 COMPOSITION OF MICROCAPULE PARTICLE, AND, PRODUCT FOR PERSONAL, THERAPEUTIC, COSMETIC OR COSMECHANIC
专利摘要:
microcapsule particle composition, microcapsule particle, personal care, therapeutic, cosmetic or cosmeceutical product, process for preparing microcapsule particles containing an oil or aqueous liquid core, and preparation of microcapsule particles, describes microcapsule particles with a core of oil or aqueous liquid, and a capsule composed of a combination of metallic or semi-metallic oxide polymers. methods for the preparation and use of microcapsule particles in products for personal, therapeutic, cosmetic or cosmeceutical care are also presented. 公开号:BR102012006009B1 申请号:R102012006009-4 申请日:2012-03-16 公开日:2020-09-24 发明作者:Yabin Lei；Lewis Michael Popplewell；Xiao Huang 申请人:International Flavors & Fragrances Inc.； IPC主号:
专利说明:
[0001] [001] The present application for a patent claims the priority benefit of US Provisional Application Serial Number 61 / 453,977 filed on March 18, 2011, the content of which is incorporated herein by reference in its entirety. History of the Invention [0002] [002] Fragrance chemicals are used in several products to improve consumer satisfaction with a product. Fragrance chemicals are added to consumer products such as laundry detergents, fabric softeners, soaps, detergents, personal care products such as, but not limited to, shampoos, body care products, deodorants and the like, as well like several other products. [0003] [003] In order to improve the effectiveness of fragrance materials for the user, several technologies have been employed to improve the delivery of fragrance materials at the desired time. A widely used technology is the encapsulation of the fragrance material in a protective coating. Often, the protective coating is a polymeric material. The polymeric material is used to protect the fragrance material from evaporation, reaction, oxidation or otherwise from dissipation before use. A brief overview of fragrance materials encapsulated with polymeric material is revealed in the following US Patents. U.S. Patent No. 4,081,384 discloses an anti-static fabric softener or core coated with a polycondensate suitable for use in a fabric conditioner. US Patent No. 5,112,688 discloses selected fragrance materials having the appropriate volatility to be coated by coacervation with microparticles on a wall that can be activated for use in fabric conditioning. U.S. Patent No. 5,145,842 discloses a solid core of a fatty alcohol, ester, or other solid plus a fragrance coated by an aminoplastic capsule. US Patent No. 6,248,703 discloses several agents including the fragrance in an aminoplastic capsule included in an extruded bar soap. [0004] [004] FR 2780901, WO 99/03450, FR 2703927, WO 94/04260 and WO 94/04261 further reveal microparticles and nanoparticles for encapsulating cosmetics, pharmaceuticals and food compositions, which include cell walls that are formed by cross-linking of organic and bio-organic polymers. [0005] [005] Although encapsulating fragrances in a polymeric capsule can help prevent fragrance degradation and loss, this is often not sufficient to significantly improve fragrance performance in consumer products. Therefore, methods to assist the deposition of encapsulated fragrances have been described. U.S. Patent No. 4,234,627 describes a liquid fragrance coated with an aminoplastic capsule additionally coated with a water-insoluble dissolvable cationic coating in order to improve the deposition of tissue conditioner capsules. U.S. Patent No. 6,194,375 suggests the use of hydrolyzed polyvinyl alcohol to aid in the deposition of polymeric particles from fragrances of cleaning products. U.S. Patent No. 6,329,057 describes the use of materials that have free hydroxy groups or pending cationic groups to assist in the deposition of fragrance-free solid particles from products intended for the consumer. [0006] [006] In addition, the prior art describes the use of silica to form microcapsule formulations specifically designed to prevent an encapsulated active ingredient from leaving the microcapsule. This is desirable when the active ingredient is irritating to the body tissue to which it is applied. This is also desired when the active ingredient acts by interacting with light, such as sunlight. See U.S. Patent No. 6,303,149 and U.S. Patent No. 6,238,650. However, these references fail to teach compositions and methods for releasing and, consequently, delivering the active ingredients. In addition, although US Patents 1 ffi. 6,337,089; 6,537,583; 6,855,335 and 7,758,888 describe inorganic capsules containing a core with an active ingredient, these references do not teach modifications that improve performance. [0007] [007] Consequently, there is a need to improve the delivery of fragrance materials for various personal care products, rinse products and cosmetics that provide improved performance. Summary of the Invention [0008] [008] The present invention is a microcapsule particle composition composed of (a) a core formed from an oil or aqueous liquid containing at least one active ingredient and (b) a capsule surrounding said core, characterized by the fact that that said capsule is composed of (i) at least one hydrolyzable metallic or semi-metallic oxide polymer, and (ii) at least one metallic or semi-metallic oxide polymer with a non-hydrolyzable substitute, characterized by the fact that the metallic or semi-metallic oxide polymer non-hydrolyzable is present in an amount of up to 10% of the total weight of the capsule and optionally (c) a surfactant or polymer. In one embodiment, the metal of the hydrolyzable metal or semi-metallic oxide polymer and at least one non-hydrolyzable metal or semi-metallic oxide polymer are aluminum, silicon, zirconium or a transition metal. In another configuration, the surfactant or polymer is a phosphate ester surfactant or polymer. The terms surfactant and polymer are often used interchangeably by those skilled in the art since the cut in molecular weight is usually imprecisely defined. A personal care, therapeutic, cosmetic or cosmeceutical product containing the microcapsule particle of the invention is also presented. [0009] [009] The present invention also describes processes for the preparation of microcapsule particles containing an oil or aqueous liquid core. In one embodiment, a first emulsion containing an oil or aqueous liquid is combined with a mixture of (i) at least one hydrolyzable sol-gel precursor and (ii) at least one sol-gel precursor containing at least one non-hydrolyzable substitute, characterized by fact that the sol-gel precursor containing at least one non-hydrolyzable substitute is present in an amount of up to 10% of the total sol-gel precursor of (ii); and the combination is cured to prepare the instant microcapsule particles and (iii) the phosphate ester surfactant is further added after step (ii) to produce the microcapsule system. [0010] [0010] In another configuration, the method involves mixing, in a sol-gel process, (i) a first emulsion containing an oil or aqueous liquid and at least one sol-gel precursor containing at least one non-hydrolyzable substitute; and (ii) a second emulsion containing at least one hydrolyzable sol-gel precursor, characterized by the fact that the sol-gel precursor of (i) is present in an amount of up to 10% of the sol-gel precursor of (i) and (ii); curing the mixture to prepare microcapsule particles; and the addition of a surfactant or polymer. [0011] [0011] In an additional configuration, the method involves mixing an oil or aqueous liquid with (i) at least one sol-gel precursor containing at least one non-hydrolyzable substitute; and (ii) at least one sol-gel precursor, characterized by the fact that at least the sol-gel precursor of (i) is present in an amount of up to 10% of the sol-gel precursor of (i) and (ii) to form a first mixture; cooling the first mixture at room temperature; adding the first mixture in an emulsifying solution at room temperature to produce a second mixture; homogenizing the second mixture to produce a homogenized mixture; adding an antifoam to the homogenized mixture; curing the mixture to prepare microcapsule particles and adding a polymer or surfactant. [0012] [0012] A microcapsule particle composition containing a core formed from an oil or aqueous liquid containing at least one active ingredient; a capsule surrounding said core, characterized by the fact that said capsule is composed of at least one hydrolyzable metallic or semi-metallic oxide polymer; and a surfactant or polymer is also provided as a process for preparing said composition. According to the method, an emulsion containing an aqueous oil or liquid and at least one hydrolyzable sol-gel precursor are combined in a sol-gel process; the product is cured and a surfactant or polymer is added to the cured product. [0013] [0013] In some configurations, the oil or aqueous liquid comprises at least one active ingredient such as a fragrance. In another configuration, the non-hydrolyzable sol-gel precursor is a monomer of the formula: M (R) n (P) m, characterized by the fact that M is a metallic or semi-metallic element, R is a hydrolyzable substitute, n is a integer 1 to 6, P is a non-hydrolyzable substitute and is an integer from 1 to 6. According to this configuration, the non-hydrolyzable sol-gel precursor can be a silicon alkoxide such as dimethyldiethoxysilane, n-octylmethyldiethoxysilane, hexadecyltriethoxysilane, diethyldiethoxysilane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane or poly (diethoxysiloxane). In an additional configuration, the hydrolyzable sol-gel precursor is a monomer of the formula M (R) n: characterized by the fact that M is a metallic or semi-metallic element, R is a hydrolyzable substitute, n is an integer from 1 to 6 According to this configuration, the hydrolyzable sol-gel precursor can be a silicon alkoxide such as tetramethyl orthosilicate, tetraethyl orthosilicate or tetrapopil orthosilicate. In still other configurations, the mixture is cured at room temperature or at a temperature between 30 ° and 70 ° C. Preparations of microcapsule particles, personal care products, therapeutic products, cosmetic products and cosmeceutical products containing the microcapsule particles are also presented. [0014] [0014] In additional configurations, the surfactant or polymer can be a surfactant or anionic polymer. The preferred anionic surfactant is a phosphate ester. Examples include CRODAFOS 010A-SS (RB), which is a polyoxyethylene (10) oleyl ether phosphate, and CRODAFOS 030A, which is a polyoxyethylene (3) oleyl ether phosphate from Croda Inc. Edison, NJ. The surfactant can be used from 0.1% to 5% of the total weight of the capsules. The most preferable range is 0.1 to 0.2%. Brief Description of Drawings [0015] [0015] Figures 1A and 1B show the particle size distribution of two different batches of Posh Special particles composed only of TEOS; Figure 1C shows the Posh Special particle size distribution composed of TEOS and 0.5% DMDEOS. [0016] [0016] Figure 1D shows the Posh Special particle size distribution composed of TEOS and 0.75% DMDEOS; Figure 1E shows the Posh Special particle size distribution composed of TEOS and 1.0% DMDEOS; Figure 2A shows the particle size distribution of Psychadelic Gourmand composed only of TEOS. [0017] [0017] Figure 2B shows the particle size distribution of Psychadelic Gourmand composed of TEOS and 0.75% DMDEOS; Figure 3A shows the particle size distribution of Urban Legend composed only of TEOS; Figure 3B shows the particle size distribution of Urban Legend composed of TEOS and 0.75% DMDEOS; Figure 4A shows the particle size distribution of Posh Special capsules composed only of TEOS compared to that of Urban Legend particles composed only of TEOS; Figure 4B shows the particle size distribution of Posh Special capsules composed of TEOS and 0.75% DMDEOS compared to that of Urban Legend particles composed of TEOS and 0.75% DMDEOS; figure 5 shows the results of skin substantivity for microcapsule particles prepared with and without a non-hydrolyzable sol-gel precursor (DMDEOS). ** Indicates a significant difference between pre and post for that sample. HT, cure at high temperature. RT, cure at room temperature. Pure core material, not encapsulated. Control, 0% DMDEOS; and Figure 6 shows the results of tissue evaluation for microcapsule particles prepared with and without