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    • 专利摘要:
    process for preparing a particle, particle obtained from the process, liquid composition, composition for home care or personal care and method of treating a substrate a process for preparing a particle, wherein the particle comprises: (a) a core comprising a hydrophobic beneficial agent; (b) an external crosslinked wrapper comprising a hydrophobically modified crosslinked polyvinyl alcohol, comprising a crosslinking agent, comprising a first dextran aldehyde with a molecular weight of 2,000 to 2,000,000 da; and (c) an inner polyamide shell, the shell comprising a polyamide, and the polyamide comprising an aromatic group; wherein the outer crosslinked wrapper is formed prior to the formation of the inner polyamide wrapper.
    公开号:BR112016001974B1
    申请号:R112016001974-1
    申请日:2014-07-28
    公开日:2021-04-06
    发明作者:Craig Warren Jones；Changxi Li；Xiaoyun Pan
    申请人:Unilever Ip Holdings B.V.；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to the distribution of particles that comprise beneficial agents for substrates, with processes for the manufacture of said particles and the manufacture and use of formulations that comprise them. The particles will be specifically described here with reference to clothing treatment compositions, but they have other, broader applications. BACKGROUND OF THE INVENTION
    [0002] [0002] Many home care and personal care formulations attempt to distribute beneficial agents to substrates, such as textiles, hard surfaces, hair and skin. Encapsulation of the particulate benefit agent has been proposed as a means of enhancing distribution. The encapsulation of perfumes has generated particular interest and activity in recent years.
    [0003] [0003] The leakage of the encapsulating particle benefit agent over time is a known problem for many encapsulators. the leak in the formulation in which the encapsulated particle was incorporated leads to instability problems, as well as performance problems. performance problems include not only the loss of perfume intensity, but also the loss of perfume delivery time.
    [0004] [0004] Encapsulants comprising polyamides are known in the art.
    [0005] [0005] WO 12/085864 (P&G) discloses a population of encapsulates, whose encapsulates comprise a wrapper and a core, said wrapper comprises a polyamide polymer that forms a wall that encapsulates said core, and said core comprises a perfume composition. The perfume composition comprises perfume raw materials with a ClogP of 2 to 4.5; the encapsulated has a diameter of 1 to 100 micrometers and a fracture resistance of 0.1 to 5 MPa.
    [0006] [0006] US4145184 (P&G) discloses a detergent composition comprising a laundry detergent composition comprising: (a) 2 to 95% of a surfactant selected from the group consisting of anionic, non-ionic, amphoteric surfactants and zwitterionics, and their mixtures; and (b) an effective amount of a perfume agent comprising a water-insoluble encapsulated perfume, friable microcapsules with an average size of 5 to 300 microns. The microcapsules have a polyamide shell wall material.
    [0007] [0007] WO 09/047745 (P&G) discloses a composition that comprises an encapsulated, comprising a core, comprising a beneficial agent and a wrapper that encapsulates at least said core, said encapsulated further comprising an density balance, said composition being a product to the consumer. The encapsulating benefit agent is selected from among perfumes, and the wrapper comprises polyamides.
    [0008] [0008] WO 11/056904 (P&G) discloses an encapsulate comprising a) a core comprising perfume and b) a wrapper comprising polyamides.
    [0009] [0009] Formaldehyde melamine capsules are known, but, disadvantageously, need to be used with a formaldehyde scavenger.
    [0010] [0010] US 2008 146478 (International Flavors and Fragrances Inc) discloses a microcapsule comprising an active material, a nanometer material and an encapsulating polymer. The encapsulating polymer is selected from the group consisting of a vinyl polymer, an acrylate polymer, an acrylamide acrylate copolymer, a melamine-formaldehyde polymer, a urea-formaldehyde polymer, and mixtures thereof, to form a fragrance encapsulated by polymer. See claims 1 and 2 and sections [0111] and [0113]
    [0011] [0011] US 2004 071742 (International Flavors and Fragrances Inc) describes a composition comprising: a fragrance material; said fragrance material encapsulated by a polymer to provide a fragrance encapsulated by polymer; the polymer encapsulated fragrance is still coated with a cationic polymer.
