Patent Application
20220133603
This invention relates to controlled release compositions, encapsulation compositions and methods for making and using them.
There are many microencapsulated delivery systems disclosed in the art to control the release of the encapsulated active, or provide release when a specific trigger is applied. Such systems have previously suffered from a number of drawbacks.
Controlled release microcapsules that provide release of active upon application of shear or friction generally suffer from several drawbacks: (1) such microcapsules are made of highly crosslinked membranes and membrane materials that cannot be broken down by microbes found in the environment, (2) despite such highly crosslinked membranes, the materials of construction of the membrane impart high permeabilities when incorporated into products that contain high levels of surfactant, solvents, and/or water, which results in the premature benefit agent release, (3) they can only effectively encapsulate a limited breadth of benefit agents, (4) they either are so stable that they do not release the benefit agent in use or have insufficient mechanical stability to withstand the processes required to incorporate them in and/or make a consumer product, (5) they do not adequately deposit on the surface that is being treated with consumer product that contains microcapsules, and/or (6) they do not comprise membrane materials that have a favorable environmental degradability profile.
Such microcapsules are made via chemical processes that require the development of a membrane at the oil-water interface. Said membrane can be developed from the oil side or the water side, or both. An emulsion comprising the active material (dispersed phase) is stabilized in a continuous phase. In one mode, a shell material is deposited from the continuous phase onto a dispersed phase via precipitation of the shell material. In another mode, the shell material is manufactured within the dispersed phase, and migration of the shell material is induced via an interfacial reaction or insolubility of the shell material in the oil phase. The two approaches could be combined to develop “multi-shell” capsules.
There is a challenge in designing a membrane that minimizes the diffusion of the encapsulated active into the surrounding formulation, and yet is environmentally biodegradable. Environmentally biodegradable polymers generally swell in water, or are soluble in water. In contrast, microcapsule membranes generally need to resist swelling or dissolution in aqueous cleaning product formulation. A high degree of crosslinking within the membrane can reduce swelling and solubility; however, such highly cross linked membranes are difficult for environmentally available microbes to digest and breakdown.
A study on biodegradability of LDPE/starch blend by Thakore et. al. [European Polymer Journal 37 (2001) 151-160] shows that a physical mixture that comprises 20% of a natural material that has 100% environmental biodegradability is combined with 80 wt % of a material 0% biodegradability, wherein there is no chemical reaction taking place between the components, one would expect that the final material would have 20% biodegradability. However, the results explicitly point out that the biodegradability is reduced to 10%. The biodegradability of a membrane is not only dependent on the components that make up the membrane, but how these components are interacting with one another (reaction vs. physical mixture), and the accessibility of the materials to the microbes that will digest these materials.
In WO2020195132A1, Fujifilm clarifies that when isocyanates dissolved in the core material are reacted with highly biodegradable resins in the water phase (e.g. gelatin, chitosan, celluloses), the resulting interfacial membrane shows an increase in biodegradability; however, it is nowhere close to the biodegradability of the biodegradable resin. The inventors also show that an increase in crosslink density is necessary to minimize the diffusion of the core material through the membrane. Such increase in crosslink density reduces the environmental biodegradability of the membrane.
Like WO2020195132A1, art that discusses polyurea capsules, made via the reaction of polyisocyanates with amines, discloses polyisocyanates dissolved in an oil phase, and the amines dissolved in the water phase. These two materials come together at the oil/water interface to produce a polyurea reaction product. Surprisingly, incorporating uniquely modified amine containing materials in the same phase as the polyisocyanate, and a separate portion of amines in the water phase, provides a membrane with better barrier properties and higher environmental biodegradability.
While others have attempted to improve the barrier properties of microcapsules, there remains significant shortcoming and limitations in the art. For example, U.S. Pat. No. 9,944,886B2 Hitchcock et. al. describes metal coated microcapsules with improved barrier properties. The Hitchcock metal coating is developed after the formation of the microcapsule membrane, via the use of sterically stabilized nanosuspension of metal particle. Such metal coated microcapsules could improve barrier properties; however, it is difficult to imagine how the encapsulated active would be released, since a metal coating would be difficult to fracture. Furthermore, the processing steps involved to achieve the metal coating are laborious and expensive. Moreover, such metal coating could render the microcapsules non-environmentally biodegradable.
US2011/0268778A1 Dihora et. al. provides microcapsules made using UV initiation in order to form membranes at lower temperatures. However, prior to the free radical polymerization to form the membrane, the hydrophobic active material needs to be heated to temperatures beyond 60 degrees Centigrade. Moreover, Example 2 of the application clearly delineates poorer barrier properties of the membrane made via UV initiator versus the same capsules made via use of thermal initiation. Because of the non-transparency of the system, UV initiation to form a membrane has low efficiency. The resulting barrier properties and biodegradability of the resulting polyacrylate microcapsules are poor.
U.S. Pat. No. 9,937,477B2 Zhang et. al. discloses core/shell microcapsules that are manufacture using free radical polymerization of acrylates; such microcapsules require multi-step reactions that require heating the capsules to 95 degrees Centigrade for up to 6 hours. It is well known that such polyacrylate capsules that are highly crosslinked have poor environmental biodegradability.
Various methods of producing silk fibroin particles are known in the art. In some embodiments, the silk particles can be produced by a polyvinyl alcohol (PVA) phase separation method as described in, e.g., WO 2011/041395. Other methods for producing silk fibroin particles are described, for example, in US 2010/0028451 and WO 2008/118133 (using oil as a template for making silk microspheres or nanospheres), and in Wenk, et al. (2008) J. Control. Release 132:26-34 (using spraying method to produce silk microspheres or nanospheres). However, none of these methods modify the zwitterionic nature of the protein to make it reactive such that it can be incorporated into the membrane of a microcapsule
Conventional controlled release particles that comprise a core and a shell have several limitations. First, such capsules prematurely release the active material when suspended in a finished product formulations, such as cleaning product formulations. Second, such capsules have poor environmental biodegradability due to the nature of materials used and the degree of crosslinking that is achieved in order to reduce the diffusion of the active. Third, it is difficult to control the release profile of the encapsulated active. Fourth, poor adhesion of particles to the substrate result in significant loss of the particles, especially when formulations containing such particles are used in rinse-off applications. Examples of such applications include laundering fabrics, shampooing hair, conditioning hair, cleansing the skin, showering, and the like. In such applications, a composition comprising microcapsules is applied to a substrate to initiate cleaning, and subsequently the composition is removed by using water.
Thus, the instant disclosure supplies least three different types of particles; one type of particles (Type A), which have a membrane that is the reaction product of a basified biodegradable resin; a second type (Type B) of particles which provide a membrane that is developed by incorporating a pre-reaction product of a polyisocyanate; and a third type (Type C) of particles which are provided by the reaction product of a pre-reacted natural material resin that is incorporated into the core material. Such Type A, Type B, and Type C particles provide better barrier properties and better environmental biodegradability.
It is desired to remove soil and dirt, but desired to retain active materials during the rinsing process by the retention of microcapsules on the substrate.
It is further desired to provide a means to manipulate the release profile of the encapsulated active.
It is further desired to provide microcapsules that are processed at temperatures at or below 60° C., with a batch cycle time of less than 12 hours, and able to achieve a degree of crosslinking that is sufficient to reduce the diffusion of the encapsulated active out of the microcapsule yet provide more than 50% environmental biodegradability of the membrane material.
Hence, it is desired to provide low permeability microcapsules that are able to retain the encapsulated active in surfactant containing solutions, or under highly dilute aqueous conditions. It is desired to improve the adhesion of microcapsules onto the desired substrate during rinse-off applications. It is desired to release the encapsulated active in larger quantities, and over a longer duration of time. It is desired to have capsules that have a favorable environmental biodegradability profile as defined by OECD 301D method (OECD 1992, Test No. 301 Ready Biodegradability, OECD Guidelines for the Testing of Chemicals, Section 3, OECD Publishing, Paris, https://doi.org/10.1787/9789264070349-en).
All references cited herein are incorporated herein by reference in their entireties. The citation of any reference is not to be construed as an admission that it is prior art with respect to the present invention. To the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
The present invention relates to microcapsules comprising a core and shell, wherein the shell comprises a membrane developed around the core material to reduce the diffusion of core material into the environment. Materials and methods are presented to seal the pores in the membrane while also improving environmental biodegradability.
Inventors have surprisingly found that incorporation of biodegradable resins in the core material during capsule making achieves a membrane with better barrier properties and better environmental biodegradability. Inventors have discovered that such biodegradable resins need to be modified prior to incorporation into the core, such modifications make them reactive. In the absence of such modification, the biodegradable resins are simply dispersed in the core material, but do not become a part of the membrane surrounding the core material. It is only when these modified resins become a part of the membrane that they impart better barrier properties and better environmental biodegradability.
The present invention relates to a method for preparing a composition comprising controlled release particles.
A first aspect of the invention is a method for preparing a composition comprising controlled release particles, said method comprising the sequential steps of:
In certain embodiments the emulsifier is a member selected from the group consisting of polyalkylene glycol ether; polyvinyl acetate; copolymers of polyvinyl acetate; polyacrylamide; poly(N-isopropylacrylamide); poly (2-hydroxypropyl methacrylate); poly(2-ethyl-2-oxazoline); poly(2-isopropenyl-2-oxazoline-co-methyl methacrylate); poly(methyl vinyl ether); polyvinyl alcohol-co-ethylene; polyvinyl pyrrolidone; copolymers of polyvinhyl pyrrolidone; 1H-Imidazolium, 1-ethenyl-3-methyl-, chloride; polymer with 1-ethenyl-2-pyrrolidinone; vinyl acetate; Hydroxypropyl methyl cellulose; gum arabic; polypeptides; gelatin, functionalized gelatin; pectin, functionalized pectin; agarose; carboxymethyl cellulose; colloidal silica; sodium alginate; palmitamidopropyltrimonium chloride; distearyl diimonium chloride; cetyltrimethylammonium chloride; quaternary ammonium compounds; fatty amines; aliphatic ammonium halides; alkyldimethyl benzylammonium halides; alkyldimethylethylammonium halides; polyethyleneimine; poly(2-dimethylamino)ethyl methacrylate)methyl chloride quaternary salt; poly(l-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate); poly(acrylamide-co-diallyldimethylammonium chloride); poly(allylamine); polybis(2-chloroethyl)ether-alt-1,3-bis(3-(dimethylamino)propylurea quaternized; and poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine.
In certain embodiments step (d) is conducted for 0.5 hours at room temperature, step (e) is conducted for 1 hour and step (f) comprises increasing a temperature of the aqueous suspension to 40° C. to 60° C. and reacting for 2 to 5 hours.
In certain embodiments the amine moiety containing material is at least one member selected from the group consisting of linear aliphatic amines, aromatic amines, silicone amines, branched amines, polyamines, polypeptides, polyetheramines, and amino acids.
In certain embodiments the at least one isocyanate is at least one member selected from the group consisting of aliphatic isocyanates, aromatic isocyanates, polymeric isocyanates, cyclic isocyanates, hydrophilic isocyanates, hydrophobic isocyanates, isocyanurates, waterborne isocyanates and urethane acrylates containing isocyanate functionalities.
In certain embodiments the organofunctional silane as at least one member selected from the group consisting of alkoxylated silane, trialkoxy silanes, functionalized trialkoxysilanes (amino, glycidoxy, methacryloxy, vinyl), tetraalkoxylated silanes including tetramethoxy silane and tetraethoxy silane, 1,2-bis(triethyxysilyl)ethane.
In certain embodiments the at least one epoxy is at least one member selected from the group consisting of epoxidized unsaturated oils, epoxidized alcohols and epoxidized polysaccharides.
In certain embodiments the at least one epoxide curing agent is at least one member selected from the group consisting of trimethylol propane triglycidyl ether, resins containing acrylate and epoxy functional groups, diepoxide of a cycloapliphatic alcohol, hydrogenated Bisphenol A, and resorcinol/bisphenol F resin with polyfunctional epoxide resin blend.
In certain embodiments the polysaccharide is included in the oil phase and is at least one member selected from the group consisting of tapioca, potato, corn, rice, wheat, carboxymethyl starch, carboxymethyl chitosan, chitosan oligosaccharide, hydroxy propyl methyl starch, hydroxy propyl cellulose, ethyl cellulose, methyl cellulose, and octenyl succinic anhydride modified starch.
In certain embodiments the basified biodegradable resin is included in the oil phase and is at least one member selected from the group consisting of casein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried particles comprising gelatin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried chitosan oligosaccharide whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried whey protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried soy protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried silk fibroin protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried lignin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried tannic acid whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; and spray dried carboxymodified cellulose whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying.
In certain embodiments the inorganic solid particle is included in the oil phase and is at least one member selected from the group consisting of organically modified or water insoluble clays, minerals, and salts.
In certain embodiments, the pre-reaction product of polyisocyanate comprises monohydroxy monomers defined by Formula 1 or Formula 2 reacted with a polymeric isocyanate. Preferably, such pre-reaction product of polyisocyanate contains active isocyanate functionalities with esters in the side chain. Nonlimiting examples of polyisocyanates comprise polymeric isocyanates containing 2 or more isocyanate functionalities, cyclic isocyanates, hydrophilic isocyanates, hydrophobic isocyanates, waterborne isocyanates and urethane acrylates containing isocyanate functionalities. Nonlimiting examples of the monohydroxy monomers comprise materials defined by Formula 1 or Formula 2:
In certain embodiments the pre-reacted natural material resin is included in the oil phase and is a spray dried composite of a polyamide epichlorohydrin and a natural material, said composite formed by curing the spray dried particle at elevated temperature to crosslink the polyamide epichlorohydrin material with amine, hydroxyl, carboxyl, and/or thiol functionalities of at least one of monosaccharides, oligosaccharides, polysaccharides, amino acids, proteins, celluloses, carboxy modified saccharides, celluloses, and mixtures thereof. In certain embodiments, the pre-reacted natural material resin is included in the oil phase and is a bulk reaction product of an epoxy or epoxide curing agent and a natural material, said composite formed by reacting the epoxy or epoxide curing agent in a reactor at elevated temperatures to crosslink the epoxy or epoxide curing agent with amine or acid functaionalities of said natural material. Such natural material could be a basified biodegradable resin.
In certain embodiments, the pre-reacted natural material resin comprises a polymer having a polyamide epichlorohydrin to natural material weight ratio of from about 1:99, from about 5:95, from about 10:90, or from about 20:80.
In certain embodiments, the pre-reacted natural material resin comprises a polymer having an epoxy or epoxide curing agent to natural material weight ratio of from about 1:99, from about 5:95, from about 10:90, or from about 20:80.
In certain embodiments, the copolymer of maleic anhydride is a reaction product of dehydrated maleic acid with an acyclic, cyclic or vinylic aromatic alkene. The presence of such acid groups allows one to utilize reaction chemistry to attach additional materials covalently to the membrane to improve permeability properties and/or environmental biodegradability.
In certain embodiments, the plasticizer is included in the oil phase and is at least one member selected from the group consisting of methyl esters of rosin, polyazelate esters, di-fatty acid esters, citrate esters, polyadipate esters and polyester resins consisting of inner and intra-esters of polyhydroxy carboxylic acids.