a non-hydrolyzable sol-gel precursor (DMDEOS). ** Indicates a significant difference between pre and post scrub for that sample. HT, cure at high temperature. RT, cure at room temperature. Pure core material, not encapsulated. Control, 0% DMDEOS. Detailed Description of the Invention [0018] [0018] It has now been shown that the inclusion of a sol-gel precursor, containing a non-hydrolyzable substitute, in a sol-gel reaction containing a hydrolysable sol-gel precursor produces a microcapsule particle that is less resistant to breakage in compared to sol-gel reactions that contain only the hydrolyzable sol-gel precursor. Given their size and the ease of releasing the active ingredients contained therein, the instant microcapsule particles are of particular use in personal, therapeutic, cosmetic or cosmeceutical applications, including topical application to the skin, hair, ears, mucous membranes, application rectal and nasal application, as well as dental or gum application within the oral cavity. [0019] [0019] Compositions for topical application typically contain, in addition to active ingredients, other ingredients such as flavoring agents, insect repellents, fragrances, colors and tinctures. These ingredients often cause complications when formulated in these compositions. For example, fragrances have no therapeutic action and often still cause skin irritation. Fragrance encapsulation can thus serve to decrease the skin's sensitivity to fragrances, while extending its period of effectiveness through sustained release. Colors and dyes are also typically incompatible with the ingredients in the formulation. In this way, using the compositions and methods of the present invention, they can be protected by the encapsulation and released in the application. [0020] Consequently, the present invention represents a microcapsule particle composed of a core formed from an oil or aqueous liquid containing an active ingredient; and a capsule surrounding said core, characterized by the fact that said capsule is composed of (i) at least one hydrolyzable metallic or semi-metallic oxide polymer, and (ii) at least one metallic or semi-metallic oxide polymer with a non-hydrolyzable substitute. , characterized by the fact that the non-hydrolyzable metallic or semi-metallic oxide polymer is present in an amount of up to 10% of the total weight of the capsule and (iii) a phosphate ester surfactant in an amount of up to 5% of the total capsule paste . [0021] [0021] For the purposes of the present invention, an aqueous oil or liquid is intended to include an oily solution, an aqueous solution, a dispersion or an emulsion such as an oil-in-water emulsion. An "active ingredient" refers to an ingredient containing a biological, therapeutic, cosmetic or cosmeceutical effect and includes, but is not limited to, biological active materials, such as cells, proteins such as antibodies, nucleic acids (for example, siRNA and molecules antisense), small organic molecules, inorganic molecules (for example, isotopes), carbohydrates, lipids, fatty acids and similar molecules. Examples of particular active ingredients that are useful for topical application and that can be beneficially encapsulated in the microcapsules of the present invention include vitamins, anti-inflammatory agents, analgesics, anesthetics, antifungal agents, antibiotics, antiviral agents, antiparasitic agents, antiacne agents, humectants, dermatological agents, enzymes and coenzymes, insect repellents, perfumes, aromatic oils, colors, tinctures, skin whitening agents, flavoring agents, antihistamines, dental agents or chemotherapeutic agents. [0022] [0022] As used here, the term "vitamins" refers to any acceptable vitamin, a derivative and a salt thereof. Examples of vitamins include, but are not limited to, Vitamin A and its analogs and derivatives (eg, retinol, retinal, retinyl palmitate, retinoic acid, retinoin and iso-tretinoin, collectively known as retinoids), vitamin E (tocopherol and its derivatives), vitamin C (L-ascorbic acid and its esters and other derivatives), vitamin B3 (niacinamide and its derivatives), alpha-hydroxy acids (such as glycolic acid, lactic acid, tartaric acid, malic acid, citric acid, etc.). ) and beta-hydroxy acids (such as salicylic acid and the like). [0023] [0023] Anti-inflammatory agents include, for example, methylsalicylate, aspirin, ibuprofen and naproxen. Additional anti-inflammatory agents useful in topical applications include corticosteroids including, but not limited to, flurandrenolide, clobetasol propionate, halobetasol propionate, fluticasone propionate, betamethasone dipropionate, betamethasone benzoate, betamethasone valetate, deoxymethoxone, diaoxamethasone, deoxamethasone, deoxamethasone, deoxamethasone, deoxamethasone diphlorasone, mometasone fuoroate, amcinodine, halcinonide, fluocinonide acetonide, desonide, triamcinolone acetonide, hydrocortisone, hydrocortisone acetate, fluorometallone, methylprednisolone and prednicarbate. [0024] [0024] Anesthetics that can be applied locally include benzocaine, butesine, butesin picrate, cocaine, procaine, tetracaine, lidocaine and pramoxin hydrochloride. [0025] [0025] Suitable analgesics include, but are not limited to, ibuprofen, diclofenac, capsaicin and lidocaine. [0026] [0026] Non-limiting examples of antifungal agents include micanazole, clotrimazole, butoconazole, fenticonazole, tioconazole, teconazole, suconazole, fluconazole, haloprogine, ketonazole, ketoconazole, oxinazole, econazole, itraconazole, terbinafine and tervine. [0027] [0027] Non-limiting examples of antibiotics include erythromycin, clindamycin, sympomycin, tetracycline, metronidazole and similar antibiotics. [0028] [0028] Antiviral agents include, but are not limited to, famciclovir, valacyclovir and acyclovir. Non-limiting examples of antiparasitic agents include scabicides, such as permethrin, crotamitone, lindane and ivermectin. [0029] [0029] Anti-infective and anti-acne agents include, but are not limited to, benzoyl peroxide, sulfur, resorcinol and salicylic acid. [0030] [0030] Non-limiting examples of humectants include glycerol, sodium pyroglutamate and ornithine. [0031] [0031] Dermatological active ingredients useful in topical applications include, for example, jojoba oil and aromatic oils such as methyl salicylate, wintergreen, peppermint oil, bay oil, eucalyptus oil and citrus oil, as well as ammonium phenolsulfonate , bismuth subgalate, zinc phenolsulfonate and zinc salicylate. [0032] [0032] Examples of enzymes and coenzymes useful for topical application include coenzyme Q10, enzyme papain, lipases, proteases, superoxide dismutase, fibinolysin, deoxoribonuclease, trypsin, collagenase and sutilain. [0033] [0033] Non-limiting examples of skin whitening agents include hydroquinone and monobenzone. [0034] [0034] Antihistamines include, but are not limited to, chlorpheniramine, bronfeniramine, dexchlorpheniramine, tripolidine, clemastine, diphenhydramine, promethazine, piperazines, piperidines, astemizole, loratadine and terfonadine. [0035] [0035] The phrase "dental agent" refers to a teeth whitener, a cleaning agent, an aroma for a toothpaste or mouthwash, a vitamin or other substance with a therapeutic effect on the teeth or on the oral cavity. Non-limiting dental agents include bleaching agents such as urea peroxide, benzoyl peroxide, sodium perborate and sodium percarbonate. [0036] [0036] Non-limiting examples of chemotherapeutic agents include 5-fluorouracil, masoprocol, mecloretamine, cyclophosphamide, vincristine, chlorambucil, streptozocin, methotrexate, bleomycin, dactinomycin, daunorubicin, coxorubicin and tamoxifen. [0037] [0037] Examples of flavoring agents are methyl salicylate and peppermint oil, which can be formulated, for example, within a composition useful for dental application. [0038] [0038] Non-limiting examples of insect repellents include pediculicides for the treatment of lice, such as pyrethrins, permethrin, malathion, lindane and similar substances. [0039] [0039] Fragrances are also considered active ingredients within the scope of the invention since they alter the aromatic characteristics of a composition by modifying the olfactory reaction contributed by another ingredient in the composition. The amount of active ingredient in the instant composition will vary depending on many factors, including other ingredients, their relative amounts and the desired effect. Fragrances suitable for use in this invention include, without limitation, any combination of fragrance, essential oil, plant extract or mixture thereof that is compatible and capable of being encapsulated by a monomer or polymer. Examples of fragrances include, but are not limited to, fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk, flower essences as similar to lavender, rose, iris and carnation. Other pleasant essences include herbal essences such as rosemary, thyme and sage; and wild essences derived from pine, spruce and other forest aromas. Fragrances can also be derived from various oils such as essential oils or from plant materials such as mint, mint and similar materials. Other familiar and popular flavors can also be used in the present invention such as talc, popcorn, pizza, cotton candy and the like. A list of suitable fragrances is provided in U.S. Patents 4,534,891. 5,112,688 and 5,145,842. Another source of suitable fragrances is found in Perfumes Cosmetics and Soaps, Second Edition, edited by WA Poucher, 1959. Among the fragrances featured in this treatise are acacia, cassie, chypre, cylamen, fern, gardenia, ripper, heliotrope, honeysuckle, hyacinth , jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly cut hay, orange blossom, orchids, reseda, sweet pea, clover, lemongrass, vanilla, violet, wallflower and similar fragrances. In particular configurations, the fragrance has a high odor activity. In additional configurations, the fragrance has a ClogP greater than 3.3, or more preferably greater than 4. These fragrances include, but are not limited to, allyl cyclohexane propionate, Ambretolide, Amyl benzoate, Amyl cinnamate, Cinnamic aldehyde of amyl, dimethyl acetal cinnamic amyl aldehyde, isoamyl salicylate, AURANTIOL, benzyl salicylate, para-tert-butyl cyclohexyl acetate, quinoline isobutyl, beta-caryophyllene, cadinene, cedrol, cedril acetate, cedril format, cinamyline Cyclohexyl salicylate, Cyclamenaldehyde, Diphenylmethane, Diphenyl oxide, Dodecalactone, ISO AND SUPER, Ethylene brassylate, Ethyl undecylenate, EXALTOLIDE, GALAXOLIDE, Geranyl anthranilate, Geranylilate, hexadicanol, hexanilicide, hexenicilide, hexenylate -Irone, LILIAL, Linalyl benzoate, Methyl dihydrojasmone, Gamma-n-Methyl ionone, Musk indanone, Musk tibetine, Oxahexadecanolida-10, Oxahexadecanolida-11, Alcohol Patchouli, FANTOLIDE, Phenylethyl benzoate, Phenylethylphenylacetate, Phenyl heptanol, Alpha-Santalol, TIBETOLIDE, Delta-Undecalactone, Gamma-Undecalactone, Vetiveryl acetate, Ylangene, Methyl Beta-Naphthyl Ketone, Terpeneol, Diether, Methyl, Methyl, Methyl and Methyl . [0040] [0040] According to one configuration, a composition for personal, therapeutic or cosmeceutical care also includes an adjuvant. As used herein, the term "adjuvant" refers to a material used in conjunction with the active ingredient to preserve the stability of the active ingredient within the composition. The adjuvant can be encapsulated with the active ingredient within the microcapsular nucleus, or be present in the acceptable carrier surrounding the microcapsules. The adjuvant can also serve to preserve the stability of non-encapsulated active ingredients within the carrier. Typical adjuvants include, for example, antioxidants, metal sequestering agents, buffering agents and mixtures thereof. In one example, a metal scavenging agent is used as an encapsulated adjuvant together with vitamin C. The encapsulating metal scavenging agent in this case can be, for example, ethylenediaminetetraacetic acid, hexamethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminopenta acid (methylenephosphonic) or hexamethylenediaminetetra acid (methylenephosphonic), derivatives, salts and / or mixtures thereof. [0041] [0041] In another example, an antioxidant is encapsulated as an adjuvant together with a retinoid. The antioxidant may be, for example, butylated hydroxytoluene (BHT), butylated hydroxyanisol (BHA), vitamin E, vitamin E acetate, vitamin E palmitate, vitamin C, a vitamin C ester, a vitamin C salt