophoretic display particles and a process for their preparation
US4898780 *Jan 7, 1988Feb 6, 1990The Standard Register CompanySalt formation of hard, thick walls containing oily soluton
US4933249 *Aug 18, 1988Jun 12, 1990Fuji Photo Film Co., Ltd.Electrostatographic pressure fixing process using encapsulated toner particles
US4940738 *Aug 11, 1989Jul 10, 1990The Standard Register CompanyCoated backside, carbonless copy paper
US4940739 *Dec 27, 1988Jul 10, 1990The Standard Register CompanyMicroencapsulation, carbonless copy paper, coated backside,
US4945121 *Aug 18, 1987Jul 31, 1990Koh-I-Noor Radiograph, Inc.Thermosetting dyed latex colorant dispersions
US4956129 *Feb 1, 1988Sep 11, 1990Ici Americas Inc.Microencapsulation process
US5050910 *Jul 13, 1989Sep 24, 1991Sheldon SchechterFragrance-releasing insert for a magazine
US5084208 *Jan 7, 1991Jan 28, 1992Isp Investments Inc.Preparation of discrete microdroplets of a high viscosity oil in water
US5102856 *Nov 7, 1990Apr 7, 1992The Standard Register CompanyCarbonless copy sheet consists of a support, a coating of nonvolatile diluent, an acidic color developer, microcapsule containing dye stuff precursor, binder and surfactant; used in computer print out and other pressure marking applications
US5135437 *Jun 24, 1991Aug 4, 1992Schubert Keith EForm for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same
US5137494 *Mar 16, 1990Aug 11, 1992Schubert Keith ETwo-sided forms and methods of laying out, printing and filling out same
US5154668 *Mar 22, 1990Oct 13, 1992Schubert Keith ESingle paper sheet forming a two-sided copy of information entered on both sides thereof
US5160530 *Jan 24, 1989Nov 3, 1992Griffin CorporationHerbicides and pesticides
US5175071 *Jun 25, 1991Dec 29, 1992Xerox CorporationEncapsulated toner composition
US5178949 *May 21, 1991Jan 12, 1993Jujo Paper Co., Ltd.Color-former
US5197922 *Nov 13, 1989Mar 30, 1993Schubert Keith EMethod and apparatus for producing two-sided carbonless copies of both sides of an original document
US5223370 *Dec 6, 1991Jun 29, 1993Xerox CorporationReprography; shell-core polymers of acrylics, polyurea, polyurethanes, polyethers, polyamides, polyesters and alkyl cellulose coating
US5224897 *Jun 29, 1992Jul 6, 1993Linden Gerald ESelf-replicating duplex forms
US5244768 *Feb 14, 1992Sep 14, 1993Fuji Xerox Co., Ltd.Manufacturing process for an electrophotographic toner
US5248279 *Dec 16, 1991Sep 28, 1993Linden Gerald ETwo-sided, self-replicating forms
US5281266 *Jun 16, 1992Jan 25, 1994The Wiggins Teape Group LimitedSolvent compositions for use in pressure-sensitive copying paper
US5325721 *Feb 17, 1993Jul 5, 1994Minnesota Mining And Manufacturing CompanySystem for indicating exposure to preselected temperatures or tampering
US5332584 *Dec 9, 1991Jul 26, 1994Zeneca Inc.Microcapsules
US5395288 *Sep 24, 1993Mar 7, 1995Linden; Gerald E.Two-way-write type, single sheet, self-replicating forms
US5401516 *Apr 22, 1993Mar 28, 1995Emisphere Technologies, Inc.Encapsulation of biologically active materials, drug delivery, reaction with benzenesulfonyl chloride or benzoyl chloride
US5443841 *Jul 27, 1992Aug 22, 1995Emisphere Technologies, Inc.Proteinoid microspheres and methods for preparation and use thereof
US5447728 *Dec 16, 1993Sep 5, 1995Emisphere Technologies, Inc.A carrier comprising an acylated amino acid; lowering iron concentration in mammals
US5461027 *Oct 27, 1993Oct 24, 1995Griffin CorporationMicroencapsulated pendimethalin and method of making and using same
US5464803 *Jun 3, 1993Nov 7, 1995The Wiggins Teape Group LimitedPressure-sensitive record material