    [0012] [0012] US 2004 072719 (International Flavors and Fragrances Inc) describes a composition comprising: a fragrance material; said fragrance material encapsulated by a polymer to provide a fragrance encapsulated by polymer; the polymer encapsulated fragrance is still coated with a polyamine polymer.
    [0013] [0013] US 5 460 817 (Allied Colloids Ltd.) discloses a particulate composition comprising particles with an anhydrous core comprising (a) a solid matrix polymer and an active ingredient distributed throughout the solid matrix polymer and ( b) a coacervate polymer casing for external protection. The outer shell is formed by a cross-linked polymer (polyvinyl alcohol).
    [0014] [0014] WO 92/06672 (Revlon Inc.) discloses a microencapsulate comprising one or more antiperspirant salts encapsulated within a shell wall that is susceptible to osmotic, enzymatic, or electrolyte degradation or degradation due to solubility in water from the enclosure wall.
    [0015] [0015] It has now been determined that the improved particles comprise a crosslinked outer shell of mPVOH, produced with a crosslinking agent that comprises a mixture of dextrans with different molecular weights, and an inner shell that comprises a polyamide (which comprises an aromatic group) and a core that comprises a perfume. The use of the particles of the invention results in a significant improvement in the deposition efficiency and a corresponding perceptible increase to the consumer in the distribution of the benefit.
    [0016] [0016] Advantageously, the new capsules incorporate materials that are made substantially from renewable raw materials, which helps to reduce the environmental impact. BRIEF DESCRIPTION OF THE INVENTION
    [0017] (a) um núcleo que compreende um agente de benefício hidrofóbico; (b) um invólucro reticulado externo que compreende um álcool polivinílico reticulado hidrofobicamente modificado, que compreende um agente de reticulação, que compreende um primeiro aldeído dextrano com um peso molecular de 2.000 a 2.000.000 Da; e (c) um invólucro de poliamida interno, em que o invólucro compreende uma poliamida, e em que a poliamida compreende um grupo aromático; em que o invólucro reticulado externo é formado antes da formação do invólucro de poliamida interno.[0017] Consequently, in a first aspect, the present invention provides a process for the preparation of a particle, wherein the particle comprises: (a) a core that comprises a hydrophobic beneficial agent; (b) an external crosslinked wrapper comprising a hydrophobically modified crosslinked polyvinyl alcohol, comprising a crosslinking agent, comprising a first dextran aldehyde with a molecular weight of 2,000 to 2,000,000 Da; and (c) an inner polyamide shell, the shell comprising a polyamide, and the polyamide comprising an aromatic group; wherein the outer crosslinked wrapper is formed prior to the formation of the inner polyamide wrapper.
    [0018] (a) um núcleo que compreende um agente de benefício hidrofóbico; (b) um invólucro reticulado externo que compreende um álcool polivinílico reticulado hidrofobicamente modificado, que compreende um agente de reticulação, que compreende um primeiro aldeído dextrano com um peso molecular de 2.000 a 2.000.000 Da; e (c) um invólucro de poliamida interno, em que o invólucro compreende uma poliamida, e em que a poliamida compreende um grupo aromático; em que o invólucro reticulado externo é formado antes da formação do invólucro de poliamida interno.[0018] A second aspect of the invention provides a particle obtained from the process of the first aspect, wherein the particle comprises: (a) a core that comprises a hydrophobic beneficial agent; (b) an external crosslinked wrapper comprising a hydrophobically modified crosslinked polyvinyl alcohol, comprising a crosslinking agent, comprising a first dextran aldehyde with a molecular weight of 2,000 to 2,000,000 Da; and (c) an inner polyamide shell, the shell comprising a polyamide, and the polyamide comprising an aromatic group; wherein the outer crosslinked wrapper is formed prior to the formation of the inner polyamide wrapper.
    [0019] a) pelo menos um agente tensoativo selecionado entre agentes tensoativos aniônicos, catiônicos, não iônicos e zwiteriônicos; e b) um solvente, de preferência água. [0019] A third aspect provides a liquid composition which comprises the particle of the second aspect which further comprises: a) at least one surfactant selected from anionic, cationic, non-ionic and zwitterionic surfactants; and b) a solvent, preferably water.