and / or their mixtures. [0042] [0042] The active ingredient can also be combined with a variety of solvents that serve to increase the compatibility of the various materials, increase the general hydrophobicity, influence the vapor pressure of the materials or serve to structure the core. Solvents that perform these functions are well known in the art and include mineral oils, triglyceride oils, silicone oils, fats, waxes, fatty alcohols, diisodecyl adipate and diethyl phthalate, among others. [0043] [0043] The active ingredient included in the microcapsule particles of the invention can be a single species or it can be a combination of active ingredients. The level of active ingredient in the microcapsule ranges from approximately 5 to approximately 95 percentage weight, preferably from approximately 30 to approximately 95 and, more preferably, from approximately 50 to approximately 90 percentage weight, on a dry basis. [0044] [0044] As the composition of the present invention is beneficial for the topical application of a wide variety of active ingredients, it can be used efficiently in the treatment of various disorders and conditions. Thus, the present invention also describes a method for treating the skin, hair, ear, mucous, rectal, nasal or dental condition in an individual in need. The method is carried out by topically applying the composition of the present invention to the area to be treated. Non-limiting examples of conditions, diseases or disorders that are treatable by the method of the present invention include, for example, acne, psoriasis, seborrhea, infections by bacteria, viruses or fungi, inflammatory processes, signs of age, dandruff and cavities. [0045] [0045] In accordance with the present invention, a microcapsule particle composition is produced with an encapsulated core material within a microcapsular capsule. In general, the microcapsule particles of the invention are prepared by mixing an oil or aqueous liquid containing an active ingredient with sol-gel precursors under suitable conditions, so that a gel is formed and the active material is encapsulated. Sol-gel precursors, that is, raw materials capable of forming gels, are known in the art and sol-gel methods are routinely practiced in the art. Sol-gel precursors suitable for practicing the present invention include, for example, metals such as silicon, boron, aluminum, titanium, zinc, zirconium and vanadium. According to one application, the preferred sol-gel precursors are silicon compounds, boron and aluminum, more particularly organosilicon compounds, organoboro and organoaluminium. Precursors can also include metal alkoxides and b-diketonates. Sol-gel precursors suitable for the purposes of the invention include di, tri and / or tetrafunctional silicic acid, boric acid and aluminum esters, more particularly alkoxysilanes (alkyl orthosilicate), alkyl alkoxysilanes and their precursors. [0046] [0046] In particular, the present invention represents mixtures of sol-gel precursors or monomers used in the preparation of microcapsule particles having modified release characteristics compared to particles produced from a single type of precursor. More specifically, the instant invention represents a mixture of sol-gel precursors that includes (1) at least one sol-gel precursor containing at least one non-hydrolyzable substitute, also referred to herein as "non-hydrolyzable sol-gel precursor" or "non-hydrolyzable precursor", and (2) at least one hydrolyzable sol-gel precursor. For the purposes of the present invention, the term "non-hydrolyzable substitute" means a substitute that does not separate from a metallic or semi-metallic atom during the sol-gel process. Each substitute is a typically organic group. In contrast, the term "hydrolyzable sol-gel precursor" means a precursor containing substitutes eliminated by hydrolysis under the same conditions. In this regard, a hydrolyzable sol-gel precursor can be a monomer represented by the formula M (R) n, characterized by the fact that M is a metallic or semi-metallic element as described here; R is a hydrolyzable substitute, for example, a C1 to C18 alkoxy group or aryloxy group; and n is an integer from 1 to 6. Similarly, a non-hydrolyzable sol-gel precursor can be a monomer represented by the formula M (R) n (P) m, characterized by the fact that M is a metallic element or semi-metallic as described here; R is a hydrolyzable substitute as described here; n is an integer from 1 to 6; P is a non-hydrolyzable substitute, for example, an alkyl, aryl or alkenyl containing from 1 to 18 carbon atoms; and m is an integer from 1 to 6. [0047] [0047] In some configurations, the mixture of sol-gel precursors includes at least one metallic or semi-metallic alkoxide sol-gel precursor containing a non-hydrolyzable substitute and at least one metallic or semi-metallic alkoxide sol-gel precursor. According to this configuration, a metallic or semi-metallic alkoxide sol-gel precursor containing a non-hydrolyzable substitute can be a monomer represented by the formula M (OR) n (P) m, characterized by the fact that M is a metallic or semi-metallic element , R is a hydrolyzable substitute, n is an integer from 1 to 6, P is a non-hydrolyzable substitute and is an integer from 1 to 6. Additionally, a hydrolyzable metallic or semimetallic precursor sol-gel may be a monomer represented by formula M (OR) n, characterized by the fact that M is a metallic or semi-metallic element as described herein; R is a hydrolyzable substitute; and n is an integer from 1 to 6. In some configurations, the alkoxy group can be replaced by a C 1 to C 4 alkyl or by an alkoxy group or by a halogen atom. In any of the precursors referenced above, R can, of course, represent identical or different alkoxy groups. By way of illustration, R can be an alkylsilane, alkoxysilane, alkyl alkoxysilane or organoalkoxysilane. In addition to the alkyl and alkoxy groups, other organic groups (for example, allyl groups, aminoalkyl groups, hydroxyalkyl groups, etc.) can be attached as substitutes for the metal. [0048] [0048] In particular configurations, the sol-gel precursors of the instant invention are alkoxysilanes represented by the formulas Si (OR) n (P) m (sol-gel precursor containing a non-hydrolyzable substitute) and Si (OR) n (sol precursor) hydrolyzable gel), characterized by the fact that R is a hydrolyzable substitute, n is an integer from 1 to 6, P is a non-hydrolyzable substitute and is an integer from 1 to 6. Particular examples of hydrolyzable alkoxysilane sol-gel precursors include esters of silicic acid such as tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS) or tetrapropyl orthosilicate. A preferred compound includes DYNASYLAN A (commercially available from Degussa Corporation, Parsippany, NJ). Specific examples of sol-gel alkoxysilane precursors containing a non-hydrolyzable substitute include, but are not limited to, dimethyldiethoxysilane (DMDEOS), n-octylmethyldiethoxysilane (OMDEOS) and hexadecyltriethoxysilane (HDTEOS), diethyldiethoxysilane, 1,1,3,3-tetraethoxy -1,3-dimethyldisiloxane or poly (diethoxysiloxane). [0049] [0049] Using the mixtures of the instant invention, the microcapsule particles are produced, with capsules composed of at least one metallic or semi-metallic inorganic oxide polymer, and at least one metallic or semi-metallic inorganic oxide polymer featuring a non-hydrolyzable substitute. Advantageously, the mixtures of the invention yield microcapsule particles in the range of 0.5 to 10 microns, which are less resistant to breakage compared to microcapsule particles produced by sol-gel reactions containing only a hydrolyzable sol-gel precursor . In this regard, instant microcapsule particles are more easily broken or broken by physical means (eg sonication or scrubbing) than microcapsule particles produced by sol-gel reactions containing only a hydrolyzable sol-gel precursor. The different physical property of the microcapsule particle prepared in accordance with the present teaching allows a person to construct and control the release property and the performance of the targeted delivery systems. [0050] [0050] As the results presented here show, the amount of non-hydrolyzable sol-gel precursor included in the instantaneous particles can be between 1% and 10%. In fact, the particle's performance in tissue evaluations was good when the level of non-hydrolyzable sol-gel precursor was present in up to 10%. However, it has been observed that on some occasions, amounts of non-hydrolyzable sol-gel precursor above 5% had an adverse effect on particle formation. Consequently, in particular applications of the present invention, the non-hydrolyzable sol-gel precursor is present in an amount of up to 5, 6, 7, 8, 9 or 10% of the total weight of the sol-gel precursor used in the reaction of sol- gel. As such, the result of the non-hydrolyzable polymer component of the microcapsule hull contains up to 10% of the non-hydrolyzable metallic or semi-metallic oxide polymer. In some configurations, the non-hydrolyzable sol-gel precursor is present in an amount between 0.1% and 10% of the total weight of the sol-gel precursor of the sol-gel reaction. In other configurations, the non-hydrolyzable sol-gel precursor is present in an amount between 0.5% and 10% of the total weight of the sol-gel precursor of the sol-gel reaction. In certain configurations, the non-hydrolyzable sol-gel precursor is present in an amount between 1% and 10% of the total weight of the sol-gel precursor of the sol-gel reaction. [0051] [0051] In addition, the wall thickness of the capsules can be controlled by varying the amount of monomer added. The proportion of monomers, such as TEOS, in relation to that of oil or aqueous liquid, can vary from approximately 2 to approximately 80 percentage weight, preferably from approximately 5 to approximately 60 percentage weight, more preferably from approximately 10 to approximately 50 percentage weight, even more preferably from about 15 to about 40 weight percent. [0052] [0052] The microcapsule particles of the present invention can be prepared by several methods. In one embodiment, the particles of the instant microcapsule are produced by emulsifying an oil or aqueous liquid, which optionally contains an active ingredient, and mixing that first emulsion with a mixture of a hydrolyzable sol-gel precursor and a non-hydrolyzable sol-gel precursor under appropriate conditions to form a sol-gel. In particular configurations, the mixture of sol-gel precursors is added slowly to this first emulsion, for example, by dripping. According to other configurations of this method, the mixture of sol-gel precursors is pure or alternatively prepared as a second emulsion. In this regard, one configuration is that of this method to describe the microcapsule particle production by emulsifying an oil or aqueous liquid, which optionally contains an active ingredient, and the mixing of this first emulsion, by dripping, with a pure mixture containing a precursor hydrolyzable sol-gel and a non-hydrolyzable sol-gel precursor under appropriate conditions to form a sol-gel. As is conventional in the art, a pure mixture means that the mixture is not diluted with a solvent or mixed with other substances. In yet other configurations of this method, the active ingredient is an oil fragrance, optionally mixed with an aqueous emulsifying solution before emulsification, and diluted with water before dripping to a second emulsion containing the sol-gel precursors under constant mixing. [0053] [0053] In another configuration, particles of the instant microcapsule are produced by emulsifying the active ingredient with the non-hydrolyzable sol-gel precursor, and mixing that first emulsion with a second emulsion containing the hydrolyzable sol-gel precursor under appropriate conditions to form a sol-gel. [0054] [0054] In yet another configuration, the particles of the instant microcapsule are produced by mixing an oil or aqueous liquid with a hydrolyzable sol-gel precursor and a non-hydrolyzable sol-gel precursor; cooling this first mixture until it reaches room temperature; adding an emulsifying solution at room temperature to the first mixture to produce a second mixture; homogenizing this second mixture to produce a homogenized mixture; and adding a defoamer to the homogenized mixture under appropriate conditions to form a sol-gel. [0055] [0055] Emulsions from instantaneous methods can be