US5472489 *Oct 27, 1993Dec 5, 1995The Wiggins Teape Group LimitedMixture of vegetable oil and fatty acid ester
US5476829 *Jul 1, 1994Dec 19, 1995The Wiggins Teape Group LimitedBlend of rapid and slow developing chromogen material in vegetable oil and an acid clay
US5478380 *Oct 14, 1993Dec 26, 1995The Wiggins Teape Group LimitedChromogenic composition for use in pressure-sensitive record material
US5518981 *Nov 30, 1994May 21, 1996Nashua CorporationXerographable carbonless forms
US5540939 *Apr 25, 1994Jul 30, 1996Emisphere Technologies, Inc.Encapsulating active materials
US5541155 *Apr 22, 1994Jul 30, 1996Emisphere Technologies, Inc.Acids and acid salts and their use in delivery systems
US5554323 *Nov 4, 1993Sep 10, 1996Fuji Photo Film Co., Ltd.Using continuous emulsification equipment
US5556583 *Feb 2, 1994Sep 17, 1996Dainippon Ink And Chemicals, Inc.Inks, paints, etc
US5578323 *Jun 14, 1993Nov 26, 1996Emisphere Technologies, Inc.Proteinoid carriers and methods for preparation and use thereof
US5601846 *May 9, 1995Feb 11, 1997Emisphere Technologies, Inc.Oligopeptide
US5605874 *Jul 20, 1995Feb 25, 1997The Wiggins Teape Group LimitedPressure-sensitive copying material
US5607738 *Aug 29, 1995Mar 4, 1997Moore Business Forms, Inc.Multiple-part carbonless pressure seal business form assembly
US5629020 *Apr 22, 1994May 13, 1997Emisphere Technologies, Inc.Delivery of sensitive agents such as bioactive peptides
US5643957 *Oct 25, 1994Jul 1, 1997Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5650386 *Mar 31, 1995Jul 22, 1997Emisphere Technologies, Inc.Compositions for oral delivery of active agents
US5650566 *Aug 12, 1996Jul 22, 1997Chou; J. P.Pressure gauge showing a current and a preset pressure
US5667806 *Jun 7, 1995Sep 16, 1997Emisphere Technologies, Inc.Spray drying method and apparatus
US5693338 *Sep 29, 1994Dec 2, 1997Emisphere Technologies, Inc.Delivery composition comprising active agent, diketopiperazine, enzyme inhibitor
US5709861 *Jan 13, 1995Jan 20, 1998Emisphere Technologies, Inc.Compositions for the delivery of antigens
US5714167 *Oct 25, 1994Feb 3, 1998Emisphere Technologies, Inc.Reversibly forming supramolecular complex of active agent with perturbant; drug delivery
US5741591 *Oct 17, 1995Apr 21, 1998Dainippon Ink And Chemicals, Inc.Microcapsules, and encapsulation method therefor
US5750147 *Jun 7, 1995May 12, 1998Emisphere Technologies, Inc.Fungicides for oral administration
US5766633 *Apr 22, 1994Jun 16, 1998Emisphere Technologies, Inc.Modified amino acid carrier, bioactive peptides
US5792451 *Mar 2, 1994Aug 11, 1998Emisphere Technologies, Inc.Oral drug delivery compositions and methods
US5804688 *Feb 7, 1997Sep 8, 1998Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5811127 *Oct 24, 1994Sep 22, 1998Emisphere Technologies, Inc.Desferrioxamine oral delivery system
US5820881 *Apr 28, 1995Oct 13, 1998Emisphere Technologies, Inc.Microspheres of diamide-dicarboxylic acids
US5824345 *Jun 7, 1995Oct 20, 1998Emisphere Technologies, Inc.Microsphere comprising active agent, proteinoid, modified hydrolyzed vegetable protein
US5840340 *Aug 30, 1996Nov 24, 1998Emisphere Technologies, Inc.Oligopeptides with fragrance, cosmetics and dye
US5863944 *Apr 30, 1997Jan 26, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5866536 *Feb 6, 1997Feb 2, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5876710 *Feb 7, 1997Mar 2, 1999Emisphere Technologies Inc.Drug delivery; using a brominated benzamide compound
US5879681 *Feb 7, 1997Mar 9, 1999Emisphere Technolgies Inc.Compounds and compositions for delivering active agents