In certain embodiments, the polyaziridine comprises a member selected from the group consisting of polymers having at least 2 aziridine functional groups as terminal or pendant groups.
The polyaziridine is present in particles of the invention in an amount effective to react with carboxylic acid moieties. The amount of polyaziridine on a dry basis (weight of polyaziridine per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.4 wt. % or 0.6 wt. % or 1.0 wt. % to 1.4 wt. % or 2.0 wt. % or 3.8 wt. %.
In certain embodiments, the polyoxazoline comprise a polymer with more than one oxazoline functional groups. The oxazolines can be present as the terminal end of a polymer or can be pendant groups attached to a polymer backbone. The oxazolines may be product of free radical polymerization of vinyl oxazolines. Oxazolines are also known as oxazaolyls.
The polyoxazoline is present in particles of the invention in an amount effective to react with carboxylic acid moieties. The amount of polyoxazoline on a dry basis (weight of polyaziridine per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.4 wt. % or 0.6 wt. % or 1.0 wt. % to 1.4 wt. % or 2.0 wt. % or 3.8 wt. %.
In certain embodiments the controlled release particles have a diameter from 0.1 microns to less than 200 microns.
In certain embodiments the composition is a powdered food product, a fluid food product, a powdered nutritional supplement, a fluid nutritional supplement, a fluid fabric enhancer, a solid fabric enhancer, a fluid shampoo, a solid shampoo, a hair conditioner, a body wash, a solid antiperspirant, a fluid antiperspirant, a solid deodorant, a fluid deodorant, a fluid detergent, a solid detergent, a fluid hard surface cleaner, a solid hard surface cleaner, a fluid fabric refresher spray, a diaper, an air freshening product, a nutraceutical supplement, a controlled release fertilizer, a controlled release insecticide, a controlled release dye or a unit dose detergent comprising a detergent and the controlled release particles in a water soluble film.
In certain embodiments the method further comprises at least one suspension agent to suspend the controlled release particles, wherein the at least one suspension agent is at least one member selected from the group consisting of a rheology modifier, a structurant and a thickener.
In certain embodiments the at least one suspension agent has a high shear viscosity at, 20 sec−1 shear rate and at 21° C., of from 1 to 7000 cps and a low shear viscosity, at 0.5 sec−1 shear rate at 21° C., of greater than 1000 cps.
In certain embodiments the composition is a fluid having a high shear viscosity, at 20 sec−1 and at 21° C., of from 50 to 3000 cps and a low shear viscosity, at 0.5 sec−1 shear rate at 21° C., of greater than 1000 cps.
In certain embodiments the at least one suspension agent is a member selected from the group consisting of polyacrylates, polymethacrylates, polycarboxylates, pectin, alginate, gum arabic, carrageenan, gellan gum, xanthan gum, guar gum, gellan gum, hydroxyl-containing fatty acids, hydroxyl-containing fatty esters, hydroxyl-containing fatty waxes, castor oil, castor oil derivatives, hydrogenated castor oil derivatives, hydrogenated castor wax, perfume oil, and mixtures thereof.
In certain embodiments the composition comprises two different controlled release particles which are friction-triggered release microcapsules which release the hydrophobic active ingredient at different rates due to a difference in shell material friability or core material viscosity.
In certain embodiments the at least one hydrophobic active ingredient comprises a mixture of a hydrophobic active and a material selected from the group consisting of brominated oils, epoxidized oils, highly nonpolar oils, hydrophobically modified inorganic particles, nonionic emulsifiers and oil thickening agents.
In certain embodiments the composition has an Environmental Biodegradability greater than 50%.
A second aspect of the invention is a composition comprising controlled release particles prepared by the method herein.
In certain embodiments each of the controlled release particles of the said composition comprise:
In certain embodiments the controlled release particles comprise:
In certain embodiments the shell is degradable by microbes found in wastewater streams to release the at least one hydrophobic active ingredient.
In certain embodiments the at least one hydrophobic active ingredient is at least one member selected from the group consisting of a flavorant, a fragrance, a chromogen, a dye, an essential oil, a sweetener, an oil, a pigment, an active pharmaceutical ingredient, a moldicide, a herbicide, a fertilizer, a phase change material, an adhesive, a vitamin oil, a vegetable oil, a triglyceride and a hydrocarbon.
In certain embodiments, the copolymer of maleic anhydride comprises the reaction products of dehydrated maleic acid with acyclic or cyclic or vinylic aromatic alkenes. Preferably, the copolymers of maleic anhydride are neutral or alkaline water soluble copolymers of isobutylene or ethylene or alkylene and maleic anhydride that may be in the form of an amide ammonium salt.
In certain embodiments, the polysaccharide comprises natural polysaccharides or modified polysaccharides. Natural polysaccharides include natural starches such as tapioca, potato, corn, rice, wheat, and the like. Modified polysaccharides comprise carboxy modified polysaccharide or cellulose such as carboxymethyl starch, carboxymethyl chitosan, chitosan oligosaccharide, hydroxy propyl methyl starch, hydroxy propyl cellulose, ethyl cellulose, methyl cellulose, and octenyl succinic anhydride modified starch.
In certain embodiments, the basified biodegradable resin comprises a protein, or polysaccharide, or oligosaccharide, or cellulose, or polyphenol, or lipid. The hydroxyl or amine functionalities of these materials have been made more reactive by altering the pH. Preferably, the pH of the protein, or polysaccharide, or oligosaccharide, or lipid is increased using an organic or inorganic base, preferably sodium carbonate, and the mixture is dehydrated to yield a powder. Nonlimiting examples of basified biodegradable resins include spray dried particle comprising casein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried particle comprising gelatin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried chitosan oligosaccharide whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried whey protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried soy protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried silk fibroin protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried lignin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried tannic acid whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried carboxymodified cellulose whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying.
In certain embodiments, the plasticizers are polymeric in nature, having a molecular weight greater than 1000 Daltons, and are preferably methyl esters of rosin, polyazelate esters, di-fatty acid esters, citrate esters, polyadipate esters, and polyester resins consisting of inner and intra-esters of polyhydroxy carboxylic acids
In certain embodiments, the pre-reacted natural material resin comprises a monomer or polymer having at least 1 functional group that is capable of reacting with isocyanate or epoxy groups. The pre-reacted natural material resin comprises a natural material and a crosslinker. The natural material is selected from the group consisting of polypeptide or protein, or polysaccharide, or oligosaccharide, or cellulose, or polyphenol, or lipid. The crosslinker is selected from the group consisting of water-based crosslinking resins that are reactive with amine, carboxyl, hydroxyl, and thiol functionality. The crosslinker is selected from the group consisting or epoxy, epoxide curing agent, or polyamide epichlorohydrin. Preferably the crosslinker is polyamide epichlorohydrin that has a high content of secondary amines. In a preferred embodiment, the pre-reacted natural material resin is made by pursuing the following procedure: 1) the natural material is mixed with the polyamide epichlorohydrin to make a homogeneous solution in water; 2) the pH of the system is adjusted to optimize conditions for the reaction; 3) the mixture is dehydrated, preferably using a spray drying process, and 4) the resulting powder is heated at a temperature greater than 100 degrees Centigrade for more than 30 minutes to assure crosslinking. Nonlimiting examples of pre-reacted natural material resin comprise polyamide epichlorohydrin, epoxy, or epoxide curing agent reaction product with proteins such as casein, whey protein, soy protein, silk protein, zein protein, and the like; reaction product with oligosaccharides and polysaccharides such as chitosan oligosaccharide, carboxymethyl starch, alginic acid, hyaluronic acid, pectin, glucuronic acid, gum Arabic, and the like; reaction products with celluloses such as carboxymethyl cellulose, microcrystalline cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropylmethyl cellulose phthalate, hydroxypropyl methyl cellulose acetate succinate, and the like; reaction products with polyphenols such as lignin, tannic acid, and the like; and mixtures thereof.
In certain embodiments, the composition comprises two different controlled release particles selected from the group consisting of friction-triggered release microcapsules and water-triggered release microcapsules.
In certain embodiments of the method, the emulsifier is a member selected from the group consisting of palmitamidopropyltrimonium chloride, distearyl dimonium chloride, cetyltrimethylammonium chloride, quaternary ammonium compounds, fatty amines, aliphatic ammonium halides, alkyldimethyl benzylammonium halides, alkyldimethylethylammonium halides, polyethyleneimine, poly(2-dimethylamino)ethyl methacrylate)methyl chloride quaternary salt, poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), poly(acrylamide-co-diallyldimethylammonium chloride), polybis(2-chloroethyl)ether-alt-1,3-bis(3-(dimethylamino)propylurea quaternized, polyalkylene glycol ether, polyvinyl acetate, copolymers of polyvinyl acetate, polyacrylamide, poly(N-isopropylacrylamide), poly (2-hydroxypropyl methacrylate), poly(2-ethyl-2-oxazoline), poly(2-isopropenyl-2-oxazoline-co-methyl methacrylate), poly(methyl vinyl ether), and polyvinyl alcohol-co-ethylene), polyvinyl pyrrolidone, copolymers of polyvinhyl pyrrolidone, 1H-Imidazolium, 1-ethenyl-3-methyl-, chloride, polymer with 1-ethenyl-2-pyrrolidinone, vinyl acetate and gum Arabic, gelatin, functionalized gelatin, pectin, functionalized pectin, agarose, carboxymethyl cellulose, colloidal silica, sodium alginate, and the like.
The invention will be described in conjunction with the following drawings, wherein:
Glossary
Throughout the description, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings also consist essentially of, or consist of, the recited components, and that the processes of the present teachings also consist essentially of, or consist of, the recited processing steps.
In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components and can be selected from the group consisting of two or more of the recited elements or components.
The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term “about” is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise.
It should be understood that the order of steps or order for performing certain actions is immaterial so long as the present teachings remain operable. Moreover, two or more steps or actions can be conducted simultaneously.
As used herein, unless otherwise noted, the terms “capsule”, “microcapsule” and “particle” are synonyms, which refer to containers for selectively retaining an active ingredient.
As used herein, unless otherwise noted, the terms “shell,” “membrane” and “wall” are synonyms, which refer to barriers at least partially surrounding the core of the particles of the invention.
As used herein, microcapsules “formed under acidic conditions” means that part of the process of forming the microcapsule involves a step where the pH of the suspension in which the microcapsules form is adjusted into the acidic region (less than 7).
As used herein, microcapsules “formed under basic conditions” means that part of the process of forming the microcapsule involves a step where the pH of the suspension in which the microcapsules form is adjusted into the alkaline region (greater than 7).
As used herein, “an unreacted amount” refers to the amount of a reactant not used up in one or more reaction. “An unreacted amount” can be zero to any amount depending on the amount of reactants added.
As used herein, unless otherwise noted, “alkyl” whether used alone or as part of a substituent group refers to straight and branched carbon chains having 1 to 20 carbon atoms or any number within this range, for example 1 to 6 carbon atoms or 1 to 4 carbon atoms. Designated numbers of carbon atoms (e.g. C1-6) shall refer independently to the number of carbon atoms in an alkyl moiety or to the alkyl portion of a larger alkyl-containing substituent. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, and the like. Alkyl groups can be optionally substituted. Non-limiting examples of substituted alkyl groups include hydroxymethyl, chloromethyl, trifluoromethyl, aminomethyl, 1-chloroethyl, 2-hydroxyethyl, 1,2-difluoroethyl, 3-carboxypropyl, and the like. In substituent groups with multiple alkyl groups, the alkyl groups may be the same or different.
The term “substituted” is defined herein as a moiety, whether acyclic or cyclic, which has one or more hydrogen atoms replaced by a substituent or several (e.g., 1 to 10) substituents as defined herein below. The substituents are capable of replacing one or two hydrogen atoms of a single moiety at a time. In addition, these substituents can replace two hydrogen atoms on two adjacent carbons to form said substituent, new moiety or unit. For example, a substituted unit that requires a single hydrogen atom replacement includes halogen, hydroxyl, and the like. A two hydrogen atom replacement includes carbonyl, oximino, and the like. A two hydrogen atom replacement from adjacent carbon atoms includes epoxy, and the like.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
As used herein “cleaning and/or treatment compositions” means products comprising fluid laundry detergents, fabric enhancers, laundry and/or rinse additives, fluid dishwashing detergents, fluid hard surface cleaning and/or treatment compositions, fluid toilet bowl cleaners that may or may not be contained in a unit dose delivery product all for consumer, agricultural, industrial or institutional use.
The term “absorbent article” is used herein in a very broad sense including any article able to receive and/or absorb and/or contain and/or retain fluids and/or exudates, especially bodily fluids/bodily exudates. Exemplary absorbent articles in the context of the present invention are disposable absorbent articles.
The term “disposable” is used herein to describe articles, which are not intended to be laundered or otherwise restored or reused as an article (i.e. they are intended to be discarded after a single use and preferably to be recycled, composted or otherwise disposed of in an environmentally compatible manner). Typical disposable absorbent articles according to the present invention are diapers, surgical and wound dressings, breast and perspiration pads, incontinence pads and pants, bed pads as well as absorbent articles for feminine hygiene like sanitary napkins, panty liners, tampons, interlabial devices or the like. Absorbent articles suitable for use in the present invention include any type of structures, from a single absorbent layer to more complex multi-layer structures. Certain absorbent articles include a fluid pervious topsheet, a backsheet, which may be fluid impervious and/or may be water vapor and/or gas pervious, and an absorbent element comprised there between, often also referred to as “absorbent core” or simply “core”.
The term “Sanitary tissue product” or “tissue product” as used herein means a wiping implement for post-urinary and/or post-bowel movement cleaning (toilet tissue products), for otorhinolaryngological discharges (facial tissue products) and/or multi-functional absorbent and cleaning uses (absorbent towels such as paper towel products and/or wipe products). The sanitary tissue products of the present invention may comprise one or more fibrous structures and/or finished fibrous structures, traditionally, but not necessarily, comprising cellulose fibers.
The term “tissue-towel paper product” refers to products comprising paper tissue or paper towel technology in general, including, but not limited to, conventional felt-pressed or conventional wet-pressed tissue paper, pattern densified tissue paper, starch substrates, and high bulk, uncompacted tissue paper. Non-limiting examples of tissue-towel paper products include towels, facial tissue, bath tissue, table napkins, and the like.
“Personal care composition” refers to compositions intended for topical application to skin or hair and can be, for example, in the form of a liquid, semi-liquid cream, lotion, gel, or solid. Examples of personal care compositions can include, but are not limited to, bar soaps, shampoos, conditioning shampoos, body washes, moisturizing body washes, shower gels, skin cleansers, cleansing milks, in-shower body moisturizers, pet shampoos, shaving preparations, etc.
“Bar soap” refers to compositions intended for topical application to a surface such as skin or hair to remove, for example, dirt, oil, and the like. The bar soaps can be rinse-off formulations, in which the product is applied topically to the skin or hair and then subsequently rinsed within minutes from the skin or hair with water. The product could also be wiped off using a substrate. Bar soaps can be in the form of a solid (e.g., non-flowing) bar soap intended for topical application to skin. The bar soap can also be in the form of a soft solid which is compliant to the body. The bar soap additionally can be wrapped in a substrate which remains on the bar during use.
“Rinse-off” means the intended product usage includes application to skin and/or hair followed by rinsing and/or wiping the product from the skin and/or hair within a few seconds to minutes of the application step.