prepared using any conventional technique such as mechanical means (for example, homogenization with a high shear mixer), ultrasound or sonification and, in some configurations, the emulsions are diluted. In addition, any conventional sol-gel process can be employed in preparing the microcapsule particles of the invention. For example, the emulsions of the invention can be mixed with constant mixing and then allowed to cure at room temperature (i.e., 20 ° C to 25 ° C) until sol-gel capsules are formed. In other applications, the emulsions of the invention are mixed under constant mixing and allowed to cure at high temperature until sol-gel capsules are formed. For the purposes of the present invention, "high temperature" means a temperature in the range of 30 ° C to 70 ° C or, more particularly, 40 ° C to 60 ° C. In other configurations, the sol-gel mixture is cured at 50 ° C. In some configurations, the method may also include the use of an emulsifier, which is combined with one or more emulsions before homogenization. [0056] [0056] As is conventional in the art, an emulsifier is a substance that stabilizes an emulsion by increasing its kinetic stability. A class of emulsifiers is known as surfactants or surfactants. According to some embodiments of the invention, the emulsifier can be an anionic or cationic emulsifier. It is preferable that a cationic emulsifier is used to form the fragrance emulsion. When preparing the instant microcapsule particles, it is considered that more than one type of non-hydrolyzable and / or hydrolyzable precursor can be used. In addition, more than one type of active ingredient can be encapsulated in a single particle of the microcapsule. In addition, a personal care, therapeutic, cosmetic or cosmeceutical product of the invention may contain more than one type of microcapsule particle, characterized by the fact that each type of microcapsule particle contains a different mixture of non-hydrolyzable precursors and / or hydrolyzables and different active ingredients, thus facilitating the delivery of combinations of active ingredients, for example, with different release rates depending on the composition and characteristics of the microcapsule particles. [0057] [0057] In a particular embodiment of the invention, a surfactant or polymer is added to the microcapsule particle composition after the composition is newly cured. It was surprisingly found that this added component provides the capsule paste with robust physical stability and superior performance. Consequently, in some embodiments, the invention involves a composition that comprises a core formed from an oil or aqueous liquid containing at least one active ingredient; a capsule surrounding said core, characterized by the fact that said capsule is composed of at least one hydrolyzable metallic or semi-metallic oxide polymer; and a surfactant or polymer and a method for preparing said composition. An especially preferred class of surfactants are phosphate ester surfactants, such as olet-3-phosphate or olet10-phosphate, for example, the CRODAOS surfactant. See U.S. Patent No. 6,117,915. The surfactant can be added from 0.1 to 0.5% of the total weight of the capsule paste. Other phosphate ester surfactants such as STEPFAC 8180 and STEPFAC 818, available from Stepan Company; and phosphate ester surfactant ETHYLAN PS-121 and ETHYLAN PS-131 from Akzo Nobel Inc. In some configurations, the neutralized phosphate ester can be used. The surfactants contemplated for use in the present invention can be anionic, nonionic or cationic surfactants known in the art. [0058] [0058] In certain embodiments of this invention, the particle composition of the microcapsule is prepared in the presence of a defoamer. [0059] [0059] Products for personal, therapeutic, cosmetic or cosmeceutical care containing the particles of the instant microcapsule are also presented. In addition to the microcapsule particles of the invention, these products may also include an acceptable carrier. As used herein, an "acceptable carrier" refers to a carrier or diluent that does not cause significant irritation to an organism and that does not negate the biological activity and properties of the applied active ingredient. Examples of acceptable carriers that are useful in the context of the present invention include, without limitation, emulsions, creams, aqueous solutions, oils, ointments, pastes, gels, lotions, milks, foams, suspensions and powders. [0060] [0060] The acceptable carrier of the present invention may include, for example, a thickener, an emollient, an emulsifier, a humectant, a surfactant, a suspending agent, a film-forming agent, a foaming agent, a preservative, a defoaming agent, a fragrance, a lower monoalcoholic polyol, a solvent with a high boiling point, a propellant, a dye, a pigment or mixtures thereof. [0061] [0061] The nature of the microcapsule particles of the present invention and the ability to control that nature, as described herein, allows the design of compositions for various applications. In this regard, the active ingredient can be encapsulated alone or with other ingredients within the same microcapsule. Co-encapsulation of compounds that improve the stability of the sensitive ingredient is beneficial. For example, antioxidants can be co-encapsulated with oxygen- or oxidant-sensitive ingredients to provide "localized protection". Similarly, base-sensitive active ingredients can be co-encapsulated with proton donor compounds that can act as a local buffering source. Acid-sensitive active ingredients can be co-encapsulated with proton acceptors in order to protect them. Water-sensitive active ingredients can improve stability by encapsulating them as solutes in a hydrophobic, water-repellent oil. Co-encapsulation with sunscreen active ingredients, can protect compounds sensitive to light. Co-encapsulation of a sensitive ingredient and a protective ingredient in a microcapsule increases the effectiveness of the protective ingredient since both ingredients are wrapped together in the capsule. In addition, by building this organized system, the overall concentration of the protective ingredient, which is present in the composition, can be significantly reduced. [0062] [0062] As the encapsulation creates specific units within the entire formulation, an active ingredient can be encapsulated while a second active ingredient can be present in the carrier that surrounds the microcapsules as an unencapsulated active ingredient. This is advantageous when the ingredients work synergistically together, even if one is chemically reactive with the other. For example, benzoyl peroxide, retinoids and certain antibiotics are all beneficial for the treatment of acne, although they cannot be formulated together, as peroxide would oxidize the other active ingredients. Therefore, benzoyl peroxide or any other strong oxidizer can be encapsulated in microcapsules and other oxidation sensitive ingredient (s) may be present in the pharmaceutical carrier. [0063] [0063] In an additional configuration, combinations of different encapsulated assets can be combined in one system. Specifically, two separate fragrances can be encapsulated and then combined in the same system to provide a double effect of the fragrance on the final product. [0064] [0064] In accordance with the present invention, instant microcapsule microparticle compositions can be applied topically to a variety of surfaces to deliver the active ingredients to the particle core. For example, the particles of the instant microcapsule can be applied to substrates such as fabric, hair and hair during the washing and rinsing processes. Furthermore, it is intended that, once deposited, the capsules release the encapsulated fragrance by diffusion through the capsule wall, through small cracks or imperfections in the capsule wall caused by drying, physical or mechanical means, or by rupture in large scale of the capsule wall. [0065] [0065] In another configuration, the microcapsules of the present invention can be combined with different types of secondary microcapsules in the same product, such as friable microcapsules, activated by moisture and activated by heat. Friability refers to the propensity of microcapsules to break or break when subjected to direct external pressure or shear forces. For the purposes of the present invention, a microcapsule is "friable" if, when affixed to tissues treated in this way, the microcapsule can be disrupted by the forces encountered when tissues containing the capsule are manipulated by use or handled (thereby releasing the capsule contents). As defined herein, a heat-activated microcapsule is one that breaks with body heat and / or heat in a dryer and moisture-activated microcapsules are those that break when in contact with moisture. Non-limiting examples of additional microcapsules include microcapsules comprising wax, such as those described in U.S. Patent No. 5,246,603 and starch-based microcapsules also described in U.S. Patent No. 5,246,603. [0066] [0066] Secondary microcapsules of the types referenced above can be prepared using a variety of conventional methods known to those skilled in the art to produce capsules, such as interfacial polymerization and polycondensation. See, for example, U.S. Patent No. 3,516,941, U.S. Patent No. 4,520,142, U.S. Patent No. 4,528,226, U.S. Patent No. 4,681,806, U.S. Patent No. 4,145,184; GB 2,073,132; WO 99/17871; and Microencapsulation: Methods and Industrial Applications, Edited by Benita and Simon (Marcel Dekker, Inc. 1996). However, it was recognized that many variations with respect to materials and process steps are possible. Non-limiting examples of materials suitable for making the hull of the microcapsule include urea-formaldehyde, melamine-formaldehyde, phenol-formaldehyde, gelatin, gelatin / gum arabic mixture, polyurethane, polyamides, or combinations thereof. [0067] [0067] Useful materials for the hull include materials such as polyethylene, polyamide, polystyrene, polyisoprene, polycarbonate, polyester, polyacrylate, polyurea, polyurethane, polyolefin, polysaccharide, epoxy resins, vinyl polymers and mixtures thereof. Suitable hull materials include materials such as products from the reaction of one or more amines with one or more aldehydes, such as urea crosslinked with formaldehyde or gluteraldehyde, crosslinked melamine with formaldehyde; gelatin-polyphosphate coacervates optionally cross-linked with gluteraldehyde; gelatin-gum arabic coacervates; cross-linked silicone liquids; polyamine reacted with polyisocyanates and mixtures thereof. In one aspect, the hull material comprises melamine crosslinked with formaldehyde. [0068] [0068] According to a configuration of the invention, the instant microcapsule particle compositions are well suited for products intended for personal care and cleaning. The present invention is also suitable for cleaning products, which are understood to be those products applied for a certain period of time and then removed. Products suitable for this invention are common in areas such as laundry products and include detergent, fabric softeners and the like; as well as personal care products, which include shampoos, hair conditioners, liquid soaps, soaps, antiperspirants, deodorants and similar products. In one configuration, a roll-on antiperspirant personal care product is presented containing an effective amount of the microcapsule particle composition of the present invention. [0069] [0069] As described herein, the present invention is well suited for use in a variety of well-known consumer products such as laundry detergent and fabric softeners, liquid dishwashing detergents, automatic dishwashing detergents, as well as shampoos and hair conditioners. These products employ surfactant and emulsifying systems that are well known. For example, fabric softening systems are described in U.S. Patents N '=. 6,335,315, 5,674,832, 5,759,990, 5,877,145, 5,574,179; 5,562,849, 5,545,350, 5,545,340, 5,411,671, 5,403,499, 5,288,417, 4,767,547, 4,424,134. Liquid dishwashing detergents are described in Patents 6,069,122 and 5,990,065; automatic dishwashing detergents are described in U.S. Patents 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464, 5,703,034, 5,703. 