US5928126 *Dec 6, 1996Jul 27, 1999Aimco Sa (Automatic Instant Mesures Et Controle Optique)Encapsulation
US5939381 *Feb 7, 1997Aug 17, 1999Emisphere Technologies, Inc.4-(4-(phenoxyacetyl)aminophenyl)butyric acid as a carrier for drug delivery
US5955503 *Feb 6, 1997Sep 21, 1999Emisphere Technologies, Inc.Modified amino acid compounds useful as carriers in the delivery of biologically active agents such as, for example, bioactive peptides and the like
US5958457 *May 10, 1995Sep 28, 1999Emisphere Technologies, Inc.Compositions for the delivery of antigens
US5962710 *May 9, 1997Oct 5, 1999Emisphere Technologies, Inc.Reacting an oligosalicylate and an amino acid
US5965121 *Feb 6, 1997Oct 12, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5972387 *Nov 21, 1994Oct 26, 1999Emisphere Technologies, Inc.Modified hydrolyzed vegetable protein microspheres and methods for preparation and use thereof
US5976569 *Apr 29, 1997Nov 2, 1999Emisphere Technologies, Inc.Diketopiperazine-based delivery systems
US5989539 *Feb 6, 1997Nov 23, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US5990166 *Feb 7, 1997Nov 23, 1999Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US6001347 *Feb 6, 1997Dec 14, 1999Emisphere Technologies, Inc.Organic acid compound of given structure having an aromatic amide group, a methoxy group in the ortho position on the aromatic ring, and a lipophilic chain terminated with a carboxylic acid is useful as a nontoxic carrier
US6051258 *Jun 7, 1995Apr 18, 2000Emisphere Technologies, Inc.Proteinoid emulsions and methods for preparation and use thereof
US6060084 *Aug 27, 1998May 9, 2000Cannon Chemical CompanyMethod for preparing a core material containment system and the core material containment system prepared thereby
US6060513 *Feb 7, 1997May 9, 2000Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US6071510 *Apr 23, 1997Jun 6, 2000Emisphere Technologies, Inc.Modified amino acids and compositions comprising the same for delivering active agents
US6071538 *Sep 30, 1997Jun 6, 2000Emisphere Technologies, Inc.Oral delivery composition comprising supramolecular complex
US6084112 *Sep 10, 1996Jul 4, 2000Emisphere Technologies, Inc.Method for preparing ω-aminoalkanoic acid derivatives from cycloalkanones
US6090958 *Feb 7, 1997Jul 18, 2000Emisphere Technologies, Inc.N-(8-carboxyoctyl)-o-hydroxybenzamide and salts
US6099856 *Dec 10, 1996Aug 8, 2000Emisphere Technologies, Inc.Increased bioavailable
US6100285 *Nov 11, 1997Aug 8, 2000Emisphere Technologies, Inc.Method of solubilizing itraconazole
US6100298 *Feb 6, 1997Aug 8, 2000Emisphere Technologies, Inc.Mixture of drug and n-(4-(carboxypropyl)phenyl-4-phenyl-butyramide for improved oral drug delivery
US6180140Jun 2, 1995Jan 30, 2001Emisphere Technologies, Inc.Modified amino acids for drug delivery
US6207080 *Mar 3, 1999Mar 27, 2001Aimco Sa ( Automatic Instant Mesures Et Controle Optique)Composite material comprising at least one reactant homogeneously dispersed in a fluid matrix; can be applied by all the conventional means, forming very fine films which have no identifiable lacunae of reactant
US6221367Sep 29, 1997Apr 24, 2001Emisphere Technologies, Inc.Exposing a biologically active agent to a complexing perturbant to reversibly transform the biologically active agent to the intermediate state and to form a transportable supramolecular complex
US6242495Jun 16, 2000Jun 5, 2001Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US6245359Sep 30, 1997Jun 12, 2001Emisphere Technologies, Inc.Active agent transport systems