“Ambient” refers to surrounding conditions at about one atmosphere of pressure, 50% relative humidity and about 25° C.
“Anhydrous” refers to compositions and/or components which are substantially free of added or free water.
“Antiperspirant composition” refers to antiperspirant compositions, deodorant compositions, and the like. For example, antiperspirant creams, gels, soft solid sticks, body sprays, and aerosols.
“Soft solid” refers to a composition with a static yield stress of about 200 Pa to about 1,300 Pa. The term “solid” includes granular, powder, bar and tablet product forms.
The term “fluid” includes liquid, gel, paste and gas product forms.
The term “situs” includes paper products, fabrics, garments, hard surfaces, hair and skin.
The term “substantially free of” refers to 2% or less of a stated ingredient. “Free of” refers to no detectable amount of the stated ingredient or thing.
As used herein, the terms “a” and “an” mean “at least one”.
As used herein, the terms “include”, “includes” and “including” are meant to be non-limiting.
Unless otherwise noted, in discussing the commercial applications below, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or byproducts, which may be present in commercially available sources of such components or compositions.
Similarly, all percentages and ratios are calculated by weight unless otherwise indicated and are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Advantages of the Invention
One or more of the following benefits are provided by preferred embodiments of the invention.
The inventive particles' shell material have an environmental biodegradability greater than 50% as measured by the OECD 301D method that utilizes biological oxygen demand as the criteria for measuring degradability. Conventional capsules utilize polymers that may be biodegradable prior to shell formation, but due to the nature of crosslinkers that are used and the chemical structure of the final crosslinked polymer, microbes are no longer able to attach to the polymer or the backbone to sufficiently degrade the shell material. The inventive particles utilize monomers and polymers that retain degradable functional groups even after the crosslinking is complete, such that microbes in the environment are able to digest the shell material.
The inventive particles adhere onto desired substrates via the use of viscoelastic and electrostatic interactions. By adhering large particles as well as small particles during the rinse off application, greater volumes of active material can be delivered with a higher delivery efficiency of the encapsulated active. Conventional capsules are limited to the deposition of small particles, which carry much less volume of active material. Only a fraction of these small microcapsules fracture during use, resulting in significantly lower delivery efficiency of the encapsulated active. Moreover, inventors have discovered formulation approaches to control the level of aggregation of capsules such that a higher quantity of microcapsules can be retained onto the substrate during a rinse-off or filtration process. Such discovery can reduce the quantity of capsules that are lost in the rinse water, and can reduce the environmental impact.
In order to deliver a consumer noticeable benefit, yet deliver that benefit at a low cost, encapsulation is used to isolate a uniquely different fragrance or flavor active from the non-encapsulated fragrance or flavor that is incorporated into the formulation. Acclamation to a flavor or fragrance requires a much higher concentration of the same fragrance or flavor to achieve noticeability. The invention allows one to encapsulate a uniquely different fragrance or flavor to incorporate into the composition, and achieve noticeability at significantly lower concentrations of the encapsulated active. Improvement of retention of capsules onto the fabric during rinse-off processes also has the potential to reduce cost.
Particles
The invention addresses one or more of the prior art deficiencies described above by providing controlled release particles. The particles are particularly well-suited for use in encapsulation of hydrophobic, nonpolar materials.
The particles are preferably used in a consumer product composition, such as, e.g., a cleaning composition, a fabric care composition and/or a personal care composition.
The particles preferably comprise a hydrophobic active ingredient surrounded by a wall material that comprises a mixture of several different polymers—a polyurea, a poly(amine alcohol), a silica, a polyamide, a polyester, polysaccharide, a polyphenol, a cellulose, and optionally, a quaternary amine.
The polyurea preferably comprises a reaction product of 1) an isocyanate functionality and 2) an amine functionality. Preferably, the isocyanate functionality is provided by polymeric isocyanates with a molecular weight greater than 300 grams per mole. Preferably, the amine functionality is provided by, for example, acidic amines such as lysine hydrochloride, urea, tryptophan hydrochloride, guanidine hydrochloride, and the like; neutral amines such as aniline, cyanamide, 4-aminobenzoic acid, and the like; and basic amines such as ethylenediamine, diethylenetriamine, guanidine, pentaethylene hexamine, hexamethylenetetramine, tetraethylene pentamine, and quaternary amines such as Girard's reagent; silicone amines such as aminopropylsilsequioxane oligomer, water borne amino alkyl silsequioxane oligomers, trihydroxysilylpropylamine condensate, 3-aminopropyl(diethoxy)methylsilane, [3-(2-aminoethyl)-aminopropyl] methyl-dimethoxysilane, [3-(2-aminoethyl)-aminopropyl]trimethoxysilane, spray dried particle comprising casein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried particle comprising gelatin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried chitosan oligosaccharide whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried whey protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried soy protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried silk fibroin protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried composite of a polyamide epichlorohydrin and a natural material, said composite formed by curing the spray dried particle at elevated temperature to crosslink amine, hydroxyl, carboxyl, and/or thiol functionality. Natural materials that generally comprise amine, hydroxyl, carboxyl, and/or thiol functionalities are monosaccharides, oligosaccharides, polysaccharides, amino acids, proteins, celluloses, carboxy modified saccharides and celluloses, and the like.
The poly(amine alcohol) preferably comprises a reaction product of 1) an epoxy and 2) an amine functionality. The silica preferably comprises the product of silica hydrolysis. The polyamide in Type B and Type C particles is preferably a reaction product of 1) a copolymer of maleic anhydride and 2) an amine functionality.
The biodegradable membrane comprising polysaccharide, polypeptide, polyphenol, or cellulose is achieved via:
1) a reaction of the primary or secondary amine groups with the isocyanate; or
2) the reaction of basified biodegradable resin with isocyanate or epoxy; or
3) the reaction of secondary amines on the pre-reacted natural material resin comprising polyamide epichlorohydrin and natural material with isocyanate or epoxy.
The quaternary amine is preferably a material that has a primary amine moiety and a quaternary amine moiety. The primary amine moiety can preferably react with isocyanate functionality to form a polyurea layer, and the highly polar quaternary amine functionality interacts with the surrounding aqueous phase. Suitable quaternary amine materials include, for example, Girard's reagent. Other suitable quaternary amines include but are not limited to compounds represented by formulas (1)-(4) below.
The hydrophobic active ingredient is a hydrophobic substance that is active (or effective) to provide a desired effect, alone or in combination with other substances and/or conditions. It is present in the particles in an amount effective to provide a desired effect. The amount can be, e.g., from 47 wt. % or 59 wt. % or 66 wt. % to 73 wt. % or 78 wt. % or 81 wt. % or 93.5 wt. %, wherein the weight percentages are based on the weight of hydrophobic active divided by the weight of dry matter in the composition.
The hydrophobic active ingredient is preferably a member selected from the group consisting of a flavorant, a fragrance, a chromogen, a dye, an essential oil, a sweetener, an oil, a pigment, an active pharmaceutical ingredient, a moldicide, a herbicide, a fertilizer, a pheromone, phase change material, an adhesive, a vitamin oil, a vegetable oil, a triglyceride and a hydrocarbon.
Suitable flavorants include but are not limited to oils derived from plants and fruits such as citrus oils, fruit essences, peppermint oil, clove oil, oil of wintergreen, anise, lemon oil, apple essence, and the like. Artificial flavoring components are also contemplated. Those skilled in the art will recognize that natural and artificial flavoring agents may be combined in any sensorially acceptable blend. All such flavors and flavor blends are contemplated by this invention. Carriers may also be mixed with flavors to reduce the intensity, or better solubilize the materials. Carriers such as vegetable oils, hydrogenated oils, triethyl citrate, and the like are also contemplated by the invention.
Suitable fragrances include but are not limited to compositions comprising materials having an LogP (logarithm of octanol-water partition coefficient) of from about 2 to about 12, from about 2.5 to about 8, or even from about 2.5 to about 6 and a boiling point of less than about 280° C., from about 50° C. to about less than about 280° C., from about 50° C. to about less than about 265° C., or even from about 80° C. to about less than about 250° C.; and optionally, an ODT (odor detection threshold) of less than about 100 ppb, from about 0.00001 ppb to about less than about 100 ppb, from about 0.00001 ppb to about less than about 50 ppb or even from about 0.00001 ppb to about less than about 20 ppb. Diluents that are miscible in the fragrance oil, and act to reduce the volatility of the fragrance oil, such as isopropyl myristate, iso E super, triethyl citrate, vegetable oils, hydrogenated oils, neobee, and the like are also contemplated by the invention.
Suitable chromogens include but are not limited to Michler's hydrol, i.e. bis(p-dimethylaminophenyl)methanol, its ethers, for example the methyl ether of Michler's hydrol and the benzylether of Michler's hydrol, aromatic sulfonic and sulfinic esters of Michler's hydrol, for example the p-toluenesulfinate of Michler's hydrol, and derivatives of bis(p-dimethylaminophenyl)methylamine, e.g., N[bis(p-dimethylaminophenyl)methyl]morpholine.
Suitable dyes include but are not limited to Sudan Red 380, Sudan Blue 670, Baso Red 546, Baso Blue 688, Sudan Yellow 150, Baso Blue 645, Flexo Yellow 110, and Flexo Blue 630, all commercially available from BASF; Oil Red 235, commercially available from Passaic Color and Chemical; Morfast Yellow 101, commercially available from Morton; Nitro Fast Yellow B, commercially available from Sandoz; Macrolex Yellow 6G, commercially available from Mobay. Preferred dyes are those having good solubility in aromatic solvents.
Suitable essential oils include but are not limited to those obtained from thyme, lemongrass, citrus, anise, clove, aniseed, roses, lavender, citronella, eucalyptus, peppermint, camphor, sandalwood, cinnamon leaf and cedar. Essential oils that exhibit antimicrobial properties are also contemplated by this invention.
Suitable sweeteners include but are not limited to materials that contain varying amounts of disaccharide and/or fructose; erythritol, honey, and/or evaporated cane juice; and rebaudioside A, and the like.
Suitable pigments include but are not limited to pearl pigments of mica group such as titanium dioxide-coated mica and colored titanium dioxide-coated mica; and pearl pigments of bismuth oxychlorides such as colored bismuth oxychloride. Such pigments are available on the market under various trade names: Flamenco series (by the Mearl Corporation), TIMIRON COLORS (by MERCK) as titanium dioxide-coated mica, Timica Luster Pigments (by MEARL). Cloisonee series (by MEARL), COLORON series (by MERCK), SPECTRA-PEARL PIGMENTS (by Mallinckrodt) as colored titanium dioxide-coated mica and MIBIRON COLORS series (by MERCK) as colored bismuth oxychloride.
Suitable active pharmaceutical ingredients include but are not limited to water insoluble materials that have a melting point below 50° C.
Suitable moldicides include but are not limited to an inorganic biocide selected from the group consisting of a metal, a metal compound and combinations thereof. Preferably, the inorganic biocide is copper, cobalt, boron, cadmium, nickel, tin, silver, zinc, lead bismuth, chromium and arsenic and compounds thereof. More preferably, the copper compound is selected from the group consisting of copper hydroxide, cupric oxide, cuprous oxide, copper carbonate, basic copper carbonate, copper oxychloride, copper 8-hydroxyquinolate, copper dimethyldithiocarbamate, copper omadine and copper borate. Suitable moldicides further include but are not limited to fungicidal compounds such as, e.g., isothiazolone compounds. Typical examples of isothiazolone compounds include but not limited to: methylisothiazolinone; 5-chloro-2-methyl-4-isothiazoline-3-one, 2-methyl-4-isothiazoline-3-one, 2-n-octyl-4-isothiazoline-3-one, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, 2-ethyl-4-isothiazoline-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazoline-3-one, 5-chloro-2-ethyl-4-isothiazoline-3-one, 2-octyl-3-isothiazolone, 5-chloro-2-t-octyl-4-isothiazoline-3-one, 1,2-benzisothiazoline-3-one, preferably 5-chloro-2-methyl-4-isothiazoline-3-one, 2-methyl-4-isothiazoline-3-one, 2-n-octyl-4-isothiazoline-3-one, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, 1,2-benzisothiazoline-3-one, etc., more preferably 5-chloro-2-methyl-4-isothiazoline-3-one, 2-n-octyl-4-isothiazoline-3-one, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, 1,2-benzisothiazoline-3-one, chloromethyl-isothiazolinone, 4,5-Dichloro-2-n-octyl-3(2H)-isothiazolone and 1,2-benzisothiazolin-3-one.
Suitable herbicides include but are not limited to 2-(2-chloro-4-methylsulfonylbenzoyl)-1,3-cyclohexanedione, 2-(2-nitrobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione, 2-(2-(nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione, and their 2-benzoylcyclohexanedione derivatives, in addition to those listed in WO2006024411A2.
Suitable phase change materials include but are not limited to a crystalline alkyl hydrocarbon which is comprised of one or more crystalline straight chain alkyl hydrocarbons having 14 or more carbon atoms and heats of fusion greater than 30 cal/g. The melting and freezing point of the alkyl hydrocarbon is in the range of 0° to 80° C., preferably 5° to 50° C., and most preferably, 18° to 33° C. Representative materials are crystalline polyolefins such as polyethylene, polypropylene, polybutene, crystalline polystyrene, crystalline chlorinated polyethylene and poly(4-methylpentene-1). Crystalline ethylene copolymers such as ethylene vinylacetate, crystalline ethylene acrylate copolymers, ionomers, crystalline ethylene-butene-1 copolymers and crystalline ethylene-propylene copolymers are also useful polyolefins. Preferably, the polyolefins are crosslinked such that they are form stable upon heating above their crystalline melting point.
Suitable adhesives include but are not limited to compositions comprising an elastomer and a tackifying agent. The elastomer adds toughness to the adhesive film and also is responsible for at least part of the required initial pressure-sensitive tackiness. The elastomeric materials are water insoluble and are inherently tacky or are capable of being rendered tacky by mixture with compatible tackifying resins. Preferably the elastomers are natural rubber or butadiene or isoprene synthetic polymers or copolymers such as butadiene-isobutylene copolymers, butadiene-acrylonitrile copolymers, butadiene-styrene copolymers, polychloroprene or similar elastomers. A combination of the above elastomers may be utilized. Preferred tackifying agents include unsaturated natural resins such as rosin or derivatives thereof, such as rosin esters of polyols such as glycerol or pentaerythritol, hydrogenated rosins or dehydrogenated rosins
Suitable vitamin oils include but are not limited to fat-soluble vitamin-active materials, pro vitamins and pure or substantially pure vitamins, both natural and synthetic, or chemical derivatives thereof, crude extractions containing such substances, vitamin A, vitamin D, and vitamin E active materials as well as vitamin K, carotene and the like, or mixtures of such materials. The oil-soluble vitamin oil concentrate may be a high potency fish liver oil containing vitamin A and/or D, a synthetic vitamin A palmitate and/or acetate concentrated in an oil solution, vitamin D, or D either concentrated in oil solution or as an oleaginous resin, vitamin E (d-alpha tocopheryl acetate) in an oil solution, or vitamin K in oil solution, or beta-carotene as a crystalline oil suspension in oil.
Suitable vegetable oils include but are not limited to oils derived from palm, corn, canola, sunflower, safflower, rapeseed, castor, olive, soybean, coconut and the like in both the unsaturated forms and hydrogenated forms, and mixtures thereof.