030, 5,679,630, 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552 and 4,714,562. Liquid laundry detergents that can use the present invention include those systems described in U.S. Patent 5,929,022, 5,916,862, 5,731,278, 5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4,550,862, 4,537,707, 4,537,706, 4,515,705, 4,446,042 and 4,318,818. Shampoos and conditioners that can use the present invention include U.S. Patents 1 g 6,162,423, 5,968,286, 5,935,561, 5,932,203, 5,837,661, 5,776,443, 5,756,436, 5,661,118, 5,618 .523, 5,275,755, 5,085,857, 4,673,568, 4,387,090 and 4,705,681. [0070] [0070] In some configurations, the water in the microcapsule particle composition can be removed to provide a final product in powder form. In this regard, dry spray carriers can be used in instant compositions. Dry spray carriers include, but are not limited to, carbohydrates such as chemically modified starches and / or hydrolyzed starches, gums such as gum arabic, proteins such as wheat protein, cellulose derivatives, clays, polymers and / or soluble synthetic copolymers in water like polyvinyl pyrrolidone, polyvinyl alcohol. Dry spray carriers can be present in an amount of approximately 1% to approximately 50%, more preferably approximately 5% to approximately 20%. [0071] [0071] Optionally, a free flow agent (anti-caking agent) can be used. Free-flowing agents include silicas that can be hydrophobic (ie, silanol surface treated with halogen silanes, alkoxysilanes, silazanes, siloxanes, etc. such as SIPERNAT D17, AEROSIL R972 and R974 (available from Degussa, etc.) and / or hydrophilic such as AEROSIL 200, SIPERNAT 22S, SIPERNAT 50S (available from Degussa), SYLOID 244 (available from Grace Davison). Free flowing agents can be present from approximately 0.01% to approximately 10%, more preferably from 0.5% approximately 5%. [0072] [0072] Suitable wetting agents and viscosity control / suspension agents may additionally also be included and are disclosed in U.S. Patent Nos. $ 4,464,271, 4,446,032 and 6,930,078. Details of hydrophobic silicas, such as functional delivery vehicles for active materials, except the free flowing / anti-caking agent, are disclosed in U.S. Patents 1 1-2-5,500,223 and 6,608,017. [0073] [0073] In other embodiments of the present invention, the final composition or product may be in the form of an oil, gel, a solid stick, a lotion, a cream, a milk, an aerosol, a spray, a powder, a foam, a shampoo, hair conditioner, hairspray or makeup. [0074] [0074] In other configurations relating to spray dried microcapsule particle compositions, such compositions may include products such as laundry powder detergents, fabric softeners, dry towels for household cleaning, washing powder for dishes, floor cleaning cloths or any dry form of personal care products (eg powdered shampoo, conditioner, personal soap, deodorant powder, foot powder, washing powder, talc), etc. Due to the high concentration of fragrance and / or active agent in the spray dried products of the present invention, the characteristics of the dry consumer products mentioned above will not be adversely affected by a small dosage of the spray dried products. [0075] [0075] The invention is described in more detail by the following non-limiting examples. Example 1: Preparation of Silica Capsules with a Single Sol-Gel Precursor [0076] [0076] This example illustrates the preparation of silica capsules using a precursor where the central silicon atom is coordinated to four alkoxy groups. The empirical formula is Si (OR) 4, where -OR is an alkoxy group and is hydrolyzable by dispersion in water. In general, the method involves preparing a concentrated fragrance emulsification, diluting the fragrance emulsion to the desired concentration and adding TEOS. [0077] [0077] Preparation of Concentrated Fragrance Emulsion. Two hundred and six grams of fragrance oil were weighed and placed in a round-bottomed flask. In a separate flask, a 1.0% aqueous solution of surfactant (120 g) was prepared by dissolving the required amount of 30% cetyltrimethylammonium chloride (CTAC) in distilled water. The oil phase was then placed in the aqueous phase and the mixture was homogenized with a high shear mixer (Ultra Turrax T 25 Basic, IKA, Werke). Four drops of defoamer were added to suppress the foam generated. [0078] [0078] Preparation of the Diluted Fragrance Emulsion. The diluted fragrance emulsion was prepared by mixing the concentrated fragrance emulsion with the desired amount of water to generate the desired concentration. [0079] [0079] Preparation of Silica Capsules. The formation of silica capsules was achieved by adding a single precursor to the diluted fragrance emulsion. The amount of precursor added was routinely determined by the required level of polymer in the wall and was generally 1% to 30% of the final formulation. Typically, the desired amount of precursor, tetraethyl orthosilicate (TEOS) was weighed (35.91 g in this example) and placed in a clean, dry drip funnel. Then, TEOS was added by dripping into the fragrance emulsion diluted under constant mixing. The mixing speed was reduced once the addition of TEOS was completed. The system was maintained at room temperature and cured for an extended period of time. The pH of the system was maintained at approximately 3 to 4. The capsule formed was well dispersed and, in general, had a particle size ranging from submicron to 1,000 microns depending on the emulsifier and the shear rates used. Example 2: Making Silica Capsules Using a Mixture of Precursors [0080] [0080] This example illustrates the preparation of silica capsules using a mixture of precursors. The mixture was prepared using a mixture of precursors whose generic formulas can be represented as Si (OR) 4 and (R ') nSi (OR) m, where -R' is a non-hydrolyzable substitute and -OR is an alkoxy group that is hydrolyzable by dispersion in water and n + m = 4. In general, the method involved preparing a concentrated fragrance emulsification, diluting the fragrance emulsion to a desired concentration and adding TEOS. [0081] [0081] Preparation of Concentrated Fragrance Emulsion. The fragrance oil (234 g) was weighed and placed in a round bottom flask. In a separate flask, a 1.0% aqueous surfactant solution (135 g) was prepared by dissolving the required amount of 30% CTAC surfactant solution in distilled water. The oil phase was then placed in the aqueous phase and the mixture was homogenized with a high shear mixer (Ultra Turrax T 25 Basic, IKA, Werke). Four drops of defoamer were added to suppress the foam generated. [0082] [0082] Preparation of the Diluted Fragrance Emulsion. The diluted fragrance emulsion was prepared by mixing the concentrated fragrance emulsion with the desired amount of water to generate the desired concentration. [0083] [0083] Preparation of Silica Capsules. The amount of precursor added was routinely determined by the required level of polymer in the wall and varied from 1% to 30% of the final formulation. In general, the desired amount of precursor, TEOS (39.6 g in this example) and DMDEOS (0.42 g in this example), was weighed and placed in a clean, dry drip funnel. The mixture of precursors (99% TEOS and 1% DMDEOS) was then added by dripping to the diluted fragrance emulsion prepared in step two under constant mixing. Optionally, DMDEOS was added to the diluted fragrance emulsion and emulsified before adding TEOS. The mixing speed was reduced once the precursor addition had been completed. The system was maintained at room temperature and cured for an extended period of time. The pH of the system was maintained at approximately 3 to 4. The capsule formed was well dispersed and, in general, had a particle size ranging from submicron to one hundred microns depending on the emulsifier and the shear rates used. Example 3: Making Silica Capsules Using a Mixture of Precursors and High Temperature Curing [0084] [0084] This example illustrates the preparation of silica capsules using a mixture of precursors, where the capsules are subsequently cured under high temperature. The mixture was prepared using a mixture of precursors whose generic formulas can be represented as Si (OR) 4 and (R ') Si (OR) 3, where -R' is a non-hydrolyzable substitute and -OR is an alkoxy group that it is hydrolyzable by dispersion in water. In general, the method involved preparing a concentrated fragrance emulsification, diluting the fragrance emulsion to the desired concentration and adding TEOS. [0085] [0085] Preparation of Concentrated Fragrance Emulsion. The fragrance oil (144 g) was weighed and placed in a round bottom flask. In a separate flask, a 1.0% aqueous solution of surfactant (96 g) was prepared by dissolving the required amount of 30% CTAC surfactant solution in distilled water. The oil phase was then placed in the aqueous phase and the mixture was homogenized with a high shear mixer (Ultra Turrax T 25 Basic, IKA, Werke). Four drops of defoamer were added to suppress the foam generated. [0086] [0086] Preparation of the Diluted Fragrance Emulsion. The diluted fragrance emulsion was prepared by mixing the concentrated fragrance emulsion with the desired amount of water (144 g in this case, the pH of the water is 3.8) to generate the desired concentration. [0087] [0087] Preparation of Silica Capsules. The amount of precursor added was routinely determined by the required level of polymer in the wall and varied from 1% to 30% of the final formulation. In general, the desired amount of precursor, TEOS (26.73 g in this example) and DMDEOS (0.27 g in this example), was weighed and placed in a clean, dry drip funnel. The mixture of recursors (99% TEOS and 1% DMDEOS) was then added by dripping to the diluted fragrance emulsion prepared in step two under constant mixing. After the mixing was completed, it was heated to 50 ° C and held at 50 ° C for 2 hours before the samples were discharged. Example 4: Preparation of silica capsules using a mixture of precursors with increased amount of DMDEOS [0088] [0088] In order to determine the effect of the non-hydrolyzable sol-gel precursor on the microcapsule particle characteristics, various amounts of non-hydrolyzable sol-gel precursor were used in the sol-gel reaction. The procedure for preparing the microcapsule particles was carried out as described in Example 2. To prepare a mixture of 2% DMDEOS / 98% TEOS, 231 g of fragrance and 39.5 g and 0.8 g of TEOS and DMEOS, respectively. To prepare a mixture of 5% DMEOS / 95% TEOS, 231 g of fragrance and 38.3 g and 2.2 g of TEOS and DMDEOS, respectively, were used. [0089] [0089] Example 5: Characteristics of Capsules Prepared with Mixtures of Precursors [0090] [0090] The effect of adding a non-hydrolyzable sol-gel precursor (DMDEOS) to the hydrolyzable sol-gel precursor (TEOS) was determined by carrying out solvent extraction experiments, and by analyzing the particle size distribution and substantivity the skin. [0091] [0091] Solvent extraction. Posh Special fragrance capsules were produced with TEOS or a mixture of TEOS and DMDEOS and the solvent extraction of the fragrance from the capsules was subsequently measured. As shown in Table 1, repeated experiments showed that the capsules made with TEOS presented slightly more extractable oil than the samples with the mixture of TEOS and DMDEOS. TABLE 1 [0092] [0092] Subsequently, the amount of extractable oil from the capsules containing the fragrance Posh Special was determined as a function of the amount of DMDEOS in the capsules. As shown in Table 2, the capsules made with a mixture of TEOS and DMDEOS had less oil extractable with solvent than the capsules made only with TEOS in different levels of DMDEOS. However, it was observed that the results of solvent extraction experiments using the Posh Special fragrance were dependent on the batch since batch 2 of the capsule made only with TEOS presented less solvent extractable oil. TABLE 2 [0093] [0093] In order to determine whether the results of solvent extraction were fragrance dependent, similar experiments were carried out with capsules containing the Urban Legend fragrance, the Perfect Match fragrance or the Psychadelic Gourmand fragrance. As shown in Tables 3-5, the capsules made with a mixture of TEOS and DMDEOS had more extractable oil with solvent than the capsules made only with TEOS. TABLE 3 [0094] [0094] In general, the analysis of solvent extraction indicated that capsules made with a mixture of DMDEOS and TEOS had more extractable oil than capsules made only with TEOS. In addition, the amount of extractable oil depended on the fragrance. [0095] [0095] Particle Size Distribution. Particles