    [0020] [0020] A fourth aspect of the present invention provides a composition for home care or personal care comprising at least one particle according to the second aspect of the invention, the composition being preferably a laundry detergent, fabric softener, deodorant, antiperspirant , shampoo, hair conditioner or skin care product or skin cleanser.
    [0021] [0021] A fifth aspect of the present invention provides a method of treating a substrate, preferably wherein the substrate is selected from material for skin, hair and / or textile, which includes the stage of treating the substrate with a composition that comprises particles according to the second aspect of the invention. DETAILED DESCRIPTION OF THE INVENTION
    [0022] [0022] So that the present invention can still be better understood, it will be further described below with reference to the specific embodiments of the invention and other preferred and / or optional features. All indicated values are in% by weight of the total composition, unless otherwise indicated.
    [0023] [0023] Except in operational and comparative examples, or when expressly stated to the contrary, all numbers in this description that indicate quantities or proportions of material or reaction conditions, physical properties of materials and / or use should be understood as modified by the expression " about".
    [0024] [0024] Whenever a characteristic is revealed in relation to a particular aspect of the invention (for example, a particle of the invention), said disclosure must also be considered in the application of any other aspect of the invention (for example, a process of the invention), mutatis mutandis. The particle
    [0025] [0025] The nucleus is typically formed in an internal region of the particle, and provides an immersion for the beneficial agent. The inner and outer "wrappers" protect the benefit agent and regulate the flow of the benefit agent in and out of the core. Particle size
    [0026] [0026] The person skilled in the art will know how to measure the particle size distribution of the capsules, for example, by using a Malvern Mastersizer 2000. Typically, the particle has an average diameter of less than 5 to 50 microns, preferably 10 to 40 microns, more preferably 25 to 35 and most preferably 30 microns. The core
    [0027] [0027] The core comprises one or more hydrophobic beneficial agents, preferably an organoleptic beneficial agent, for example, an aroma or fragrance (the terms "fragrance" and "perfume" are used here interchangeably). The benefit agent
    [0028] [0028] Various beneficial agents can be incorporated into the particles. When the end use of the particles is in connection with a system that contains a surfactant, any compatible benefit agent that can provide a benefit to a substrate that is treated with a surfactant composition can be used. Preferred benefit agents are in the laundry domain, for example, fabric benefit agents, and benefit agents that provide a benefit to a laundry and / or rinse medium. Alternatively, the benefit agents can provide a benefit related to the skin or hair. The advantages of the particles of the invention in the presence of surfactant are good retention of the beneficial agent in the storage of a formulation and controlled release of the beneficial agent during and after using the product.
    [0029] [0029] During the process of the invention, the hydrophobic benefiting agent is preferably emulsified by mPVOH. If the beneficial agent is solid, it must first be dissolved in oil before use.
    [0030] [0030] Preferred examples include flavors, fragrances, enzymes, antifoaming agents, fluorescent agents, shading dyes and / or pigments, conditioning agents (e.g. water-insoluble quaternary ammonium materials and / or silicon), sunscreens, ceramides , antioxidants, reducing agents, sequestrants, color care additives, polymers with corresponding densities, photobleaching agents, lubricants, unsaturated oils, emollients / moisturizers and antimicrobial agents, and the most preferred are fragrances and antimicrobial agents.
    [0031] [0031] Preferred antimicrobial agents include Triclosan ™, climbazole, octapirox, ketoconazole, zinc pyrithione and quaternary ammonium compounds.
    [0032] [0032] The preferred sunscreens and / or skin lightening agents are vitamin B3 compounds. Suitable vitamin B3 compounds are selected from niacin, niacinamide, nicotinyl alcohol, or their derivatives or salts. Other vitamins that act as skin lightening agents can advantageously be included in the skin lightening composition to provide additional skin lightening effects. They include vitamin B6, vitamin C, vitamin A or its precursors. Mixtures of vitamins can also be used in the composition of the invention. An especially preferred additional vitamin is vitamin B6. Other non-limiting examples of skin lightening agents useful here include adapalene, aloe extract, ammonium lactate, arbutin, azelaic acid, hydroxy-butyl-anisol, hydroxy-butyl-toluene, citrate esters, deoxyarbutin, derivatives of 1, 3 diphenyl-propane, 2,5-dihydroxyl-benzoic acid and its derivatives, 2- (4-acetoxyphenyl) -1,3-ditane, 2- (4-Hydroxylphenyl) -1,3-ditane, ellagic acid, gluco pyranosyl-1-ascorbate, gluconic acid, glycolic acid, green tea extract, 4-Hydroxy-5-methyl-3 [2H] -furanone, hydroquinone, 4-hydroxyanisole and its derivatives, derivatives of 4-hydroxy-benzoic acid , hydroxycaprylic acid, ascorbate, inositol, kojic acid, lactic acid, lemon extract, linoleic acid, ascorbyl magnesium phosphate, 5-octanoyl salicylic acid, derivatives of 2.4 resorcinol, derivatives of 3.5 resorcinol, salicylic acid, derivatives of 3,4,5 trihydroxybenzyl, and mixtures thereof.