Suitable triglycerides include but are not limited to those disclosed in U.S. Pat. No. 6,248,909B1.
Suitable hydrocarbons that can be the active or can be used in combination with the active in order to change the physical or chemical properties of the active, include but are not limited to, waxes, density modifiers, surface tension modifiers, melting point modifiers, viscosity modifiers, and mixtures thereof. Examples include animal waxes such as beeswax, plant waxes such as carnauba wax, candelilla wax, bayberry wax, castor wax, tallow tree wax, soya wax, rice bran wax, hydrogenated rice bran wax, soya wax, hydrogenated soya wax, hydrogenated vegetable oil. Examples of petroleum derived waxes are paraffin waxes and microcrystalline waxes. An example of synthetic wax is polyethylene wax. Examples of materials that can modify the density of the active phase in the particle are brominated vegetable oil, nanoclays such as montmorrilonite or kaolin, hydrophobically modified clays, hydrophobically modified precipitated silicas or fumed silicas. Examples of oil thickening agents are waxes mentioned above, modified organopolysiloxanes, silicone gums, hydrogenated castor oil, paraffin oils, polyolefins, and the like.
The emulsifier is present in the suspension, on a dry basis (weight of emulsifier per weight of dry matter in the suspension), of the invention in an amount effective to achieve the desired particle size distribution. The amount can be, e.g., from about 1.5 wt. % to about 10 wt. % or at least 1.5 wt. %, or at least 5 wt. % or at least 7.4 wt. % or at least 8.2 wt. %, or at least 10 wt. % or not greater than 20 wt. %.
Emulsifiers of all types are suitable for use in the practice of the present process though it is to be appreciated, and those skilled in the art will readily recognize that different systems, e.g., different core monomer and/or core materials, will be better suited with one or more classes of emulsifiers than others. Specifically, while the present teachings are applicable to anionic, cationic, non-ionic and amphoteric emulsifiers generally, preferred emulsifiers are non-ionic emulsifiers, particularly those having polyalkylether units, especially polyethylene oxide units, with degrees of polymerization of the alkylene ether unit of greater than about 6. Preferred emulsifiers are those which significantly reduce the interfacial tension between the continuous water phase and dispersed oil phase composition, and thereby reduce the tendency for droplet coalescence. In this regard, generally the emulsifiers for use in the water phase for aiding in the oil in water emulsion or dispersion will have HLB values of from 11 to 17. Of course, emulsifiers/surfactants of lower and higher HLB values that achieve the same objective as noted are also included.
Exemplary emulsifiers include, but are not limited to gums such as acacia gum, gum arabic, konjac gum, and xantham gum; poly(meth)acrylic acids and derivatives. Most preferably, the emulsifier/emulsion stabilizer is a polyvinyl pyrrolidone, copolymers of polyvinyl pyrrolidone with vinyl acetate, vinyl alcohol, vinyl imidazole; polyglycerol oleates, polypeptides, gelatin, functionalized gelatin, pectin, functionalized pectin, agarose, carboxymethyl cellulose, colloidal silica, sodium alginate.
Additional exemplary anionic surfactants and classes of anionic surfactants suitable for use in the practice of the present invention include: sulfonates; sulfates; sulfosuccinates; sarcosinates; alcohol sulfates; alcohol ether sulfates; alkylaryl ether sulfates; alkylaryl sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates and salts thereof; alkyl sulfonates; mono- or di-phosphate esters of polyalkoxylated alkyl alcohols or alkylphenols; mono- or di-sulfosuccinate esters of C12 to C15 alkanols or polyalkoxylated C12 to C15 alkanols; ether carboxylates, especially alcohol ether carboxylates; phenolic ether carboxylates; polybasic acid esters of ethoxylated polyoxyalkylene glycols consisting of oxybutylene or the residue of tetrahydrofuran; sutfoalkylamides and salts thereof such as N-methyl-N-oleoyltaurate Na salt; polyoxyalkylene alkylphenol carboxylates; polyoxyalkylene alcohol carboxylates alkyl polyglycosidelalkenyl succinic anhydride condensation products; alkyl ester sulfates; naphthalene sulfonates; naphthalene formaldehyde condensates; alkyl sulfonamides; sulfonated aliphatic polyesters; sulfate esters of styrylphenyl alkoxylates; and sulfonate esters of styrylphenyl alkoxylates and their corresponding sodium, potassium, calcium, magnesium, zinc, ammonium, alkylammonium, diethanolammonium, or triethanolammonium salts; salts of ligninsulfonic acid such as the sodium, potassium, magnesium, calcium or ammonium salt; polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; and sulfated alkyl phenol ethoxylates and phosphated alkyl phenol ethoxylates; sodium lauryl sulfate; sodium laureth sulfate; ammonium lauryl sulfate; ammonium laureth sulfate; sodium methyl cocoyl taurate; sodium lauroyl sarcosinate; sodium cocoyl sarcosinate; potassium coco hydrolyzed collagen; TEA (triethanolamine) lauryl sulfate; TEA (Triethanolamine) laureth sulfate; lauryl or cocoyl sarcosine; disodium oleamide sulfosuccinate; disodium laureth sulfosuccinate; disodium dioctyl sulfosuccinate; N-methyl-N-oleoyltaurate Na salt; tristyrylphenol sulphate; ethoxylated lignin sulfonate; ethoxylated nonylphenol phosphate ester calcium alkylbenzene sulfonate; ethoxylated tridecylalcohol phosphate ester, dialkyl sulfosuccinates; perfluoro (C6-C18)alkyl phosphonic acids; perfluoro(C6-C18)alkyl-phosphinic acids; perfluoro(C3-C20)alkyl esters of carboxylic acids; alkenyl succinic acid diglucamides; alkenyl succinic acid alkoxylates; sodium dialkyl sulfosuccinates; and alkenyl succinic acid alkylpolyglykosides. Further exemplification of suitable anionic emulsifiers include, but are not limited to, water-soluble salts of alkyl sulfates, alkyl ether sulfates, alkyl isothionates, alkyl carboxylates, alkyl sulfosuccinates, alkyl succinamates, alkyl sulfate salts such as sodium dodecyl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolyzates, acyl aspartates, alkyl or alkyl ether or alkylaryl ether phosphate esters, sodium dodecyl sulphate, phospholipids or lecithin, or soaps, sodium, potassium or ammonium stearate, oleate or palmitate, alkylarylsulfonic acid salts such as sodium dodecylbenzenesuifonate, sodium dialkylsulfosuccinates, dioctyl sulfosuccinate, sodium dilaurylsulfosuccinate, poly(styrene sulfonate) sodium salt, alkylene-maleic anhydride copolymers such as isobutylene-maleic anhydride copolymer, or ethylene maleic anhydride copolymer gum arabic, sodium alginate, carboxymethylcellulose, cellulose sulfate and pectin, poly(styrene sulfonate), pectic acid, tragacanth gum, almond gum and agar; semi-synthetic polymers such as carboxymethyl cellulose, sulfated cellulose, sulfated methylcellulose, carboxymethyl starch, phosphated starch, lignin sulfonic acid; maleic anhydride copolymers (including hydrolyzates thereof), polyacrylic acid, polymethacrylic acid, acrylic acid alkyl acrylate copolymers such as acrylic acid butyl acrylate copolymer or crotonic acid homopolymers and copolymers, vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid homopolymers and copolymers, and partial amide or partial ester of such polymers and copolymers, carboxymodified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol, phosphated or sulfated tristyrylphenol ethoxylates.
Exemplary amphoteric and cationic emulsifiers include alkylpolyglycosides; betaines; sulfobetaines; glycinates; alkanol amides of C8 to C18 fatty acids and C8 to C18 fatty amine polyalkoxylates; C1 to C18 alkyldimethylbenzylammonium chlorides; coconut alkyldimethylaminoacetic acids: phosphate esters of C8 to C18 fatty amine polyalkoxylates; alkylpolyglycosides (APG) obtainable from an acid-catalyzed Fischer reaction of starch or glucose syrups with fatty alcohols, in particular C8 to C18 alcohols, especially the C8 to C10 and C12 to C14 alkylpolyglycosides having a degree of polymerization of 1.3 to 1.6, in particular 1.4 or 1.5. Additional cationic emulsifiers include quaternary ammonium compounds with a long-chain aliphatic radical, e.g. distearyldiammonium chloride, and fatty amines. Among the cationic emulsifiers which may be mentioned are alkyldimethylbenzylammonium halides, alkyldimethylethyl ammonium halides, etc. specific cationic emulsifiers include palmitamidopropyl trimonium chloride, distearyl dimonium chloride, cetyltrimethylammonium chloride, 1H-Imidazolium, 1-ethenyl-3-methyl-, chloride, polymer with 1-ethenyl-2-pyrrolidinone, and polyethyleneimine. Additional amphoteric emulsifiers include alkylaminoalkane carboxylic acids betaines, sulphobetaines, imidazoline derivatives, lauroamphoglycinate, sodium cocoaminopropionate, and the zwitterionic emulsifier cocoamidopropyl betaine.
Suitable non-ionic emulsifiers are characterized as having at least one non-ionic hydrophilic functional group. Preferred non-ionic hydrophilic functional groups are alcohols and amides and combinations thereof. Examples of non-ionic emulsifiers include: mono and diglycerides; polyarylphenol polyethoxy ethers; polyalkylphenol polyethoxy ethers; polyglycol ether derivatives of saturated fatty acids; polyglycol ether derivatives of unsaturated fatty acids; polyglycol ether derivatives of aliphatic alcohols; polyglycol ether derivatives of cycloaliphatic alcohols; fatty acid esters of polyoxyethylene sorbitan; alkoxylated vegetable oils; alkoxylated acetylenic diols; polyalkoxylated alkylphenols; fatty acid alkoxylates; sorbitan alkoxylates; sorbitol esters; C8 to C22 alkyl or alkenyl polyglycosides; polyalkoxy styrylaryl ethers; amine oxides especially alkylamine oxides; block copolymer ethers; polyalkoxylated fatty glyceride; polyalkylene glycol ethers; linear aliphatic or aromatic polyesters; organo silicones; sorbitol ester alkoxylates; ethoxylated castor oil; amides of fatty acids such as stearamide, lauramide diethanolamide, and lauramide monoethanolamide; aryl ethers of polyoxyalkylene glycols such as polyoxyethylene glycol nonylphenyl ether and polypropylene glycol stearyl ether. Also preferred as non-ionic emulsifiers are various latex materials, stearates, lecithins,
The amine comprises linear aliphatic amines, aromatic amines, silicone amines, branched amines, polypeptides, polyamines, and amino acids. Generally, amines are listed by their pKa values, and this defines whether the amine is acidic, basic, or neutral. Acidic amines such as lysine hydrochloride, urea, tryptophan hydrochloride, guanidine hydrochloride, and the like; neutral amines such as aniline, cyanamide, 4-aminobenzoic acid, and the like; and basic amines such as ethylenediamine, diethylenetriamine, guanidine, guanidine carbonate. pentaethylene hexamine, hexamethylenetetramine, tetraethylene pentamine, and Girard's reagent; silicone amines such as aminopropylsilsequioxane oligomer, water borne amino alkyl silsequioxane oligomers, trihydroxysilylpropylamine condensate, 3-aminopropyl(diethoxy)methylsilane, [3-(2-aminoethyl)-aminopropyl]methyldimethoxysilae, [3-(2-aminoethyl)-aminopropyl]tri-methoxysilane; guanidine carbonate; amino acids such as Aspartic acid, glutamic acid, lysine, arginine, histidine, glycine, alanine, serine, threonine, tyrosine, asparagine, glutamione, cysteine.
The amine is present in particles of the invention in an amount effective to react with the isocyanate moiety, the organofunctional silane moiety, the epoxy moieties to an extent effective to provide the particles with desired durability. The amount of amine on a dry basis (weight of amine per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.7 wt. % or 1.0 wt. % or 1.5 wt. % to 2.0 wt. % or 2.5 wt. % or 3.6 wt. %.
In certain embodiments, the isocyanate comprises aliphatic isocyanates, aromatic isocyanates, polymeric isocyanates, cyclic isocyanates, hydrophilic isocyanates, hydrophobic isocyanates, waterborne isocyanates. Exemplary isocyanates are selected from the group consisting of hexamethylene diisocyanates (Desmodur N3600, Desmodur N3800, Desmodur N3900, Desmodur N3200, Desmodur N3300, Desmodur N3400, Takenate D-170N), isophorone diisocyanates (Desmodur XP2565, Desmodur Z4470), blends of hexamethylene diisocyanate and isophorone diisocyanate (Desmodur XP2847, Desmodur XP2489, Desmodur XP2838, Desmodur XP2763), pentane-1,5-diisocyanate (Stabio D-370N, Stabio D-376N), xylylene diisocyanate (Takenate 500, Takenate 600, Takenate D-110N, Takenate D-131N), polymeric methylene diphenyl diisocyanate (Mondur MR Lite), polymeric MDI (Desmodur VK 5, Desmodur VL R10, Desmodur 44V40L, Desmodur 44V70L), polyether modified hydrophilic polyisocyanates (Bayhydur XP2451/1, Bayhydur XP2547, Bayhydur XP2759, Bayhydur Ultra 304, Bayhydur Ultra 2487/1), CN9302, ionically modified isocyanates (Bayhydur 2858 XP, Bayhydur XP2759, Bayhydur eco 7190), and the like.
In certain embodiments, the organofunctional silane as at least one member selected from the group consisting of alkoxylated silane, trialkoxy silanes, functionalized trialkoxysilanes (amino, glycidoxy, methacryloxy, vinyl), tetraalkoxylated silanes including tetramethoxy silane and tetraethoxy silane, 1,2-bis(triethyxysilyl)ethane.
The organofunctional silane is present in particles of the invention in an amount effective to hydrolyze in water and react with the amine moiety to create Si—O—Si bonds. The amount of amine on a dry basis (weight of organofunctional silane per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.7 wt. % or 1.0 wt. % or 1.5 wt. % to 2.0 wt. % or 2.5 wt. % or 3.6 wt. %.
In certain embodiments, the epoxide curing agent is at least one member selected from the group consisting of low temperature curing agents having 2 or more epoxy functional groups which are terminally located. Suitable materials include trimethylol propane triglycidyl ether, resins containing acrylate and epoxy functional groups, diepoxide of the cycloapliphatic alcohol, hydrogenated Bisphenol A, resorcinol/bisphenol F resin with polyfunctional epoxide resin blend.
The epoxide curing agent is present in particles of the invention in an amount effective to react with amine moiety, isocyanate moiety, and/or the hydrolyzed organofunctional silane moiety. The amount of epoxide curing agent on a dry basis (weight of epoxide curing agent per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.2 wt. % or 0.3 wt. % or 0.5 wt. % to 0.7 wt. % or 1.0 wt. % or 1.8 wt. %.