of the microcapsule composed only of TEOS or with mixtures of DMDEOS and TEOS were repaired with various fragrances and particle size distribution and the resistance to breakage was analyzed by sonication. The results of this analysis are shown in Figures 1-3, which show the distribution of particles of Posh Special particles composed of TEOS and 0.5% DMDEOS (Figure 1C), Posh Special particles composed of TEOS and 0.75% DMDEOS (Figure 1D), Posh Special particles composed of TEOS and 1.0% DMDEOS (Figure 1E), Psychadelic Gourmand particles composed only of TEOS (Figure 2A), Psychadelic Gourmand particles composed of TEOS and 0.75 % of DMDEOS (Figure 2B), Urban Legend particles composed only of TEOS (Figure 3A), and Urban Legend particles composed of TEOS and 0.75% of DMDEOS (Figure 3B). Except in the case of Urban Legend, capsules made only with TEOS were more resistant to sonication than capsules made with a mixture of TEOS with DMDEOS at any level (see comparisons in Figures 4A and 4B), indicating that capsules made only with TEOS are more resistant to breakage. In this regard, it is possible to take advantage of the difference in physical properties of capsules prepared from the present invention to adjust the release properties of consumer delivery systems. [0096] [0096] Sensory Evaluation and Skin Analysis. One way of evaluating wear resistance is by determining the value of the substantivity of a composition (McNamara, et al. (1965) J. Soc. Cosmet. Chem. 16: 499-506). The value of the substantivity or percentage substantivity is the amount or percentage of the composition submitted to the test remaining on the skin following a standard physical interaction or wear procedure, which, in the present case, also fragments the particles of the instant microcapsule releasing the active ingredient. Figure 5 shows the results of the analysis of the substantivity to the skin of particles produced with TEOS containing between 0% and 10% of DMDEOS, which were cured at room temperature or at high temperature (50 ° C). [0097] [0097] An additional analysis comparing the TEOS particles from the microcapsule produced with (1%) or without DMDEOS and cured at room temperature indicated that DMDEOS improved the substantivity of the skin (Table 6). TABLE 6 [0098] [0098] Sensory Evaluation and Tissue Analysis. Figure 6 shows the results of the tissue evaluation (LYCRA) of the microcapsule particle prepared according to the present invention. All samples performed significantly better than the pure fragrance and had a strong post-rub intensity, indicating the release of the encapsulated fragrance under physical force. The greatest difference observed between post-scrub and pre-scrub in the evaluation of the tissue in comparison with that observed in the evaluation of the skin reflected the effect of the different substrates used. Example 6: Silica capsule with improved performance and physical stability [0099] [0099] This example illustrates the preparation of silica capsules using a mixture of precursors. The mixture was prepared using a mixture of precursors whose generic formulas can be represented as Si (OR) 4 and (R ') ,, Si (OR)., Where -R' is a non-hydrolyzable component and -OR is an alkoxy group that it is hydrolyzable by dispersion in water and n + m = 4. In general, the method involved preparing a concentrated fragrance emulsification, diluting the fragrance emulsion to a desired concentration and adding TEOS. [0100] [00100] Preparation of Concentrated Fragrance Emulsion. The fragrance oil (234 g) was weighed and placed in a round bottom flask. In a separate flask, a 1.0% aqueous surfactant solution (135 g) was prepared by dissolving the required amount of 30% CTAC surfactant solution in distilled water. The oil phase was then placed in the aqueous phase and the mixture was homogenized with a high shear mixer (Ultra Turrax T 25 Basic, IKA, Werke). Four drops of defoamer were added to suppress the foam generated. [0101] [00101] Preparation of the Diluted Fragrance Emulsion. The diluted fragrance emulsion was prepared by mixing the concentrated fragrance emulsion with the desired amount of water to generate the desired concentration. [0102] [00102] Preparation of Silica Capsules. The amount of precursor added was routinely determined by the required level of polymer in the wall and varied from 1% to 30% of the final formulation. In general, the desired amount of precursor, TEOS (39.6 g in this example) and DMDEOS (0.30 g in this example), was weighed and placed in a clean and dry drip funnel. The mixture of precursors (99% TEOS and 0.75% DMDEOS) was then added by dripping to the diluted fragrance emulsion prepared in step two under constant mixing. Optionally, DMDEOS was activated to the diluted and emulsified fragrance emulsion before the addition of TEOS. The mixing speed was reduced once the precursor addition had been completed. The mixture was kept at room temperature and cured for an extended period of time. The pH of the mixture was maintained at approximately 3 to 4. The capsule formed was well dispersed and, in general, had a particle size ranging from submicron to one hundred microns depending on the emulsifier and the shear rates used. [0103] [00103] Preparation of Silica Capsule Paste with Improved Stability. In order to improve stability, thirty grams of the capsule paste prepared above were weighed and 0.15 g of emulsifier CRODAFOS 010ASS- (RB) (olet-10-phosphate, a complex ester of phosphoric acid and cosmetic grade ethoxylated alcohol ; Croda, Edison, NJ) was added to it after CRODAFOS 010ASS- (RB) was gently heated to its liquid state. The mixture was stirred for approximately 30 minutes using a vertical IKA laboratory mixer until the surfactant is completely dissolved and homogeneous. [0104] [00104] Alternatively, a 10% solution of CRODAFOS 010a-SS- (RB) emulsifier was prepared by dissolving 10 grams of the material in 90 grams under heating. The stabilized paste of the capsule was prepared by mixing 570 grams of the fragrance capsule paste prepared above with 30 grams of the emulsifier solution CRODAFOS 010A-SS- (RB) 10% under consistent mixing for 30 minutes. [0105] [00105] Evaluation of the Stability of the Capsule by Microscopy. The stability of the capsules was assessed by diluting the paste with water. The diluted sample was placed on microscopic slides and monitored overnight. Microscopic analysis indicated that well-formed silica capsules were prepared as a fresh sample in water. A break in the capsules was observed after they were dried overnight on a microscopic slide. However, in general, the capsules maintained their structural integrity after drying for 3 days on a microscope slide. [0106] [00106] Evaluation of the Stability of the Capsule Paste. The stability of the paste was evaluated by aging the samples with and without the emulsifier CRODAFOS 010A-SS- (RB) over a period of 4 weeks and photographic images were taken to illustrate the stability of the samples. The results of this analysis indicated that no separation of the capsule paste prepared with the emulsifier CRODAFOS 010A-SS- (RB) was observed, while samples without the emulsifier CRODAFOS 010A-SS- (RB) exhibited significant separation, demonstrating the benefit of the phosphate ester. . Example 7: Sensory Performance of Antiperspirant Prepared with Silica Capsules Showing Improved Performance and Physical Stability [0107] [00107] The benefit of applying the capsules prepared with or without the emulsifier CRODAFOS 010A-SS- (RB) on the base of the antiperspirant (AP) roll-on has been determined. The fragrance capsule paste was prepared, where the silica precursor was a mixture of TEOS and DMDEOS. The fragrance used was an IFF Posh Special. The capsule paste was dispersed on an AP-roll base in an equivalent to 0.75% pure fragrance. The base typically contained 1 to 3% anionic surfactant, 10 to 20% aluminum hydrochloride, less than 1% silica, 1 to 2% Helianthus annuus and water. [0108] [00108] AP / DEO Sample Application (Roll-On). A technician applied 0.35 ml of the pre-measured roll on of a syringe directly to the upper forearm of the person using the fragrance. The roll on was then passed evenly over the skin by the technician using a clean glass stick. Eight arms were tested per sample using 15 trained judges. The judges rated the intensity of the product on the skin 5 hours after application under two conditions, before activation (pre-scrub) and again in the post-scrub condition. For the post-scrub assessment, each user gently rubbed the upper forearm up and down up to six times with two fingers. The judges smelled the upper part of the forearm when they evaluated the sample. The two-way analysis of variance was performed with the samples and panel members as independent variables and intensity as the dependent variable and, again, with the condition (pre and post) and panel members as independent variables and intensity as the dependent variable. A post-hoc analysis was performed using Duncan's Multiple Comparison with significance established at a 95% CI. The results of this analysis are shown in Table 7. TABLE 7 [0109] [00109] These results indicate that the capsule prepared with emulsifier CRODAFOS 010A-SS- (RB) had significantly higher post-rub intensity. The Ipós / Ipré ratio also increased by almost 40%. This can lead to a higher intensity perceived by the consumer, demonstrating the benefit of the instant invention. Example 8: Sensory Performance of Apple Fragrance Prepared with Silica Capsules Showing Improved Performance and Physical Stability [0110] [00110] This example illustrates the benefits and versatility of the present invention using another fragrance, that of Apple. The two fragrances, Posh Special and Apple have different physical properties. Capsules containing Apple fragrance were prepared using the procedure of Example 6 containing the surfactant CRODAFOS 010A-SS- (RB). The precursors used were only TEOS in one case and a mixture of TEOS / DMDEOS in another. The sensory results of these preparations are listed in Table 8. TABLE 8 [0111] [00111] This analysis indicated that the instant capsules can deliver significantly higher post-rub and Ipós / Ipré intensity in both cases compared to the pure fragrance. Example 9: Stability Improvements in Storage [0112] [00112] The samples prepared in Example 7 were also tested for stability at elevated temperature. The samples were aged at 50 ° C and the amount of oil leached from the fragrance was analyzed by gas chromatography sampling the concentration of the head space. The results of this analysis are shown in Table 9. TABLE 9 [0113] [00113] These results clearly established the excellent long-term stability of the capsules prepared by the present invention.
权利要求:
Claims (9) [0001] COMPOSITION OF MICROCAPULE PARTICLE, comprising: (a) a core formed from an oil or aqueous liquid containing at least one active ingredient; (b) a capsule encapsulating said nucleus, characterized by the fact that said capsule is composed of (i) at least one hydrolyzable metallic or semi-metallic oxide polymer, and (ii) at least one metallic or semi-metallic oxide polymer with a non-hydrolyzable substitute, wherein the polymer of (i) is formed from a silicon alkoxide selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate or tetrapopyl orthosilicate, and where the polymer of (ii) is present in an amount of up to 10% by weight total capsule and is formed from dimethyldiethoxysilane, n-octylmethyldiethoxysilane, hexadecyltriethoxysilane, diethyldiethoxysilane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane or poly (diethoxysiloxane); and (c) a surfactant or phosphate ester polymer. [0002] MICROCAPULE PARTICLE, according to claim 1, characterized by the fact that the at least one metallic or semi-metallic oxide polymer having a non-hydrolyzable substitute is dimethyldiethoxysilane, n-octylmethyldiethoxysilane or hexadecyltriethoxysilane. [0003] MICROCAPULE PARTICLE, according to claim 2, characterized by the fact that the phosphate ester is an olet-10-phosphate. [0004] MICROCAPULE PARTICLE, according to claim 3, characterized by the fact that the olet10-phosphate comprises up to 5% of the total particle composition of the microcapsule. [0005] MICROCAPULE PARTICLE, according to claim 3, characterized by the fact that the olet10-phosphate comprises up to 2% of the total particle composition of the microcapsule. [0006] MICROCAPULE PARTICLE, according to any one of claims 1 to 5, characterized by the fact that the active ingredient is a fragrance oil. [0007] MICROCAPULE PARTICLE, according to any one of claims 1 to 6, characterized by the fact that at least the metal or semi-metallic oxide polymer having a non-hydrolyzable substitute is dimethyldiethoxysilane. [0008] MICROCapsule particle according to any one of claims 1 to 7, characterized in that the polymer of (i) is formed from tetraethyl orthosilicate. [0009] PRODUCT FOR PERSONAL, THERAPEUTIC, COSMETIC OR COSMECEPTIC CARE, characterized by the fact that it comprises the microcapsule particle as defined in any one of claims 1 to 8.