US6280322Feb 27, 1995Aug 28, 2001Gerald E. LindenSingle sheet of paper for duplicating information entered on both surfaces thereof
US6310002Mar 7, 2000Oct 30, 2001Appleton Papers Inc.Record material
US6313088Feb 7, 1997Nov 6, 2001Emisphere Technologies, Inc.Carriers used to deliver various active agents through various biological, chemical, and physical barriers
US6331318Sep 30, 1994Dec 18, 2001Emisphere Technologies Inc.Carbon-substituted diketopiperazine delivery systems
US6346242Feb 8, 2000Feb 12, 2002Emishpere Technologies, Inc.Compounds and compositions for delivering active agents
US6348207Sep 30, 1997Feb 19, 2002Emisiphere Technologies, Inc.Exposing biologically active agent to complexing perturbant to reversibly transform biologically active agent to intermediate state and form orally deliverable supramolecular complex, orally administering complex to subject
US6375872Nov 17, 1992Apr 23, 2002Moore Business FormsMicroencapsulated adhesive
US6375983Jun 12, 1997Apr 23, 2002Emisphere Technologies, Inc.Microencapsulated fragrances and method for preparation
US6413550Nov 23, 1998Jul 2, 2002Emisphere Technologies, Inc.Proteinoid carriers and methods for preparation and use thereof
US6428780May 5, 1999Aug 6, 2002Emisphere Technologies, Inc.Modified amino acid
US6461545Jan 6, 2000Oct 8, 2002Emisphere Technologies, Inc.Method of solubilizing and encapsulating itraconazole
US6508604Mar 17, 2000Jan 21, 2003The Procter & Gamble CompanyArticle comprising a cell system
US6544926Oct 11, 2001Apr 8, 2003Appleton Papers Inc.Microcapsules having improved printing and efficiency
US6562755Oct 31, 2000May 13, 2003Ncr CorporationThermal paper with security features
US6803344Dec 21, 2001Oct 12, 2004Ncr CorporationHeat sensitive element with image on backing
US6858564Apr 14, 2004Feb 22, 2005Ncr CorporationUsed as a security feature
US7417022Apr 11, 2005Aug 26, 2008Mhr Institutional Partners Iia LpAmino acid for deliverying active materials; bioavailability
US7497351May 30, 2006Mar 3, 2009Kimberly-Clark Worldwide, Inc.Wet wipe dispensing system
US7517582May 10, 2007Apr 14, 2009Kimberly-Clark Worldwide, Inc.warming sensation on the skin when the wet wipe is used; contact sodium acetate, sodium sulfate, sodium sulfate activator in aqueous sugar solution, release heat to cause a warming sensation on the skin; personal care products
US7553872Feb 13, 2006Jun 30, 2009Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
US7597954Dec 14, 2006Oct 6, 2009Kimberly-Clark Worldwide, Inc.warming sensation on the skin when the wet wipe is used; contact sodium acetate, sodium sulfate, sodium sulfate activator in aqueous sugar solution, release heat to cause a warming sensation on the skin; personal care products
US7645719Oct 13, 2004Jan 12, 2010Ncr CorporationThermal paper with security features
US7648046 *May 30, 2006Jan 19, 2010Kimberly-Clark Worldwide, Inc.Dispensing system for dispensing warm wet wipes
US7654412 *May 30, 2006Feb 2, 2010Kimberly-Clark Worldwide, Inc.Wet wipe dispensing system for dispensing warm wet wipes
US7820193Oct 7, 2004Oct 26, 2010Angiotech Pharmaceuticals, Inc.Anticancer agents; prevent forming blood vessels; removal blockage
US7850041Nov 7, 2008Dec 14, 2010John David AmundsonWet wipes dispensing system
US7914891Dec 28, 2005Mar 29, 2011Kimberly-Clark Worldwide, Inc.Wipes including microencapsulated delivery vehicles and phase change materials
US8034325 *Jun 24, 2003Oct 11, 2011Drug Delivery Solutions LimitedPowder formed of particles of biliquid foam entrapped within polymeric matrix