In certain embodiments, the copolymer of maleic anhydride is at least one member selected from the group consisting of unsaturated acidic reagents which readily react with nucleophiles such as alcohols and amines to form corresponding esters and amides. Preferably, such reagents hydrolyze in presence moisture to deliver a free acid. Suitable materials include the free radical polymerization reaction products of maleic anhydride with acyclic or cyclic or vinylic aromatic alkenes to form co-polymers with varying molecular weights and degree of maleic anhydride levels. Suitable materials include poly (ethylene-alt-maleic anhydride), poly(methyl vinyl ether-alt-maleic acid), poly(methyl vinyl ether-alt-maleic acid monoethyl ester), poly(isobutylene-alt-maleic anhydride) amide ammonium salts, poly(styrene-alt-maleic acid) sodium salt, poly(4-styrenesulfonic acid-co-maleic acid) sodium salt, poly(isobutylene-alt-maleic anhydride), and the like.
The copolymer of maleic anhydride is present in particles of the invention in an amount effective to react with amine moiety to a carboxylate anion. Acidification of the anion results in the generation of an acid. Subsequently, the acid can react with the isocyanate moiety, and/or aziridine moiety, and/or oxazoline containing moiety. The amount of copolymer of maleic anhydride on a dry basis (weight of copolymer of maleic anhydride per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.2 wt. % or 0.3 wt. % or 0.5 wt. % to 0.7 wt. % or 1.0 wt. % or 1.8 wt. %.
In certain embodiments, the polyaziridine comprises a member selected from the group consisting of polymers having at least 2 aziridine functional groups as terminal or pendant groups.
The polyaziridine is present in particles of the invention in an amount effective to react with carboxylic acid moieties. The amount of polyaziridine on a dry basis (weight of polyaziridine per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.4 wt. % or 0.6 wt. % or 1.0 wt. % to 1.4 wt. % or 2.0 wt. % or 3.8 wt. %.
In certain embodiments, the polyoxazoline comprise a polymer with more than one oxazoline functional groups. The oxazolines can be present as the terminal end of a polymer or can be pendant groups attached to a polymer backbone. The oxazolines may be product of free radical polymerization of vinyl oxazolines. Oxazolines are also known as oxazaolyls.
The polyoxazoline is present in particles of the invention in an amount effective to react with carboxylic acid moieties. The amount of polyoxazoline on a dry basis (weight of polyaziridine per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.4 wt. % or 0.6 wt. % or 1.0 wt. % to 1.4 wt. % or 2.0 wt. % or 3.8 wt. %.
In certain embodiments, the basified biodegradable resin comprises a protein, or polysaccharide, or oligosaccharide, or cellulose, or polyphenol, or lipid. The hydroxyl or amine functionalities of these materials have been made more reactive by altering the pH. Preferably, the pH of the protein, or polysaccharide, or oligosaccharide, or lipid is increased using an organic or inorganic base, preferably sodium carbonate, and the mixture is dehydrated to yield a powder. Nonlimiting examples of basified biodegradable resins include spray dried particle comprising casein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried particle comprising gelatin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried chitosan oligosaccharide whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried whey protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried soy protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried silk fibroin protein whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried lignin whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried tannic acid whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying; spray dried carboxymodified cellulose whose pH is adjusted to 8.0 or higher using sodium carbonate prior to spray drying.
Commercially available examples of proteins of use in preparing the basified biodegadable resin comprise proteins including, but are not limited to, unmodified silk protein, zein, gelatin, keratin, collagen and any polypeptide, such as polylysine; hydrolyzed proteins such as COLLASOL (high molecular weight, soluble, marine collagen; Croda), CROPEPTIDE (hydrolyzed wheat protein and hydrolyzed wheat starch; Croda), CROSILK 10000 (hydrolyzed silk protein; Croda), CROTEIN (hydrolyzed collagen; Croda), HYDROLACTIN 2500 (hydrolyzed milk protein; Croda), HYDROSOLANUM (hydrolyzed vegetable protein; Croda), HYDROSOY 2000 PE (hydrolyzed soy protein; Croda), HYDROTRITICUM 2000 PE (hydrolyzed wheat protein; Croda), KERASOL (hydrolyzed keratin; Croda), PROLEVIUM (cottonseed protein hydrolyzate; Croda), PROSINA (hydrolyzed keratin; Croda), TRITISOL (Hydrolyzed wheat protein; Croda), Fision KeraVeg 18 (wheat amino acids, soy amino acids; Tri-K), MILK-TEIN (hydrolyzed milk protein; Tri-K), Rice PRO-TEIN (hydrolyzed rice protein; Tri-K), RICE-QUAT C (cocodimonium hydroxypropyl hydrolyzed rice protein; Tri-K), SOY-QUAT L (laurdimonium hydroxypropyl hydrolyzed soy protein; Tri-K), WHEAT-QUAT C (cocodimonium hydroxypropyl hydrolyzed wheat protein; Tri-K), QUINOA PRO EX (hydrolyzed quinoa; Tri-K), BARLA-TEIN Pro (hydrolyzed barley protein; Tri-K), KERA-QUAT WKP (hydrolyzed keratin; Tri-K), KERA-TEIN 1000 (hydrolyzed keratin; Tri-K), KERA-TEIN 1000 SD (hydrolyzed keratin; Tri-K), Proto-lan 8 (cocoyl hydrolyzed collagen; Tri-K), Proto-lan KT (cocoyl hydrolyzed collagen; Tri-K), SILK AA-QUAT C (cocodimonium hydroxypropyl silk amino acids; Tri-K), AMINO SILK SF (silk amino acids; Tri-K), Collagen Hydrolyzate Cosmetic N-55 (Tri-K), FLAX-TEIN Pro (hydrolyzed linseed protein; Tri-K), SOY-TEIN NL (hydrolyzed soy protein; Tri-K), Silk PRO-TEIN (hydrolyzed silk; Tri-K), WHEAT-TEIN W (hydrolyzed wheat protein; Tri-K), and MARI-COLL N-30 (hydrolyzed collagen; Tri-K).
The basified biodegradable resin is present in particles of the invention in an amount effective to react with isocyanate and epoxy moieties. The amount of basified biodegradable resin on a dry basis (weight of basified biodegradable resin per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.4 wt. % or 0.6 wt. % or 1.0 wt. % to 1.4 wt. % or 2.0 wt. % or 3.8 wt. %.
In certain embodiments, the inorganic solid particles comprise a member selected from the group consisting of organically modified or water insoluble clays, minerals, salts such as talc, calcium carbonate, bentonite.
The inorganic solid particles are present in particles of the invention in an amount effective to improve the barrier properties of the membrane. The amount of inorganic solid particles on a dry basis (weight of inorganic solid particles per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.2 wt. % or 0.3 wt. % or 0.5 wt. % to 0.7 wt. % or 1.0 wt. % or 1.8 wt. %.
In certain embodiments, the polysaccharide comprise a member selected from the group consisting of natural starches such as tapioca, potato, corn, rice, wheat; modified starches such as carboxy modified polysaccharide or cellulose such as carboxymethyl starch, carboxymethyl chitosan, chitosan oligosaccharide, hydroxy propyl methyl starch, hydroxy propyl cellulose, ethyl cellulose, methyl cellulose, and octenyl succinic anhydride modified starch.
The polysaccharides are present in particles of the invention in an amount effective to improve the environmental biodegradability of the particles. The amount of polysaccharides on a dry basis (weight of polysaccharide per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.4 wt. % or 0.6 wt. % or 1.0 wt. % to 1.4 wt. % or 2.0 wt. % or 3.8 wt. %.
In certain embodiments, the pre-reacted natural material resin comprises a monomer or polymer having at least 1 functional group that is capable of reacting with isocyanate or epoxy groups. The pre-reacted natural material resin comprises a natural material and a crosslinker. The natural material is selected from the group consisting of polypeptide or protein, or polysaccharide, or oligosaccharide, or cellulose, or polyphenol, or lipid. The crosslinker is selected from the group consisting of water-based crosslinking resins that are reactive with amine, carboxyl, hydroxyl, and thiol functionality such as epoxy, expoxide curing agent, or polyamide epichlorohydrin. Preferably the crosslinker is polyamide epichlorohydrin that has a high content of secondary amines. In a preferred embodiment, the pre-reacted natural material resin is made by pursuing the following procedure: 1) the natural material is mixed with the polyamide epichlorohydrin to make a homogeneous solution in water; 2) the pH of the system is adjusted to optimize conditions for the reaction; 3) the mixture is dehydrated, preferably using a spray drying process, and 4) the resulting powder is heated at a temperature greater than 100 degrees Centigrade for more than 30 minutes to assure crosslinking. Nonlimiting examples of pre-reacted natural material resin comprise polyamide epichlorohydrin, epoxy, or epoxide curing agent reaction product with proteins such as casein, whey protein, soy protein, silk protein, zein protein, and the like; reaction product with oligosaccharides and polysaccharides such as chitosan oligosaccharide, carboxymethyl starch, alginic acid, hyaluronic acid, pectin, glucuronic acid, gum Arabic, and the like; reaction products with cellloses such as caroxymethyl cellulose, microcrystalline cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropylmethyl cellulose phthalate, hydroxypropyl methyl cellulose acetate succinate, and the like; reaction products with polyphenols such as lignin, tannic acid, and the like; and mixtures thereof.
The pre-reacted natural material comprises a polyamide epichlorohydrin to natural material weight ratio of from 1:99, from 4:96, from 8:92, from 10:90, from 20:80, from 50:50.
The pre-reacted natural material comprises an epoxide curing agent to natural material weight ratio of from 1:99, from 4:96, from 8:92, from 10:90, from 20:80, from 50:50.
The pre-reacted natural material is present in particles of the invention in an amount effective to improve the barrier properties and environmental biodegradability of the membrane. The amount of pre-reacted natural material resin on a dry basis (weight of pre-reacted natural material resin per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.2 wt. % or 0.3 wt. % or 0.5 wt. % to 0.7 wt. % or 1.0 wt. % or 1.8 wt. %.
In certain embodiments, the pre-reaction product of polyisocyanate comprises a monohydroxy monomer of Formula 1 or Formula 2 (as defined above) reacted with a polymeric isocyanate. Preferably, such a pre-reaction product of polyisocyanate contains active isocyanate functionalities with esters in the side chain. Nonlimiting examples of polyisocyanates comprise polymeric isocyanates containing 2 or more isocyanate functionalities, cyclic isocyanates, hydrophilic isocyanates, hydrophobic isocyanates, waterborne isocyanates and urethane acrylates containing isocyanate functionalities. Nonlimiting examples of monohydroxy monomers of Formulas 1 or 2 are disclosed above.
The pre-reaction product of isocyanate comprises residual isocyanate of from 5% to 20%, from 7 to 15%, from 8% to 10%.
The pre-reaction product of isocyanate is present in particles of the invention in an amount effective to improve the barrier properties and environmental biodegradability of the membrane. The amount of pre-reaction product of isocyanate on a dry basis (weight of pre-reaction product of isocyanate per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.2 wt. % or 0.3 wt. % or 0.5 wt. % to 0.7 wt. % or 1.0 wt. % or 1.8 wt. %.
In certain embodiments the epoxy is at least one member selected from the group consisting of epoxidized unsaturated oils such as epoxidized soybean oil, epoxidized vegetable oil, and the like; epoxidized alcohols such as isoborbide glycidyl ether, polyglycerol-3-glycidyl ether, castor oil glycidyl ether; epoxidized polysaccharides such as sorbitol polyglycidyl ether, EX-201: Resorcinol Diglycidyl Ether; EX-211: Neopentyl Glycol Diglycidyl Ether; EX-212: 1,6-Hexanediol Diglycidyl Ether; EX-252: Hydrogenated Bisphenol A Diglycidyl Ether; EX-313: Glycerol Polyglycidyl Ether; EX-314: Glycerol Polyglycidyl Ether; EX-321: Trimethylolpropane Polyglycidyl Ether; EX-411: Pentaerythritol Polyglycidyl Ether; EX-421: Diglycerol Polyglycidyl Ether; EX-512: Polyglycerol Polyglycidyl Ether; EX-612: Sorbitol Polyglycidyl Ether; EX-711: Diglycidyl Terephthalate; EX-721: Diglycidyl o-Phthalate; EX-731: N-Glycidyl Phthalimide; EX-810: Ethylene Glycol Diglycidyl Ether; EX-811: Ethylene Glycol Diglycidyl Ether; EX-850: Diethylene Glycol Diglycidyl Ether; EX-851: Diethylene Glycol Diglycidyl Ether; EX-821: Polyethylene Glycol Diglycidyl Ether; EX-920: Polypropylene Glycol Diglycidyl Ether; EM-160: Emulsion of Epoxy Cresol Novolac Resin; DENACOL FCA-640: Hexahydrophthalic acid diglycidyl ester; and the like, available from Nagase.
The epoxy is present in particles of the invention in an amount effective to react with the amine moiety, the isocyanate moiety, and/or the hydrolyzed organofunctional silane moieties. The amount of epoxy on a dry basis (weight of epoxy per weight of dry matter in the suspension) can be, e.g., from 0.1 wt. % or 0.7 wt. % or 1.0 wt. % or 1.5 wt. % to 2.0 wt. % or 2.5 wt. % or 3.6 wt. %.
Cationic particles have a higher probability of adhering to anionic fabric in the laundering environment. Amine-functionality containing materials that can be incorporated into the spray-ready emulsion, which may have a favorable effect on adhesion of particles onto skin, hair, or fabric substrates comprise a polymer selected from the group consisting of polysaccharides, in one aspect, cationically modified starch and/or cationically modified guar; polysiloxanes; poly diallyl dimethyl ammonium halides; copolymers of poly diallyl dimethyl ammonium chloride and polyvinyl pyrrolidone; a composition comprising polyethylene glycol and polyvinyl pyrrolidone; acrylamides; imidazoles; imidazolinium halides; polyvinyl amine; copolymers of poly vinyl amine and N-vinyl formamide; polyvinylformamide, copolymers of polyvinylamine and polvyinylalcohol oligomers of amines, in one aspect a diethylenetriamine, ethylene diamine, bis(3-aminopropyl)piperazine, N,N-Bis-(3-aminopropyl)methylamine, tris(2-aminoethyl)amine and mixtures thereof; polyethyleneimime, a derivatized polyethyleneimine, in one aspect an ethoxylated polyethyleneimine; diester quaternary ammonium surfactants such as methyl bis-[ethyl(coconut)]-2-hydroxyethyl ammonium methyl sulfate, methyl bis-[ethyhdecyl)]-2-hydroxyethyl ammonium methyl sulfate, methyl bis-[ethyl(dodeceyl)]-2-hydroxyethyl ammonium methyl sulfate, methyl bis-[ethyl(lauryl)]-2-hydroxyethyl ammonium methyl sulfate, methyl bis-[ethyl(palmityl)]-2-hydroxyethyl ammonium methyl sulfate, methyl bis-[ethyl(soft-tallow)]-2-hydroxyethyl ammonium methyl sulfate, and the like; diester quat combined with laminate nanoclays such as laponite, bentonite, montmorillonite, and the like; chitosan with various degrees of deacetylation, carboxymethyl chitosans, glycol chitosans, whey protein, sodium caseinate, silk protein, 1H-Imidazolium, 1-ethenyl-3-methyl-, chloride, polymer with 1-ethenyl-2-pyrrolidinone, polyamines, polysaccharides with cationic modification, and mixtures thereof. Polysaccharides can be employed with cationic modification and alkoxy-cationic modifications, such as cationic hydroxyethyl, cationic hydroxy propyl. For example, cationic reagents of choice are 3-chloro-2-hydroxypropyl trimethylammonium chloride or its epoxy version. Furthermore, up to 5 different types of functional groups may be attached to the polysaccharides. Also, polymer graft chains may be differently modified than the backbone. The counterions can be any halide ion or organic counter ion. The preferred cationic starch has a molecular weight of from about 100,000 to about 500,000,000, preferably from about 200,000 to about 10,000,000 and most preferably from about 250,000 to about 5,000,000. The preferred cationic starch products are HI-CAT CWS42 and HI-CAT 02 and are commercially available from ROQUETTE AMERICA, Inc. The preferred cationic guar has a molecular weight of from about 50,000 to about 5,000,000. The preferred cationic guar products are Jaguar C-162 and Jaguar C-17 and are commercially available from Rhodia Inc.