类似技术:
公开号 | 公开日 | 专利标题 US20190076811A1|2019-03-14|Microcapsules produced from blended sol-gel precursors and method for producing the same US9532933B2|2017-01-03|Microcapsules containing active ingredients US20100143422A1|2010-06-10|Microcapsules Containing Active Ingredients EP2244689B1|2017-08-23|Deposition of lipophilic active material in surfactant containing compositions EP3210666B1|2021-02-03|High stability microcapsule product JP2018518479A|2018-07-12|Microcapsules with high deposits on the surface JP6598781B2|2019-10-30|Hybrid microcapsule US20070138672A1|2007-06-21|Process for preparing a high stability microcapsule product and method for using same EP1589092A1|2005-10-26|Stable Fragrance microcapsule suspension and process for using same US8974709B2|2015-03-10|Ceramic encapsulation with controlled layering by use of prehydrolyzed functionalized silanes BRPI0915934A2|2020-08-18|distribution particle BR112014013458B1|2020-09-24|MICROCAPULES, PROCESS OF PRODUCTION OF SUCH MICROCAPULES AND COMPOSITIONS USING SUCH MICROCAPULES KR20130029401A|2013-03-22|Capsule comprising active ingredient US20180272308A1|2018-09-27|Hybrid capsules CN107809994A|2018-03-16|Include the composition of multiple microcapsules colonies BR112021011942A2|2021-09-08|MICROCAPSULA, PROCESS FOR PREPARING A MICROCAPSULA COMPOSITION, MICROCAPSULA COMPOSITION, AND, CONSUMABLES US20120104638A1|2012-05-03|Ceramic Encapsulation By Use of One or More Silanes To Template Water Soluble Actives In A Water-In-Oil Emulsion US20120093899A1|2012-04-19|Process for Preparing a High Stability Microcapsule Product and Method for Using Same KR20220010734A|2022-01-26|Core-Shell Encapsulated Compositions Comprising Active Agents JP2021515794A|2021-06-24|Improvements in or with respect to organic compounds BR112020021814A2|2021-02-23|microcapsule composition, methods for preparing a microcapsule composition and for imparting a clean, fresh feel to a fabric product or hair care product, and, consumer product EP2911779B1|2018-12-12|Process BR112018016806B1|2021-11-16|COMPOSITION OF MICROCAPSULA, E, CONSUMER PRODUCTS
同族专利:
公开号 | 公开日 EP2500087B1|2018-10-10| MX2012003321A|2013-03-21| MX369325B|2019-11-05| BR102012006009A2|2013-07-02| EP2500087A3|2015-06-10| US10099194B2|2018-10-16| CN108465446A|2018-08-31| US20120237578A1|2012-09-20| US20190076811A1|2019-03-14| EP3444026A1|2019-02-20| CN102755868A|2012-10-31| EP2500087A2|2012-09-19|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US3516941A|1966-07-25|1970-06-23|Minnesota Mining & Mfg|Microcapsules and process of making| US4081384A|1975-07-21|1978-03-28|The Proctor & Gamble Company|Solvent-free capsules and fabric conditioning compositions containing same| US4145184A|1975-11-28|1979-03-20|The Procter & Gamble Company|Detergent composition containing encapsulated perfume| US4234627A|1977-02-04|1980-11-18|The Procter & Gamble Company|Fabric conditioning compositions| US4318818A|1979-11-09|1982-03-09|The Procter & Gamble Company|Stabilized aqueous enzyme composition| GB2073132B|1980-04-08|1983-12-14|Wiggins Teape Group Ltd|Production of microcapsules| US4387090A|1980-12-22|1983-06-07|The Procter & Gamble Company|Hair conditioning compositions| US4605554A|1981-06-19|1986-08-12|Ae Development Corporation|Roll-on application of aqueous microencapsulated products| US4428869A|1981-08-20|1984-01-31|International Flavors & Fragrances Inc.|Cologne consisting of microcapsule suspension| US4464271A|1981-08-20|1984-08-07|International Flavors & Fragrances Inc.|Liquid or solid fabric softener composition comprising microencapsulated fragrance suspension and process for preparing same| US4446032A|1981-08-20|1984-05-01|International Flavors & Fragrances Inc.|Liquid or solid fabric softener composition comprising microencapsulated fragrance suspension and process for preparing same| US4561998A|1982-05-24|1985-12-31|The Procter & Gamble Company|Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid| US4446042A|1982-10-18|1984-05-01|The Procter & Gamble Company|Brightener for detergents containing nonionic and cationic surfactants| US4534891A|1982-11-12|1985-08-13|International Flavors & Fragrances Inc.|Branched C13 -alk-1-en-5-ones and use thereof in perfumery| US4550862A|1982-11-17|1985-11-05|The Procter & Gamble Company|Liquid product pouring and measuring package with self draining feature| US4597898A|1982-12-23|1986-07-01|The Proctor & Gamble Company|Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties| US4424134A|1983-06-15|1984-01-03|The Procter & Gamble Company|Aqueous fabric softening compositions| US4528226A|1983-10-11|1985-07-09|Minnesota Mining And Manufacturing Co.|Stretchable microfragrance delivery article| US4515705A|1983-11-14|1985-05-07|The Procter & Gamble Company|Compositions containing odor purified proteolytic enzymes and perfumes| US4520142A|1984-02-17|1985-05-28|Minnesota Mining And Manufacturing Company|Aerosol application of encapsulated materials| AT45085T|1984-03-21|1989-08-15|Richardson Vicks Ltd|HAIR TREATMENT.| LU85303A1|1984-04-13|1985-11-27|Oreal|HAIR COMPOSITION AND METHOD FOR TREATING HAIR| US4537706A|1984-05-14|1985-08-27|The Procter & Gamble Company|Liquid detergents containing boric acid to stabilize enzymes| US4537707A|1984-05-14|1985-08-27|The Procter & Gamble Company|Liquid detergents containing boric acid and formate to stabilize enzymes| US4681806A|1986-02-13|1987-07-21|Minnesota Mining And Manufacturing Company|Particles containing releasable fill material and method of making same| GB2188653A|1986-04-02|1987-10-07|Procter & Gamble|Biodegradable fabric softeners| US5145842A|1986-06-11|1992-09-08|Alder Research Center Limited Partnership|Protein kinase c. modulators. d.| US4714562A|1987-03-06|1987-12-22|The Procter & Gamble Company|Automatic dishwasher detergent composition| US4968451A|1988-08-26|1990-11-06|The Procter & Gamble Company|Soil release agents having allyl-derived sulfonated end caps| CA2009047C|1989-02-27|1999-06-08|Daniel Wayne Michael|Microcapsules containing hydrophobic liquid core| US5169552A|1989-10-04|1992-12-08|The Procter & Gamble Company|Stable thickened liquid cleaning composition containing bleach| PH27596A|1989-12-04|1993-08-31|Unilever Nv|Hair treatment composition| FR2662175B1|1990-05-18|1994-05-13|Oreal|WASHING COMPOSITIONS BASED ON SILICONE AND FATTY ALCOHOLS WITH ETHER AND / OR THIOETHER OR SULFOXIDE GROUPS.| GB9021061D0|1990-09-27|1990-11-07|Unilever Plc|Encapsulating method and products containing encapsulated material| US5194639A|1990-09-28|1993-03-16|The Procter & Gamble Company|Preparation of polyhydroxy fatty acid amides in the presence of solvents| US5176903A|1990-12-13|1993-01-05|Revlon Consumer Products Corporation|Antiperspirant/deodorant containing microcapsules| FR2673179B1|1991-02-21|1993-06-11|Oreal|CERAMIDES, THEIR PREPARATION PROCESS AND THEIR APPLICATIONS IN COSMETICS AND DERMOPHARMACY.| US5246603A|1991-09-25|1993-09-21|Lever Brothers Company, Division Of Conopco, Inc.|Fragrance microcapsules for fabric conditioning| DE69333120T2|1992-05-12|2004-07-01|The Procter & Gamble Company, Cincinnati|Concentrated fabric softener compositions with biodegradable fabric softeners| AU4398793A|1992-06-15|1994-01-04|Procter & Gamble Company, The|Liquid laundry detergent compositions with silicone antifoam agent| US5288417A|1992-07-06|1994-02-22|Lever Brothers Company, Division Of Conopco, Inc.|Fabric conditioning compositions and process for making them| US5458809A|1992-07-15|1995-10-17|The Procter & Gamble Co.|Surfactant-containing dye transfer inhibiting compositions| EP0581753B1|1992-07-15|1998-12-09|The Procter & Gamble Company|Dye transfer inhibiting compositions comprising polymeric dispersing agents| EP0581752B1|1992-07-15|1998-12-09|The Procter & Gamble Company|Built dye transfer inhibiting compositions| US5458810A|1992-07-15|1995-10-17|The Procter & Gamble Co.|Enzymatic detergent compositions inhibiting dye transfer| FR2694895B1|1992-08-20|1994-11-10|Coletica|Process for the production of emulsion microparticles by modification of the chemical composition of the dispersed phase after emulsification.| FR2694894B1|1992-08-20|1994-11-10|Coletica|Use of a transacylation reaction between an esterified polysaccharide and a polyamine or polyhydroxylated substance for the manufacture of microparticles, process and composition.| DK0687291T4|1993-03-01|2005-12-05|Procter & Gamble|Concentrated, biodegradable, quaternary ammonium softener compositions and compounds containing unsaturated fatty acid chains with high iodine levels| FR2703927B1|1993-04-13|1995-07-13|Coletica|Use of a transacylation reaction between an esterified polysaccharide and a polyamine to form in an aqueous medium a membrane at least on the surface of gelled particles.| US5403499A|1993-04-19|1995-04-04|Lever Brothers Company, Division Of Conopco, Inc.|Concentrated fabric conditioning compositions| WO1995010591A1|1993-10-14|1995-04-20|The Procter & Gamble Company|Protease-containing cleaning compositions| US5466802A|1993-11-10|1995-11-14|The Procter & Gamble Company|Detergent compositions which provide dye transfer inhibition benefits| US5492870A|1994-04-13|1996-02-20|The Board Of Trustees Of The University Of Illinois|Hollow ceramic microspheres by sol-gel dehydration with improved control over size and morphology| FR2718961B1|1994-04-22|1996-06-21|Oreal|Compositions for washing and treating hair and skin based on ceramide and polymers with cationic groups.| PE6995A1|1994-05-25|1995-03-20|Procter & Gamble|COMPOSITION INCLUDING A PROPOXYLATED POLYKYLENE OAMINE POLYKYLENE OAMINE POLYMER AS DIRT SEPARATION AGENT| US5916862A|1995-06-20|1999-06-29|The Procter & Gamble Company|Detergent compositions containing amines and anionic surfactants| ZA959368B|1994-11-04|1996-01-01|Croda Inc|Fatty alcohol phosphate ester emulsifier compositions| US5968881A|1995-02-02|1999-10-19|The Procter & Gamble Company|Phosphate built automatic dishwashing compositions comprising catalysts| DE69608541T2|1995-02-02|2001-01-18|Procter & Gamble|MACHINE DISHWASHER COMPOSITIONS WITH COBALT CHELATE CATALYSTS| US5674832A|1995-04-27|1997-10-07|Witco Corporation|Cationic compositions containing diol and/or diol alkoxylate| WO1997000311A1|1995-06-16|1997-01-03|The Procter & Gamble Company|Bleach compositions comprising cobalt catalysts| US5597936A|1995-06-16|1997-01-28|The Procter & Gamble Company|Method for manufacturing cobalt catalysts| US5581005A|1995-06-16|1996-12-03|The Procter & Gamble Company|Method for manufacturing cobalt catalysts| ES2158320T3|1995-06-16|2001-09-01|Procter & Gamble|COMPOSITIONS FOR AUTOMATIC DISHWASHERS THAT INCLUDE COBALT CATALYSTS.| US5559261A|1995-07-27|1996-09-24|The Procter & Gamble Company|Method for manufacturing cobalt catalysts| US5929022A|1996-08-01|1999-07-27|The Procter & Gamble Company|Detergent compositions containing amine and specially selected perfumes| EP0859594B1|1995-10-16|2001-08-22|The Procter & Gamble Company|Conditioning shampoos containing polyalkylene glycol| US5703034A|1995-10-30|1997-12-30|The Procter & Gamble Company|Bleach catalyst particles| WO1997016517A1|1995-10-30|1997-05-09|The Procter & Gamble Company|Thickened, highly aqueous, cost effective liquid detergent compositions| CZ191598A3|1995-12-20|1998-11-11|The Procter & Gamble Company|Combined particles containing bleaching catalyst and enzyme, their composition and preparation as well as their incorporation into cleansing agent| US5776443A|1996-03-18|1998-07-07|Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.