US8192841Dec 14, 2006Jun 5, 2012Kimberly-Clark Worldwide, Inc.Personal care products for the skin comprising an encapsulation layer surrounding an aqueous core composition of an encapsulating activator, a matrix, and an active agent where the microencapsule has a diameter of 5-5000 micrometers; stability; moisturizers, conditioners, cleaning compounds, wipes
US8686154Jun 10, 2009Apr 1, 2014Emisphere Technologies, Inc.Compounds and compositions for delivering active agents
USRE32162 *Aug 29, 1979May 27, 1986Nippon Petrochemicals Co., Ltd.Pressure sensitive record material employing diaryl alkane solvents
USRE33113 *Sep 17, 1976Nov 14, 1989Fuji Photo Film Co., Ltd.Pressure sensitive recording paper
USRE35862 *Aug 14, 1987Jul 28, 1998Emisphere Technologies, Inc.Delivery systems for pharmacological agents encapsulated with proteinoids
DE1771622B1 *Jun 18, 1968Sep 9, 1971Baumgartner Papiers SaAromatisierendes Zigarettenpapier
DE2134326A1 *Jul 9, 1971Jan 13, 1972 Title not available
DE2210133A1 *Mar 2, 1972Oct 26, 1972 Title not available
DE2251350A1 *Oct 19, 1972Apr 26, 1973Monsanto CoFarbstoffloesungsmittel fuer druckempfindliche aufzeichnungsmaterialien
DE2612036A1 *Mar 22, 1976Oct 14, 1976Moore Business Forms IncKohlefreies mehrfach-kopierblattsystem
DE2719914A1 *May 4, 1977Nov 17, 1977Mead CorpDruckempfindliche, kohlefreie durchschreibepapierblaetter mit neuartigen heissen schmelzsystemen und verfahren zu deren herstellung
DE2820600A1 *May 11, 1978Dec 21, 1978Mead CorpVerfahren zur herstellung von mikrokapsel-beschichtungskompositionen mit pigmentartikeln und daraus hergestellten kompositionen
DE2919838A1 *May 16, 1979Nov 22, 1979Minnesota Mining & MfgTrockene mikrokapseln als druckempfindliche markierungssubstanz sowie druckempfindliches, kohlefreies papier
DE3335174A1 *Sep 28, 1983Apr 12, 1984Mitsubishi Paper Mills LtdProcess for the production of heat-fusible and cold-hardenable printing inks including microcapsules
EP0005921A1 *May 10, 1979Dec 12, 1979Monsanto Europe S.A.Mark-recording systems
EP0037477A2 *Mar 13, 1981Oct 14, 1981Bayer AgCopying system and method for its manufacture, and offset or printing dyes useful in this system
EP0064204A1 *Apr 19, 1982Nov 10, 1982Bayer AgProduction of carbonless copying papers by flexography
EP0593192A2 *Oct 5, 1993Apr 20, 1994The Wiggins Teape Group LimitedChromogenic composition for use in pressure-sensitive record material
EP0697292A1Jul 12, 1995Feb 21, 1996The Wiggings Teape Group LimitedPressure-sensitive copying material
EP0697293A1Jul 24, 1995Feb 21, 1996CopigraphNew organic solvent for microcapsules useful notably for pressure-sensitive copy paper and pressure-sensitive copy coated with such microcapsules
EP0714786A1Dec 1, 1995Jun 5, 1996CopigraphNew microcapsules comprising as solvent a terpene derivative or an abietic acid derivative, notably for chemical copy papers and messure sensitive papers coated with such microcapsules
WO1991015947A1 *Mar 22, 1991Oct 31, 1991Isp Investments IncPreparation of discrete microdroplets of an oil in water stabilized by in situ polymerization of a water-soluble vinyl monomer
WO2013150085A1 *Apr 4, 2013Oct 10, 2013Basf SeAmino plastic containing porous particles
Classifications
U.S. Classification503/200, 521/920, 106/31.69, 106/31.33, 503/215, 101/491, 430/138, 428/402.2, 428/402.22, 428/327, 428/402.24, 503/214, 101/DIG.290, 264/4.4, 106/31.65, 106/31.29, 206/524.1, 264/4.6, 106/31.61
International ClassificationB41M5/165, B01J13/12
Cooperative ClassificationY10S101/29, B01J13/125, Y10S521/92, B41M5/165
European ClassificationB01J13/12B, B41M5/165