The deposition aid is present in the controlled release particles in an amount on a dry basis (weight of deposition aid per weight of dry matter in the suspension) from 0.5 wt. % or 1 wt. % or 1.5 wt. % or 3.5 wt. % to 5 wt. % or 7 wt. % of the weight of the particle.
The controlled release particles are preferably spherical but non-spherical shapes are also within the scope of the invention. The particles preferably have a diameter from 0.05-250 microns, or from 0.1 microns to less than 100 microns.
Method of Making the Particles
The controlled release particles according to the present teaching are made in a multi-step process as described below. For convenience, the process is presented in the preferred mode which involves one aqueous phase composition and one hydrophobic oil phase composition. Nonetheless, those skilled in the art will readily appreciate that the aqueous phase composition may be prepared as a dual phase composition to which the hydrophobic oil phase composition is added or a three or more components composition where various ingredients are preferably isolated from one another until desired so as to avoid undue or undesired activation of the aqueous phase monomers or oligomers.
The hydrophobic oil phase composition is formed by combining the hydrophobic active core material with oil soluble monomers and oligomers. Most preferably this is conducted under moderate increased temperature so as to facilitate the solubilization or suspension of the monomers, oligomers, and other ingredients that may be present, including nucleating agents, in the core material. This is particularly useful if the core material is a solid or wax or a high viscosity material. Once again, if the temperature of the mixture had been elevated to aid in getting the hydrophobic oil phase monomer into solution/suspension, then the mixture should be cooled or allowed to cool to ambient temperature.
Materials that are not necessarily soluble or miscible in the oil phase can also be dispersed in the oil phase. The purpose is to maintain these materials at the oil-water interface to improve the properties of the membrane. In the present invention, polysaccharides, inorganic solid particles, basified biodegradable resins, pre-reacted natural material resin, and plasticizers are often materials that are not miscible in oil; however, they influence the barrier properties, flexibility, and biodegradability properties of the membrane.
The hydrophobic oil phase composition is added to an aqueous phase to form an emulsion. The mixture is agitated until the desired droplet size of oil phase composition is attained. In order to establish a wall at the oil-water interface, an amine is added to the aqueous phase followed by pH adjustment. Droplets are preferably from about 10 microns to about 75 microns, and more preferably from about 20 microns to about 50 microns in volume average diameter.
Not to be limited by theory, the amine added in the aqueous phase can react with several functional groups present in the hydrophobic oil phase, including isocyanate, epoxy, and organofunctional silane. The reactivity of amine is higher with isocyanate, and therefore provides the outer membrane via an interfacial polymerization reaction that limits the diffusion of the hydrophobic oil phase into the surrounding aqueous phase. Not to be limited by theory, the amine next reacts with epoxy functionality to form amino alcohols. The amino alcohols can in turn react with the isocyanates, such reaction will lead to the possible formation of polyurethanes and polyureas which will reduce the permeability of the membrane. The basified biodegradable resins already have amine functionalities; however, these amine functionalities may exist as carboxylate salts due to the zwitterionic effect. i.e. proteins have both amine functionality and acid functionality; hence the acids could be neutralized by the amines, or exist as a polyelectrolyte complex wherein the amine functionality is folded inward and unable to react with the isocyanate or epoxy functionalities. Basifying these materials reduces the zwitterionic effect, causes a desired unfolding of the protein material, and makes the amine more reactive. Not to be limited by theory, natural materials are generally inert and non-reactive. Pre-reacting such natural materials with epoxy, epoxide curing agent, or polyamide epicholorhydrin creates a covalent bond with specific functional groups of the natural material, and the pre-reacted polymer brings secondary amine functionalities. The secondary amines can further react with isocyanate and epoxy functionalities. Introduction of the hydrophobic oil phase into the aqueous phase can hydrolyze the organofunctional silanes. Such silanes self-condense in the presence of amine to form a cage structure comprising Si—O—Si bonds to reduce permeability of the membrane. In Type B particles, once the amine has reacted and is present on the surface of the particle, it can react with the copolymer of maleic anhydride to open up the anhydride ring to produce amide and carboxylate anion.
Inventors have discovered that pursuing a high degree of crosslinking in making polyurea, polyurethane, polyester, polyamide, poly(amine-alcohol), and the like, via chemical reaction processes that comprise interfacial polymerization, polycondensation reactions, addition reactions, free radial polymerization reactions, and the like, may provide a membrane with good barrier properties and mechanical properties; however, such membranes have poor environmental biodegradability. Not to be limited by theory, a high degree of crosslinking results in the absence of both functional groups and flexibility that hinders the ability of microbes to form a biofilm around the polymer membrane followed by digestion of membrane to improve biodegradability. Incorporation of biodegradable materials into the membrane via the use of basified biodegradable resins, pre-reaction products of polyisocyanate, and pre-reacted natural material resin can improve barrier properties of the membrane (more tortuous path for the encapsulated material to diffuse, poor miscibility of the encapsulated active material in the polymer, biodegradable polymer segments swell with water reducing the diffusion of the encapsulated active), and improved environmental biodegradability of the membrane due to the presence of amino acids, glucose units, esters, amides, and other functional groups whose breakdown is enabled by enzymes that the microbes readily secrete.
Once this membrane is established, no further decrease in particle size of the oil droplets is observed. The reactor contents are agitated for 30 minutes to 5 hours, depending on the emulsifying properties of the hydrophobic oil phase. It is desired to maintain a temperature of the reactor below 40° C., in order to facilitate controlled membrane formation. It is desired to increase the temperature of the reactor contents to 60° C. for an additional 2 to 5 hours to complete the reaction.
In certain embodiments, the suspension of controlled release particles is dehydrated in order to expose the particles to a higher temperature to achieve a higher degree of crosslinking of the monomers.
In certain embodiments of providing a powder composition of the invention, or making the dehydrated forms of basified biodegradable resin, or making the pre-reacted natural material resin, spray drying is an economical process that can be used. Spray drying of the particle suspension is preferably conducted in a co-current spray dryer, at an inlet air temperature of 325 to 415° F. (163-213° C.), preferably from 355 to 385° F. (179-196° C.) and an outlet air temperature of 160 to 215° F. (71-101° C.), preferably from 175-195° F. (79-91° C.).
In certain powder composition embodiments, the silica flow aid is added to the dry powder to improve the flowability of the powder. Addition of the silica flow aid minimizes the agglomeration of particles during the heating, packing, and conveyance processes.
Advantages of at least some embodiments of the inventive method include at least one or at least two or at least three or at least four or at least five or at least six or all seven of the following:
Compositions Containing the Particles
The invention further comprises compositions (e.g., products, articles of manufacture, etc.) comprising the controlled release particles. Such compositions include but are not limited baby care, beauty care, fabric & home care, family care, feminine care, health care, snack and/or beverage products or devices intended to be used or consumed in the form as sold, and not intended for subsequent commercial manufacture or modification. Such products include but are not limited to fine fragrances (e.g., perfumes, colognes eau de toilettes, after-shave lotions, pre-shave, face waters, tonics, and other fragrance-containing compositions for application directly to the skin), diapers, bibs, wipes; products for and/or methods relating to treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use; and shaving products, products for and/or methods relating to treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care, car care, dishwashing, fabric conditioning (including softening), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment, and other cleaning for consumer or institutional use; products and/or methods relating to bath tissue, facial tissue, paper handkerchiefs, and/or paper towels; tampons, feminine napkins; products and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening; over-the-counter health care including cough and cold remedies, pain relievers, RX pharmaceuticals, pet health and nutrition, and water purification; processed food products intended primarily for consumption between customary meals or as a meal accompaniment (non-limiting examples include potato chips, tortilla chips, popcorn, pretzels, corn chips, cereal bars, vegetable chips or crisps, snack mixes, party mixes, multigrain chips, snack crackers, cheese snacks, pork rinds, com snacks, pellet snacks, extruded snacks and bagel chips); and coffee. Moreover, such products include, but are not limited to, a powdered food product, a fluid food product, a powdered nutritional supplement, a fluid nutritional supplement, a fluid fabric enhancer, a solid fabric enhancer, a fluid shampoo, a solid shampoo, hair conditioner, body wash, solid antiperspirant, fluid antiperspirant, solid deodorant, fluid deodorant, fluid detergent, solid detergent, fluid hard surface cleaner, solid hard surface cleaner, a fluid fabric refresher spray, a diaper, an air freshening product, a nutraceutical supplement, a controlled release fertilizer, a controlled release insecticide, a controlled release dye, and a unit dose detergent comprising a detergent and the controlled release particles in a water soluble film.
Fluid compositions of the invention preferably further comprise at least one suspension agent to suspend the controlled release particles, wherein the at least one suspension agent is at least one member selected from the group consisting of a rheology modifier, a structurant and a thickener. The at least one suspension agent preferably has a high shear viscosity at, 20 sec−1 shear rate and at 21° C., of from 1 to 7000 cps and a low shear viscosity, at 0.5 sec−1 shear rate and at 21° C., of greater than 1000 cps or 1000-200,000 cps. In certain embodiments, the composition has a high shear viscosity, at 20 sec−1 and at 21° C., of from 50 to 3000 cps and a low shear viscosity, at 0.5 sec−1 shear rate and at 21° C., of greater than 1000 cps or 1000-200,000 cps.
Preferably, the at least one suspension agent is selected from the group consisting of polyacrylates, polymethacrylates, polycarboxylates, pectin, alginate, gum arabic, carrageenan, gellan gum, xanthan gum, guar gum, gellan gum, hydroxyl-containing fatty acids, hydroxyl-containing fatty esters, hydroxyl-containing fatty waxes, castor oil, castor oil derivatives, hydrogenated castor oil derivatives, hydrogenated castor wax and mixtures thereof.
The invention further encompasses a slurry comprising particles of the invention. Said slurry may be combined with an adjunct ingredient to form a composition, for example, a consumer product. In certain embodiments, the slurry comprises at least one processing aid selected from the group consisting of water, aggregate inhibiting materials such as divalent salts, particle suspending polymers, and mixtures thereof. Examples of aggregate inhibiting materials include salts that can have a charge shielding effect around the particle, such as, e.g., magnesium chloride, calcium chloride, magnesium bromide, magnesium sulfate and mixtures thereof. Examples of particle suspending polymers include polymers such as xanthan gum, carrageenan gum, guar gum, shellac, alginates, chitosan; cellulosic materials such as carboxymethyl cellulose, hydroxypropyl methyl cellulose and cationically charged cellulosic materials; polyacrylic acid; polyvinyl alcohol; hydrogenated castor oil; ethylene glycol distearate; and mixtures thereof.
In certain embodiments, the slurry comprises at least one carrier selected from the group consisting of polar solvents, including but not limited to, water, ethylene glycol, propylene glycol, polyethylene glycol, glycerol, non-polar solvents including but not limited to mineral oil, perfume raw materials, silicone oils, hydrocarbon paraffin oils, and mixtures thereof.
In certain embodiments, a perfume oil is combined with the slurry comprising microcapsules to provide multiple benefits. The emulsified perfume oil will increase the viscosity of the slurry and prevent the phase separation of the microcapsule particles. The mixture provides a way to deliver non-encapsulated and encapsulated fragrance from the same slurry.
In certain embodiments, the composition has at least two controlled release technologies, which release different hydrophobic oil compositions and are selected from the group consisting of neat oils, friction-triggered release microcapsules and water-triggered release microcapsules.
The invention will be illustrated in more detail with reference to the following Examples, but it should be understood that the present invention is not deemed to be limited thereto.
Materials and Methods
The following is a representative perfume oil composition used for capsule making.
Scanning Electron Microscopy
A Phenom Pure (Nanoscience Instruments Model PW-100-019) Scanning Electron Microscope is used to understand the particle morphology, and nature of particle deposits on fabrics. PELCO tabs carbon tape (12 mm OD, Ted Pella product number 16084-1) is applied to an aluminum specimen mount (Ted Pella Product No 16111). Next, the powder sample is placed onto the carbon tape using a transfer spatula. Excess powder is removed by blowing Dust-Off compressed gas onto the sample. The stub is then left in a desiccator under vacuum for 16 hours to flash off any volatiles. The sample is then placed into the Phenom Pure, and imaged to visualize particle morphology.
Detergent/Water Dissolution+Fabric Preparation
To 9.75 grams of a detergent solution (1 gram of liquid detergent added to 99 grams of water, then filtered through Whatman 597 filter catalog number 10311808) is added powder or slurry that achieves a concentration of approximately 1 wt. % perfume oil in the detergent solution. For water solubility, the powder is simply dosed into water rather than detergent solution. For the Detergent Dissolution Test, the sample is mixed at 200 RPM for 30 minutes at 33.3° C. A pre-weighed 3 inch diameter circle of black 100% cotton fabric is placed in a Buchner funnel attached to a vacuum line. 2 mL of the solution is then poured through the fabric, followed by a wash of 2 mL water. The fabric is allowed to air dry overnight.
Odor Evaluation
There are two techniques utilized to evaluate odor of fabrics:
1) The dried fabrics from the Detergent Dissolution Test+Fabric Preparation test are evaluated olfactively by a panel before and after rubbing. A subjective grading scale is used to grade fabrics before rubbing and after rubbing. In the case of before rubbing, the control that is used is a fabric treated with neat fragrance oil in the detergent solution. In the case of rubbed fabric, the control is the fabric before rubbing is performed.
The dried fabrics from the Detergent Dissolution Test+Fabric Preparation test are evaluated by an Odor Meter (Shinyei Technology model OMX-SRM) before and after rubbing. This method reports the total concentration of volatiles in the headspace and is reported in milligrams per cubic meter as a function of time
Free Oil
Approximately 0.20 grams to 0.27 grams of microcapsule slurry is preweighed in a 20 mL glass scintillation vial. 10 mL of hexane is added to the slurry. The scintillation vial is overturned 10 times to allow for mixing. The scintillation vial is then placed on a platform shaker that shakes the vial at a frequency of 1/sec to allow for mixing of the contents, for 10 minutes. The scintillation vial is allowed to sit unagitated at room temperature for 10 minutes. Sodium sulfate or sodium chloride could be added if there is a lack of phase separation of the hexane layer observed. Approximately 3 mL of the clear hexane layer is removed, placed into a syringe filter (0.45 micron, 25 mm diameter Acrodisc PTFE filter), and decanted into a GC vial. The sample is analyzed by Gas Chromatography. GC conditions are shown in Table 3 below.