|Hair care compositions| AR006355A1|1996-03-22|1999-08-25|Procter & Gamble|BIODEGRADABLE SOFTENING ASSET AND CONTAINING COMPOSITION| US5756436A|1996-03-27|1998-05-26|The Procter & Gamble Company|Conditioning shampoo compositions containing select cationic conditioning polymers| US5935561A|1996-03-27|1999-08-10|Procter & Gamble Company|Conditioning shampoo compositions containing select hair conditioning agents| US5932203A|1996-03-27|1999-08-03|Proctor & Gamble Company|Conditioning shampoo compositions containing select hair conditioning esters| FR2751532B1|1996-07-23|1998-08-28|Oreal|WASHING AND CONDITIONING COMPOSITIONS BASED ON SILICONE AND DIALKYLETHER| US5914307A|1996-10-15|1999-06-22|The Procter & Gamble Company|Process for making a high density detergent composition via post drying mixing/densification| BR9713263A|1996-10-21|2000-10-24|Procter & Gamble|Concentrated fabric softener composition| US5759990A|1996-10-21|1998-06-02|The Procter & Gamble Company|Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor| US5990065A|1996-12-20|1999-11-23|The Procter & Gamble Company|Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution| WO1998028398A1|1996-12-23|1998-07-02|Quest International B.V.|Particles containing absorbed liquids and methods of making them| US6069122A|1997-06-16|2000-05-30|The Procter & Gamble Company|Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution| EP0966268B1|1997-07-15|2003-05-21|Coletica|Cross-linked plant protein particles, in particular microparticles or nanoparticles, preparation method and cosmetic, pharmaceutical or food compositions containing same| US5968286A|1997-10-03|1999-10-19|Helene Curtis, Inc.|Heat-mediated conditioning from shampoo and conditioner hair care compositions containing silicone| US6045835A|1997-10-08|2000-04-04|Givaudan Roure Sa|Method of encapsulating flavors and fragrances by controlled water transport into microcapsules| EP0934773B1|1998-02-06|2004-02-04|Seiwa Kasei Co., Ltd.|Microcapsule having a specific wall and method for producing the same| FR2780901B1|1998-07-09|2000-09-29|Coletica|PARTICLES, IN PARTICULAR MICRO- OR NANOPARTICLES OF CROSSLINKED MONOSACCHARIDES AND OLIGOSACCHARIDES, THEIR PREPARATION METHODS AND COSMETIC, PHARMACEUTICAL OR FOOD COMPOSITIONS CONTAINING THE SAME| EP1104287B9|1998-08-13|2012-12-19|Sol-Gel Technologies Ltd.|Method for the preparation of oxide microcapsules loaded with functional molecules and the products obtained thereof| FR2785199B1|1998-10-30|2001-01-05|Rhodia Chimie Sa|PROCESS FOR THE PREPARATION OF CAPSULES CONSISTING OF A CORE OF LIQUID ACTIVE MATERIAL SURROUNDED BY A MINERAL BARK| US6238650B1|1999-05-26|2001-05-29|Sol-Gel Technologies Ltd.|Sunscreen composition containing sol-gel microcapsules| BR0012673B1|1999-07-20|2011-01-25|encapsulated oil particle, process for its preparation, and granular cleaning composition or its component containing an encapsulated oil particle.| FI19991806A|1999-08-25|2001-02-26|Yli Urpo Antti|New compositions for controlled release of a biologically active substance, and their preparation| AUPQ573300A0|2000-02-21|2000-03-16|Australian Nuclear Science & Technology Organisation|Controlled release ceramic particles, compositions thereof, processes of preparation and methods of use| US6248703B1|2000-03-15|2001-06-19|Unilever Home & Personal Care Usa, Division Of Conopco, Inc.|Extruded soap and/or detergent bar compositions comprising encapsulated benefit agent| US7758888B2|2000-04-21|2010-07-20|Sol-Gel Technologies Ltd.|Composition exhibiting enhanced formulation stability and delivery of topical active ingredients| US6723359B2|2001-10-18|2004-04-20|Firmenich Sa|Spray-dried compositions and method for their preparation| GB0202853D0|2002-02-07|2002-03-27|Dow Corning|Encapsulation process and encapsulated compositions| US20040175404A1|2002-04-15|2004-09-09|Adi Shefer|Moisture triggered sealed release system| CA2482038A1|2002-04-22|2003-10-30|The Procter & Gamble Company|Shampoo containing a cationic guar derivative| US7147915B2|2003-03-06|2006-12-12|Seiko Epson Corporation|Microcapsule and its uses| JP4370111B2|2003-03-06|2009-11-25|日華化学株式会社|Hydrophilic treatment agent composition and hydrophilic protective film forming method| DE20305679U1|2003-04-07|2003-06-18|Igus Gmbh|cable management| KR100524820B1|2003-06-17|2005-10-31|한국화학연구원|A preparation method of silica microcapsule| US20050112152A1|2003-11-20|2005-05-26|Popplewell Lewis M.|Encapsulated materials| US20070190325A1|2003-12-04|2007-08-16|Katja Berg-Schultz|Microcapsules with uv filter activity and process for producing them| EP1781250A2|2004-05-25|2007-05-09|E-L Management Corp.|Novel color cosmetic compositions| GB2416524A|2004-07-24|2006-02-01|Dow Corning|Microcapsules with siloxane walls formed in situ| EP1627573A1|2004-08-20|2006-02-22|Firmenich Sa|A process for the incorporation of a flavor or fragrance ingredient or composition into a carbohydrate matrix| KR100880992B1|2005-05-10|2009-02-03|삼성전자주식회사|System and method for interworking between ims network and h.323 network| US9345667B2|2005-06-17|2016-05-24|Australian Nuclear Science And Technology Organisation|Particles having hydrophobic material therein| US20070078071A1|2005-09-30|2007-04-05|Kaiping Lee|Spray dry capsule products and methods for preparing and using same| WO2007099814A1|2006-03-02|2007-09-07|Kaneka Corporation|Process for production of hollow silicone fine particles| WO2007112356A2|2006-03-24|2007-10-04|University Of Florida Research Foundation, Inc.|Core-shell nanocapsules and applications thereof| EP2004772A1|2006-03-29|2008-12-24|Cargill Incorporated|Improved deicer composition| WO2008047248A2|2006-10-19|2008-04-24|L'oreal|Aqueous delivery system for water-insoluble materials| WO2008144734A1|2007-05-21|2008-11-27|Aquea Scientific Corporation|Highly charged microcapsules| EP2173315B1|2007-07-27|2014-09-03|Croda, Inc.|Use of phosphorous-containing surfactants as polymeric cationic compound deposition aids| EP2025364A1|2007-08-13|2009-02-18|Procter & Gamble International Operations SA.|Compositions comprising dye-loaded particles| GB0803538D0|2008-02-27|2008-04-02|Dow Corning|Deposition of lipophilic active material in surfactant containing compositions| US20100143422A1|2008-12-04|2010-06-10|Lewis Michael Popplewell|Microcapsules Containing Active Ingredients| EP2335818A1|2009-07-09|2011-06-22|Altachem Holdings NV|Leach-proof microcapsules, the method for preparation and use of leach-proof microcapsules| WO2011124706A1|2010-04-09|2011-10-13|Basf Se|In-situ sol-gel encapsulation of fragrances, perfumes or flavours| CN103140208A|2010-06-25|2013-06-05|奇华顿股份有限公司|Encapsulated compositions comprising aldehyde fragrance precursors| US9192548B2|2010-06-25|2015-11-24|CoLabs International Corporation|Ceramic encapsulation with controlled layering by use of functionalized silanes| BR102012006009B1|2011-03-18|2020-09-24|International Flavors & Fragrances Inc.|COMPOSITION OF MICROCAPULE PARTICLE, AND, PRODUCT FOR PERSONAL, THERAPEUTIC, COSMETIC OR COSMECHANICAL CARE| CN104039295A|2011-12-22|2014-09-10|奇华顿股份有限公司|Improvements in or relating to the encapsulation of perfumes|ES2658226T3|2013-10-18|2018-03-08|International Flavors & Fragrances Inc.|Fluid and stable formulation of silica capsules| CN104560398A|2013-10-18|2015-04-29|国际香料和香精公司|Hybrid fragrance encapsulate formulation and method for using the same| US9763861B2|2008-12-04|2017-09-19|International Flavors & Fragrances Inc.|Stable, flowable silica capsule formulation| BR102012006009B1|2011-03-18|2020-09-24|International Flavors & Fragrances Inc.|COMPOSITION OF MICROCAPULE PARTICLE, AND, PRODUCT FOR PERSONAL, THERAPEUTIC, COSMETIC OR COSMECHANICAL CARE| MX2014006040A|2011-12-07|2014-07-11|Givaudan Sa|Microcapsules, a process of making such microcapsules and compositions utilising such microcapsules.| US20130171216A1|2011-12-30|2013-07-04|L'oreal Usa Products, Inc.|Aqueous-based personal care product formula that combines friction-controlled fragrance encapsulation technology with a film forming compound| WO2014162311A1|2013-04-01|2014-10-09|Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd.|Adjustable sol-gel-based capsules comprising fragrances and aromas, and uses thereof| EP2826384A1|2013-07-16|2015-01-21|Evonik Industries AG|Method for drying biomass| WO2015055416A1|2013-10-15|2015-04-23|Unilever N.V.|Cosmetic composition with increased opacity| CN105636573B|2013-10-15|2020-02-28|荷兰联合利华有限公司|Cosmetic compositions with increased opacity| US10071029B2|2013-10-15|2018-09-11|Conopco, Inc.|Cosmetic composition with increased opacity| US9770608B2|2013-11-11|2017-09-26|International Flavors & Fragrances Inc.|Multi-capsule compositions| BR112016029721A2|2014-06-27|2017-08-22|Firmenich & Cie|hybrid perfume capsules| WO2016050559A1|2014-10-02|2016-04-07|Evonik Degussa Gmbh|Process for producing a pufa-containing feedstuff by extruding a pufa-containing biomass| BR112017006838B1|2014-10-02|2021-07-06|Evonik Operations Gmbh|PROCESS TO PRODUCE AN ANIMAL FOOD COMPRISING BIOMASS CONTAINING PUFFA, ANIMAL FOOD AND AN ANIMAL BREEDING METHOD| US9944887B2|2014-12-16|2018-04-17|Noxell Corporation|Coated microcapsules| WO2016100479A1|2014-12-16|2016-06-23|The Procter & Gamble Company|Coated microcapsules| BR112017012068B1|2014-12-16|2021-04-06|Noxell Corporation|CONSUMER PRODUCT PROVIDING DELAYED ASSET RELEASE| CN106999896B|2014-12-16|2020-10-30|诺赛尔股份有限公司|Coated microcapsules| CN107001979B|2014-12-16|2021-05-28|诺赛尔股份有限公司|Coated microcapsules| US11129776B2|2015-04-30|2021-09-28|Kpt Ltd.|Compositions for cosmetic raw material and methods for making the same| US11129363B2|2015-05-08|2021-09-28|The Florida International University Board Of Trustees|Polymer-based training aids and methods of use| US9732303B2|2016-01-06|2017-08-15|The Procter & Gamble Company|Microcapsules formed from phosphate esters and compositions containing same| US10154947B2|2016-01-06|2018-12-18|The Procter & Gamble Company|Antiperspirant composition| US9803157B2|2016-01-06|2017-10-31|The Procter & Gamble Company|Starch benefit agent delivery vehicle| US9730867B2|2016-01-06|2017-08-15|The Procter & Gamble Company|Methods of forming a slurry with microcapsules formed from phosphate esters| ES2876160T3|2016-03-18|2021-11-12|Int Flavors & Fragrances Inc|Silica microcapsules and methods to prepare them| EP3299083A1|2016-09-23|2018-03-28|Greenseal Research Ltd|Custom-tailored sol-gel derived matrixes for chemical immobilization| WO2018077570A1|2016-10-28|2018-05-03|Unilever N.V.|A personal care composition comprising particles| EP3535359B1|2016-11-03|2020-05-13|Unilever PLC|Laundry treatment compositions comprising perfume and silica microparticles| EP3641725A1|2017-06-23|2020-04-29|The Procter and Gamble Company|Composition and method for improving the appearance of skin| CN108887291A|2018-06-21|2018-11-27|同济大学|A kind of natural pyrethrin microcapsules and preparation method thereof| CN108739872A|2018-06-21|2018-11-06|同济大学|A kind of natural pyrethrin microcapsules and preparation method thereof| CN109170889B|2018-09-20|2021-09-28|浙江大学|Preparation method of honey pear fruit polyphenol microcapsules| EP3952648A1|2019-04-12|2022-02-16|International Flavors & Fragrances Inc.|Controlled release, biodegradable core-shell microcapsule compositions| CN113950315A|2019-04-12|2022-01-18|国际香料和香精公司|Consumer products with controlled release biodegradable core-shell microcapsule compositions| US10959933B1|2020-06-01|2021-03-30|The Procter & Gamble Company|Low pH skin care composition and methods of using the same| FR3112494A1|2020-07-16|2022-01-21|Lifescientis|Synthesis process by soft chemistry of micron particles|
法律状态:
2013-07-02| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention| 2017-10-10| B07D| Technical examination (opinion) related to article 229 of industrial property law| 2018-07-24| B07E| Notice of approval relating to section 229 industrial property law|Free format text: NOTIFICACAO DE ANUENCIA RELACIONADA COM O ART 229 DA LPI | 2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law| 2020-01-07| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: B01J 13/02 , B01J 13/18 , A61K 8/11 , A61K 9/50 Ipc: A61K 8/11 (2006.01), A61K 9/50 (1974.07), B01J 13/ | 2020-01-07| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure| 2020-04-22| B09A| Decision: intention to grant| 2020-09-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |
优先权:
[返回顶部]
申请号 | 申请日 | 专利标题 US201161453977P| true| 2011-03-18|2011-03-18| US61/453,977|2011-03-18| 相关专利
Sulfonates, polymers, resist compositions and patterning process
Washing machine
Washing machine
Device for fixture finishing and tension adjusting of membrane
Structure for Equipping Band in a Plane Cathode Ray Tube
Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
国家/地区
|