Biodegradability
Biodegradability testing is carried out according to protocol OECD 301D. The microcapsule membrane is isolated by going through the following steps: (1) dilute the microcapsule slurry 1:10 with water (2) centrifuge the slurry at 5000 RPM to isolate the capsules and remove all water soluble materials, (3) repeat these steps 3 times, (4) dry the isolated capsules in a vacuum oven at 25 degrees Centigrade for 48 hours, (5) mill the powder using ceramic beads, (6) toluene extraction of the milled powder, followed by filtration to recover the particles, 7) vacuum drying of the powder to remove residual toluene at 0.3 torr for 2 days at 25 degrees Centrigrade, (7) repeat milling of the powder using ceramic beads, (8) water extraction of the milled powder to remove any water soluble components in the membrane, followed by filtration to recover the particles, 9) vacuum dry the powder to remove residual oil at 0.3 torr for 1 day at room temperature. In order to assure that residual oil has been removed, perform hexane extraction followed by Gas Chromatography analysis on the dried powder to assure less than 5% residual oil. The isolated polymer is then subjected to OECD 301D protocol, available at https://www.oecd.org/chemicalsafety/risk-assessment/1948209.pdf, with the following experimental conditions:
1) test substance concentration in the mineral medium is 5 mg/L
2) 300 mL BOD bottles with glass stoppers are used
3) An incubator at 20 C is used to age the samples in the dark
4) The mineral stock solutions as provided in the method are prepared
5) The inoculum comprises Interlab Polyseed seed BOD inoculum tablets. Such tablets are EPA accepted, non-pathogenic, free of nitrifying microorganisms. 1 capsule is mixed with 0.5 L of APHA standard dilution water at 20 C, and stirred for 60 minutes.
6) COD of the isolated polymer is measured using Hach kit
The bottles are checked for dissolved oxygen at 0 days, 7, 14, 21, and 28 days. The percent degradation is analyzed via the calculations taught in the OECD 301D method.
Polyacrylate and Polyurea Hybrid Capsule
The following capsules are prepared by free radical polymerization of acrylate monomers in situ with polyisocyanate-amine reaction to yield a hybrid organic wall. High temperature is required to make a membrane. The membrane does not have any additional coatings to provide enhanced barrier properties of the present invention.
Prepare Oil Phase: mix 60 g of Perfume oil, 1.18 g of urethane acrylate oligomer, 2.36 g of aromatic acid acrylate half ester, 5.16.3 g of polyisocyanate and 0.34 g of Vazo-68 respectively. Contents of the mixture are allowed to stir at room temperature using a magnetic stir bar at 100-150 rpm for 20 minutes.
Prepare Aqueous Phase: 210 grams of 5 wt. % aqueous solution of polyvinyl pyrrolidone is prepared
Emulsion Formation: The prepared oil phase is added into the aqueous phase while agitating the aqueous phase using a Caframo BDC6015, 4-blade pitched agitator shaft 1″ diameter, at 750 rpm for 25 minutes to form a premix emulsion. An aliquot is analyzed by optical microscopy to understand particle size of the emulsion. 2 grams of water borne silsesquioxane oligomer is added dropwise and the reaction mixture is allowed to stir for next 5 hr at room temperature. The reaction mixture is then heated to 85° C. for 4 hours, followed by overnight stirring while cooling the batch.
Basified Chitosan Oligosaccharide: 150 grams of chitosan oligosaccharide (TCI Chemicals C2849) is dissolved in 1350 grams of distilled water. Approximately 265 grams of a 10 wt % solution of sodium carbonate is added to achieve a pH of 9.7 The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer.
Basified Gelatin: 300 grams of gelatin (260 bloom pig skin Gelita) is dissolved in 998 grams of distilled water at 60 C. Approximately 28 grams of a 10 wt % solution of sodium carbonate is added to achieve a pH of 9.7 The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer.
Basified Casein: 100 grams of casein (Naked Casein, Amazon.com) is dissolved in 1900 grams of distilled water at room temperature. Approximately 15 grams of a 10 wt % solution of sodium carbonate is added to achieve a pH of 9.7 The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer.
Basified Silk Protein: 100 grams of silk protein is dissolved in 1900 grams of distilled water at room temperature. Approximately 15 grams of a 10 wt % solution of sodium carbonate is added to achieve a pH of 8.8 The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer.
Basified Tannic Acid: 150.5 grams of tannic acid powder is dissolved in 1352 grams of deionized water by heating to 60 degrees Centigrade to achieve a clear homogeneous solution. The solution is cooled to room temperature and ammonium hydroxide (74 g) is added to achieve a pH of 9.1. The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer.
A four neck round bottom flask is charged with 75.6 g polyisocyanate. 75.06 g monoester solvent (e.g. hexyl acetate or isopropyl myristate) is added to flask under agitation at 25 degrees Centigrade with N2 blanket. 63 g triethyl citrate is dissolved in the same ester solvent used to dissolve polyisocyanate in a separate glass container and 4-6 drops of dibutyl tin dilaurate catalyst is added to this solution. This triethyl citrate solution is added dropwise (for a period of 30 minutes) into polyisocyanate solution at 55 degrees Centigrade. The reaction is continued at 70 degrees Centrigrade for 1 hour, then 95 degrees Centigrade for 3 hours, then 115 degrees Centigrade for 1 hour, under agitation with N2 protection. Flask is cooled down to room temperature. Residual isocyanate in product is confirmed by FT-IR. Isocyanate titration is conducted to determine the residual isocyanate content in the product.
P-CMS: 101.05 grams of carboymethyl starch (Patel Chem Industries) is dissolved in 1824 grams of distilled water at room temperature. The pH of the solution is adjusted to 8.0 using 10 wt % hydrochloric acid. After 10 minutes of mixing, a homogeneous solution is obtained. Next, 160 grams of Polycup 9700 (Solenis) is added to the suspension. The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer. The powder is then heated at 110° C. for 30 minutes in an oven.
P-Casein: 150 grams of Casein (Naked Casein, amazon.com) is dissolved in 2850 grams of distilled water at room temperature. Approximately 22.5 grams of 10 wt % sodium carbonate is added to achieve a pH of 8.0 Next, 128.2 grams of Polycup 9700 (Solenis) is added to the suspension. The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer. The powder is then heated at 110° C. for 30 minutes in an oven.
P-Chitosan Oligosaccharide: 100 grams of chitosan oligosaccharide (TCI Chemicals C2849) is dissolved in 900 grams of distilled water at room temperature. The pH of the solution is adjusted to 9 by adding approximately 300 grams of 10 wt % sodium carbonate solution in water. Approximately 780 grams of this solution is preweighed into a beaker, and 400 grams of Polycup 9700 (Solenis) is added to yield a solution. The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 385 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer. The powder is then heated at 110° C. for 30 minutes in an oven.
P-Gelatin-Glycerin: 150 grams of Gelatin high bloom strength is dissolved in 1350 grams of water at 40 degrees Centigrade. 31 grams of glycerine is added to the solution. Approximately 8.5 grams of a 20% solution of sodium carbonate is added to adjust the pH to 10.2. Approximately 81 grams of Crepetrol 9200 (Solenis) is added to yield a homogeneous solution. The homogeneous suspension is spray dried in a Bowen 3 ft diameter co-current spray drying tower using a 2-fluid nozzle at 70 psi air pressure, an inlet air temperature of 350 degrees Fahrenheit and an outlet temperature of 185 degrees Fahrenheit. Dry powder with a median size of 19 microns is collected from the spray dryer. The powder is then heated at 110° C. for 60 minutes in an oven.
4A:
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.02 g of diepoxy of aliphatic dimer acid, 0.86 g of Trimethylolpropoane triglycidyl ether, 1.32 g of Tetraethyl orthosilicate, 0.77 g of 1,2-Bis(Triethoxysilyl)ethane, 1.17 g of methyl ester of Rosin, 0.72 g of Nano Talc, 1 g of pre-reacted natural material resin of Example 3, 2.36 g of polyisocyanate and 3.19 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine is added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. An aqueous solution of 2.2 g of Chitosan Oligosaccharide, with pH adjusted to 9 (using 10% Sodium carbonate) is added dropwise and the reaction mixture is allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1.02 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
4B:
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.02 g of diepoxy of aliphatic dimer acid, 0.86 g of Trimethylolpropoane triglycidyl ether, 1.26 g of Tetraethyl orthosilicate, 0.8 g of 1,2-Bis(Triethoxysilyl)ethane, 1.32 g of methyl ester of Rosin, 0.73 g of Nano Talc, 1 g of pre-reacted natural material resin of Example 3, 2.36 g of polyisocyanate and 3.23 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of Pigskin Gelatin (260 Bloom) is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once desired particle size is achieved, an aqueous solution of 10% Sodium carbonate is added dropwise to increase the pH of the solution to 9 and the reaction mixture was allowed to stir for next 90 minutes at room temperature followed by heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature. The material becomes a solid gel.
Observation: Increasing the pH results in increase in viscosity of the emulsion. After overnight stirring the slurry appeared thick solid gel.
4C:
36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.02 g of diepoxy of aliphatic dimer acid, 0.86 g of Trimethylolpropoane triglycidyl ether, 1.34 g of Tetraethyl orthosilicate, 0.75 g of 1,2-Bis(Triethoxysilyl)ethane, 1.26 g of methyl ester of Rosin, 0.75 g of Nano Talc, 1 g of pre-reacted natural material resin of Example 3, 2.44 g of polyisocyanate and 3.16 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of Polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once desired particle size is achieved, an aqueous solution of Casein (2.34 g), with pH adjusted to 9 (using 10% Sodium carbonate) is added dropwise and the reaction mixture is allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature.
4D:
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.02 g of diepoxy of aliphatic dimer acid, 0.86 g of Trimethylolpropoane triglycidyl ether, 1.32 g of Tetraethyl orthosilicate, 0.77 g of 1,2-Bis(Triethoxysilyl)ethane, 1.17 g of methyl ester of Rosin, 0.72 g of Nano Talc, 2.36 g of polyisocyanate and 3.19 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine is added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. An aqueous solution of 2.2 g of Chitosan Oligosaccharide, with pH adjusted to 9 (using 10% Sodium carbonate) is added dropwise and the reaction mixture is allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1.02 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature.
4E:
Prepare Oil Phase: 40 grams of perfume oil, 3.6 grams of sorbitol glycidyl ether, 1.12, g of Trimethylolpropoane triglycidyl ether, 3.0 grams of P-Gelatin-Glycerine powder of example 3, 3.2 g of polyisocyanate and 2.2 g of cycloaliphatic diisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 17 grams of Nexsil colloidal silica suspension is diluted with 96 grams of wear.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. An aqueous solution of 10 g of basified gelatin of example 2 is added dropwise and the reaction mixture is allowed to stir for next 90 minutes at room temperature. Subsequently, the contents are set for heating to 60° C. for next 6 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature. The next day, approximately 0.6 grams of tannic acid previously dissolved in water is added and agitated for 2 hours at 50 degrees Centigrade.
4F:
Prepare Oil Phase: 90 g of Perfume oil, 3.7 g of sorbitol diglycidyl ether, 1.56 g of Trimethylolpropoane triglycidyl ether, 0.4 g of triethylamine, 2.94 g of polyisocyanate and 5.33 g of cyanurate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 10 g of gelatin is dissolved in 190 g of water and held at 40 degrees Centigrade.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 120 minutes to form a premix emulsion at 40 degrees Centigrade. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. An aqueous solution of lysine methyl ester (3.44 grams diluted in 20 mL of water), with pH adjusted to 9 (using 10% Sodium carbonate) is added dropwise and the reaction mixture is allowed to stir for next 120 minutes at 40 degrees Centigrade. Subsequently, the contents are set for heating to 60° C. for next 6 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature.
4G:
Prepare Oil Phase: 90 g of Perfume oil, 0.53 g basified tannic acid of Example 2, 2 g P-Gelatin-Glycerine of example 3, 4.6 g of soribitol glycidyl ether, 1.88 g of Trimethylolpropoane triglycidyl ether, 2.82 g of Tetraethyl orthosilicate, 1.68 g of 1,2-Bis(Triethoxysilyl)ethane, 2.96 g of methyl ester of Rosin, 1.4 g of Nano Talc, 5.97 g of polyisocyanate, 3.3 g of cyanurate, 2.1 g of cycloaliphatic diisocyanate, 2.6 grams of hexamethylene diisocyanate, 2.2 g of isophorone diisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 300 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. A mixture of an aqueous solution of lysine methyl ester (8.33 grams in 50 mL of water), 200 grams of a 5 wt % solution of gelatin is added to the emulsion, followed by addition of 10 wt % sodium carbonate to maintain a solution pH of 9. The contents are set for heating to 60° C. for next 6 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature. Approximately 2 g of Pectin is added, followed by addition of 1M HCl to adjust pH to 6.5. Next, 11 mL of a 3 wt % aqueous solution of polyaziridine, PZ-28, is added while agitating at 700 RPM. Contents area allowed to mix for 3 hours at room temperature.
5A: (Capsules with Pre-Reacted Natural Resin+Basified Biodegradable Resin)
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.04 g of diepoxy of aliphatic dimer acid, 0.9 g of Trimethylolpropoane triglycidyl ether, 1.45 g of Tetraethyl orthosilicate, 0.75 g of 1,2-Bis(Triethoxysilyl)ethane, 1.24 g of methyl ester of Rosin, 0.71 g of Nano Talc, 1.07 g of pre-reacted natural resin of Example 3, 1.02 g Basified Chitosan Oligosaccharide of Example 1, 2.56 g of polyisocyanate and 3.67 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.2 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1.06 g) is added dropwise and the contents were set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
5B: (Capsules with Pre-Reacted Natural Resin+Basified Biodegradable Resin)
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.13 g of diepoxy of aliphatic dimer acid, 0.83 g of Trimethylolpropoane triglycidyl ether, 1.4 g of Tetraethyl orthosilicate, 0.8 g of 1,2-Bis(Triethoxysilyl)ethane, 1.22 g of methyl ester of Rosin, 0.74 g of Nano Talc, 1.08 g of pre-reacted natural resin of Example 3, 0.72 g Basified Pigskin Gelatin of Example 1, 2.6 g of polyisocyanate and 3.62 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.31 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1.02 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
5C: (Basified Biodegradable Resin Only)
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2 g of diepoxy of aliphatic dimer acid, 0.74 g of Trimethylolpropoane triglycidyl ether, 1.23 g of Tetraethyl orthosilicate, 0.69 g of 1,2-Bis(Triethoxysilyl)ethane, 1.31 g of methyl ester of Rosin, 0.7 g of Nano Talc, 1 g of Basified Chitosan oligosaccharide of Example 1, 2.4 g of polyisocyanate and 3.35 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.2 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
5D: (Basified Biodegradable Resin Only)
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.04 g of diepoxy of aliphatic dimer acid, 0.77 g of Trimethylolpropoane triglycidyl ether, 1.26 g of Tetraethyl orthosilicate, 0.68 g of 1,2-Bis(Triethoxysilyl)ethane, 1.3 g of methyl ester of Rosin, 0.73 g of Nano Talc, 0.7 g of Basified Casein of Example 1, 2.4 g of polyisocyanate and 3.2 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.1 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture is allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1 g) is added dropwise and the contents were set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature.
5E: (basified biodegradable resin only)
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.1 g of diepoxy of aliphatic dimer acid, 0.76 g of Trimethylolpropoane triglycidyl ether, 1.27 g of Tetraethyl orthosilicate, 0.71 g of 1,2-Bis(Triethoxysilyl)ethane, 1.3 g of methyl ester of Rosin, 0.7 g of Nano Talc, 0.74 g of Basified Pigskin Gelatin of Example 1, 2.47 g of polyisocyanate and 3.3 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.13 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
5F: (Basified Biodegradable Resin Only)
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.1 g of diepoxy of aliphatic dimer acid, 0.76 g of Trimethylolpropoane triglycidyl ether, 1.27 g of Tetraethyl orthosilicate, 0.71 g of 1,2-Bis(Triethoxysilyl)ethane, 1.3 g of methyl ester of Rosin, 0.7 g of Nano Talc, 0.74 g of Basified Silk Protein of Example 1, 2.47 g of polyisocyanate and 3.3 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.13 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
6A:
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2 g of diepoxy of aliphatic dimer acid, 0.8 g of Trimethylolpropoane triglycidyl ether, 1.31 g of Tetraethyl orthosilicate, 0.7 g of 1,2-Bis(Triethoxysilyl)ethane, 1.22 g of methyl ester of Rosin, 0.76 g of Nano Talc, 1.08 g of pre-reacted natural material resin of Example 3, 2.26 g of polyisocyanate and 3.17 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.2 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
6B:
Prepare Oil Phase: 36 g of Perfume oil, 9 g of Isopropyl Myristate, 2.11 g of diepoxy of aliphatic dimer acid, 0.73 g of Trimethylolpropoane triglycidyl ether, 1.23 g of Tetraethyl orthosilicate, 0.72 g of 1,2-Bis(Triethoxysilyl)ethane, 1.16 g of methyl ester of Rosin, 0.72 g of Nano Talc, 1.02 g of pre-reacted natural resin of Example 3, 2.38 g of polyisocyanate and 3.2 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.12 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1.01 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
Prepare Oil Phase: 41 g of Perfume oil, 2.02 g of diepoxy of aliphatic dimer acid, 0.86 g of Trimethylolpropoane triglycidyl ether, 1.43 g of Tetraethyl orthosilicate, 0.82 g of 1,2-Bis(Triethoxysilyl)ethane, 1.24 g of methyl ester of Rosin, 0.71 g of Nano Talc, 1.02 g of pre-reacted natural resin of Example 3, 14 g of pre-reaction product of polyisocyanate of Example 2, 1.19 g of polyisocyanate and 3.12 g of pentane-1,5-diisocyanate based polyisocyanate are added respectively and stirred for 10 minutes at 100-150 rpm using a magnetic stir bar for homogeneity.
Prepare Aqueous Phase: 125 g of 5 wt % aqueous solution of polyvinyl pyrrolidone is prepared to this 0.15 g of Triethanolamine was added and allowed to stir for 5 minutes at 500 rpm.
Emulsion Formation: The prepared oil phase and aqueous phase are mixed using a propeller mixer at 1100 rpm for 25 minutes to form a premix emulsion. Aliquot is analyzed by optical microscopy to understand particle size of the emulsion. Once the desired particle size is achieved, an aqueous solution of 2.24 g amine functionalized trialkoxy silane is added dropwise and the reaction mixture was allowed to stir for next 90 minutes at room temperature. Later, an aqueous solution of isobutylene-maleic anhydride polymer (1.03 g) is added dropwise and the contents are set for heating to 60° C. for next 4 hr. Allow the contents to stir overnight at above mentioned agitation rate to gradually cool emulsion slurry to room temperature
Microcapsules slurries are formulated into liquid detergent (PUREX FREE & CLEAR), to deliver approximately 0.3 wt % fragrance usage level in the liquid suspension, via the microcapsules or neat perfume oil. These samples are used for leakage stability testing. Equivalent samples are made with 0.5 wt % fragrance usage level in the suspension. Both mixtures are aged for 1 week at 40° C. After ageing, several tests are performed to evaluate the behavior of the capsules
1) Optical microscopy to observe capsule deflation
2) Approximately 5 grams of the detergent mixture is diluted with 5 grams of water to yield a dilute detergent solution containing approximately 0.15 wt % fragrance oil. This diluted suspension is mixed for 30 minutes at a temperature of 33 C at 250 RPM using a magnetic stirrer. Next, approximately 2 mL of the mixed solution is filtered through a black fabric, and allowed to dry overnight. The fabric odor intensity before rubbing and after rubbing is noted.
3) Laundry performance testing is performed with samples containing 0.5 wt % fragrance oil. Approximately 3.0 kg of fabrics are loaded into a Samsung front load washing machine consisting of 5 bath towels, 3 polycotton T-shirts, one 100% cotton t-shirt. No fabric softener or bleach is used. A cold wash is done (approximately 26 minute cycle time shown below). The fabrics are then dried in a Samsung machine dryer on hot cotton cycle for 45 minutes.
Fabrics are graded before rub and after rub. The results of such testing is shown in the table below. The formulations according to this invention are able to survive the liquid laundry matrix (to retain perfume inside the capsule), are able to survive the dilution in the washing machine, are able to deposit onto the fabric, and are able to deliver a noticeable fragrance intensity on fabric, before and after rubbing the fabric. Such capsules are expected to provide fragrance longevity on laundered fabrics.
Microcapsules of various examples above were evaluated for environmental biodegradability by adapting the OCDE/OECD 301D Closed Bottle Test method, as described in the Biodegradability test method description.
To 996 mL of the APHA standard dilution water is added 2 polyseed BOD tablets, followed by addition of 1 mL each of mineral solutions A, B, C, and D. Prepare approximately 300 mL solutions containing the particles to be tested (approximately 1.5 milligrams of the isolated polymer is added to each BOD bottle). Fill BOD bottles (300 mL capacity) just past the neck of the bottle. Insert stopper. Store BOD bottles in the dark in an incubator maintained at 20 degrees Centigrade. Use dissolved oxygen meter (YSI 5000), and YSI5905 Dissolved Oxygen meter probe to measure oxygen at specific time points.
The dissolved oxygen measured values as a function of time, and the calculation methods presented in OECD 301D method are utilized to calculate the % biodegradability. The Environmental Biodegradability index is calculated by multiplying the measured % biodegradability by 100. The results are listed in Table 7 below.
A biodegradability index greater than 60 meets current ECHA requirements for microplastics biodegradability (2019). We anticipate 4E, 4F, and 4G to continue to increase in biodegradability to 60% in 60 days.
Selected microcapsules from the above examples are formulated into a leave-on-conditioner formulation as follows: to 98.0 grams of leave-on-conditioner (with a typical formulation given below) is added an appropriate amount of microcapsule slurry of Examples 1 to 7, to deliver an encapsulated oil usage level of 0.5 wt. %. The microcapsules are added on top of the conditioner formulation, then the contents are mixed at 1000 RPM for 1 minute.
A typical composition of a leave-on conditioner formulation is given in Table 10.1 below.
Selected microcapsules from the above examples are formulated into a rinse-off shampoo formulation as follows: to 90.0 grams of shampoo formulation is added an appropriate amount of microcapsule slurry of Examples 1 to 7, to deliver an encapsulated oil usage level of 0.5 wt. %. The microcapsules and water are added on top of the shampoo formulation, then the contents are mixed at 1850 RPM for 1 minute. Typical shampoo formulations are shown in Tables 11.1, 11.2 and 11.3 below.
1 Mirapol AT-1, Copolymer of Acrylamide(AM) and TRIQUAT, MW = 1,000,000; CD = 1.6 meq./gram; 10% active; Supplier Rhodia
2 Jaguar C500, MW − 500,000, CD = 0.7, supplier Rhodia
3 Mirapol 100S, 31.5% active, supplier Rhodia
4 Sodium Laureth Sulfate, 28% active, supplier: P&G
5 Sodium Lauryl Sulfate, 29% active supplier: P&G
6 Glycidol Silicone VC2231-193C
7 Tegobetaine F-B, 30% active supplier: Goldschmidt Chemicals
8 Monamid CMA, 85% active, supplier Goldschmidt Chemical
9 Ethylene Glycol Distearate, EGDS Pure, supplier Goldschmidt Chemical
10 Sodium Chloride USP (food grade), supplier Morton; note that salt is an adjustable ingredient, higher or lower levels may be added to achieve target viscosity.
1 Glycidol Silicone
4 Cyclopentasiloxane: SF1202 available from Momentive Performance Chemicals
5 Behenyl trimethyl ammonium chloride/Isopropyl alcohol: Genamin TM KMP available from Clariant
6 Cetyl alcohol: Konol TM series available from Shin Nihon Rika
7 Stearyl alcohol: Konol TM series available from Shin Nihon Rika
8 Methylchloroisothiazolinone/Methylisothiazolinone: Kathon TM CG available from Rohm & Haas
9 Panthenol: Available from Roche
10 Panthenyl ethyl ether: Available from Roche
1 Jaguar C17 available from Rhodia
2 N-Hance 3269 (with Mol. W. of ~500,000 and 0.8 meq/g) available from Aqulaon/Hercules
3 Viscasil 330M available from General Electric Silicones
4 Gel Networks; See composition in Table 14.4 below. The water is heated to about 74° C. and the Cetyl Alcohol, Stearyl Alcohol, and the SLES Surfactant are added to it. After incorporation, this mixture is passed through a heat exchanger where it is cooled to about 35° C. As a result of this cooling step, the Fatty Alcohols and surfactant crystallized to form a crystalline gel network.
For the examples shown in Table 12 below, in a suitable container, combine the ingredients of Phase A. In a separate suitable container, combine the ingredients of Phase B. Heat each phase to 73° C.-78° C. while mixing each phase using a suitable mixer (e.g., Anchor blade, propeller blade, or IKA T25) until each reaches a substantially constant desired temperature and is homogenous. Slowly add Phase B to Phase A while continuing to mix Phase A. Continue mixing until batch is uniform. Pour product into suitable containers at 73-78° C. and store at room temperature. Alternatively, continuing to stir the mixture as temperature decreases results in lower observed hardness values at 21 and 33° C.
1 12.5% Dimethicone Crosspolymer in Cyclopentasiloxane. Available from Dow Corning.
2 E.g., TOSPEAR 145A or TOSPEARL 2000. Available from GE Toshiba Silicon.
3 25% Dimethicone PEG-10/15 Crosspolymer in Dimethicone. Available from Shin-Etsu.
4 JEENATE 3H polyethylene wax from Jeen.
5 Stearyl Dimethicone. Available from Dow Corning.
6 Hexamidine diisethionate, available from Laboratoires Serobiologiques.
7 Additionally or alternatively, the composition may comprise one or more other skin care actives, their salts and derivatives, as disclosed herein, in amounts also disclosed herein as would be deemed suitable by one of skill in the art.
Example 13A of Table 13.1 below can be made via the following general process, which one skilled in the art will be able to alter to incorporate available equipment. The ingredients of Part I and Part II are mixed in separate suitable containers. Part II is then added slowly to Part I under agitation to assure the making of a water-in-silicone emulsion. The emulsion is then milled with a suitable mill, for example a Greeco 1L03 from Greeco Corp, to create a homogenous emulsion. Part III is mixed and heated to 88° C. until the all solids are completely melted. The emulsion is then also heated to 88° C. and then added to the Part 3 ingredients. The final mixture is then poured into an appropriate container, and allowed to solidify and cool to ambient temperature.
1 DC 246 fluid from Dow Corning
2 from Dow Corning
3 Standard aluminum chlorohydrate solution
Examples 13B to 13E of Table 13.2 below can be made as follows: all ingredients except the fragrance, and fragrance capsules are combined in a suitable container and heated to about 85° C. to form a homogenous liquid. The solution is then cooled to about 62° C. and then the fragrance, and fragrance microcapsules are added. The mixture is then poured into an appropriate container and allowed to solidify up cooling to ambient temperature.
Example 13F of Table 13.2 can be made as follows: all the ingredients except the propellant are combined in an appropriate aerosol container. The container is then sealed with an appropriate aerosol delivery valve. Next air in the container is removed by applying a vacuum to the valve and then propellant is added to container through the valve. Finally an appropriate actuator is connected to the valve to allow dispensing of the product.
The conditioning compositions of Examples 14A through 14F of Table 14 are prepared as follows: cationic surfactants, high melting point fatty compounds are added to water with agitation, and heated to about 80° C. The mixture is cooled down to about 50° C. to form a gel matrix carrier. Separately, slurries of perfume microcapsules and silicones are mixed with agitation at room temperature to form a premix. The premix is added to the gel matrix carrier with agitation. If included, other ingredients such as preservatives are added with agitation. Then the compositions are cooled down to room temperature.
The conditioning composition of Example 14B of Table 14 is prepared as follows: cationic surfactants, high melting point fatty compounds are added to water with agitation, and heated to about 80° C. The mixture is cooled down to about 50° C. to form a gel matrix carrier. Then, silicones are added with agitation. Separately, slurries of perfume microcapsules, and if included, other ingredients such as preservatives are added with agitation. Then the compositions are cooled down to room temperature.
1 Aminosilicone-1 (AMD): having an amine content of 0.12-0.15 m mol/g and a viscosity of 3,000-8,000 mPa · s, which is water insoluble
2 Aminosilicone-2 (TAS): having an amine content of 0.04-0.06 m mol/g and a viscosity of 10,000-16,000 mPa · s, which is water insoluble
3Comparative example with PDMS instead of amino silicone
The body cleaning compositions of Examples 15A-15C are prepared as follows.
The cleansing phase composition is prepared by adding surfactants, guars, and Stabylen 30 to water. Sodium chloride is then added to the mixture to thicken the cleansing phase composition. Preservatives and chelants are added to the formulation. Finally, perfume is added to the suspension.
The Benefit phase composition is prepared by mixing petrolatum and mineral oil to make a homogeneous mixture. Fragrance microcapsules are added to the suspension. Finally, the cleansing phase (e.g. surfactant phase) and benefit phase are mixed in different ratios to yield the body cleansing composition.
Non-limiting examples of product formulations containing purified perfume microcapsules of the aforementioned examples are summarized in the following table.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
f Copolymer of ethylene oxide and terephthalate having the formula described in US 5,574,179 at col. 15, lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R1 is essentially 1,4-phenylene moieties, each R2 is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
g SE39 from Wacker
h Diethylenetriaminepentaacetic acid.
i KATHON CG available from Rohm and Haas Co. “PPM” is “parts per million.”
j Gluteraldehyde
k Silicone antifoam agent available from Dow Corning Corp. under the trade name DC2310.
l Hydrophobically-modified ethoxylated urethane available from Rohm and Haas under the tradename Aculyn ™ 44.
Non-limiting examples of product formulations containing purified perfume microcapsules of the aforementioned examples are summarized in the following table.
Non-limiting examples of product formulations containing purified perfume microcapsules of the aforementioned examples are summarized in Tables 18.1, 18.2 and 18.3 below.
Non-limiting examples of product formulations containing purified perfume microcapsules of the aforementioned examples are summarized in Table 19 below.
The following are examples of unit dosage forms wherein the liquid composition is enclosed within a PVA film. The preferred film used in the present examples is Monosol M8630 76 μm thickness.
1Polyethylenimine (MW = 600) with 20 ethoxylate groups per —NH.
2 RA = Reserve Alkalinity (g NaOH/dose)
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
This application claims priority to U.S. Provisional Application No. 63/109,833 filed on Nov. 4, 2020, whose entire disclosure is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63109833 | Nov 2020 | US |