    [0033] Preferred sunscreens useful in the present invention are 2-ethylhexyl-p-methoxycinnamate, butyl-methoxy-dibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl dimethyl-p-aminobenzoic acid and mixtures thereof. The particularly preferred sunscreen is chosen from 2-ethylhexyl-p-methoxycinnamate, 4-t-butyl-4'-methoxydibenzoylmethane or mixtures thereof. Other conventional sunscreen agents that are suitable for use in the compositions of the invention include 2-hydroxy-4-methoxybenzophenone, octyldimethyl-p-aminobenzoic acid, digaloyltrioleate, 2,2-dihydroxy-4-methoxybenzophenone, ethyl-4- (bis ( hydroxypropyl)) aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate, glyceryl-p-aminobenzoate, 3,3,5-trimethylcyclohexyl-salicylate, methylanthranylate, p-dimethyl-aminenzoic acid 2-ethylhexyl-p-dimethyl-amino-benzoate, 2-phenylbenzimidazole-5-sulfonic acid, 2- (p-dimethylaminophenyl) -5-sulfonic benzoxazoic acid and mixtures of these compounds.
    [0034] [0034] Preferred antioxidants include vitamin E, retinol, hydroxytoluene-based antioxidants, such as Irganox ™, or commercially available antioxidants, such as those in the Trollox ™ series.
    [0035] [0035] Perfume and fragrance materials (which include pro-fragrances) are a particularly preferred benefit agent.
    [0036] [0036] The pro-fragrance can be, for example, a food lipid. Food lipids typically contain structural units with pronounced hydrophobicity. Most lipids are derived from fatty acids. In these "acyl" lipids, fatty acids are predominantly present as esters, and include mono-, di-, triacyl glycerols, phospholipids, glycolipids, diol lipids, waxes, sterol esters and tocopherols. In their natural state, vegetable lipids comprise antioxidants to prevent their oxidation. Although they may be at least partly removed during the isolation of plant oils, some antioxidants may remain. These antioxidants may be pro-fragrances. In particular, carotenoids and related compounds, the which includes vitamin A, retinol, retinal, retinoic acid and provitamin A, are capable of being converted into aromatic species that include ionones, apricots and damscenones. canola, squalene, sunflower seed oil, wheat germ oil, almond oil, coconut oil, grape seed oil, rapeseed oil, castor oil, o corn oil, cottonseed oil, safflower oil, peanut oil, poppy seed oil, palm seed oil, rice bran oil, sesame oil, soybean oil, pumpkin seed oil, jojoba oil and mustard seed oil. The perfume components that are odorous materials are described in more detail below.
    [0037] [0037] The perfume is typically present in an amount of 10 to 85% by weight of the particle, preferably 15 to 75% by weight of the particle. The perfume has an appropriate molecular weight of 50 to 500 Dalton. Pro-fragrances can be of higher molecular weight, typically from 1 to 10 kD.
    [0038] [0038] The useful components of the perfume include materials of both natural and synthetic origin. They include individual compounds and mixtures. Specific examples of said compounds can be found in the current literature, for example, in Fenaroli’s Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, odorizing and / or flavoring consumer products, that is, to impart an odor and / or aroma or flavor to a traditionally perfumed or flavored product to the consumer, or to modify the odor and / or taste of said product to the consumer.
    [0039] [0039] Perfume, in this context, is not only a fully formulated product fragrance, but also the selected components of that fragrance, in particular those that are prone to loss, such as so-called "starting notes".
    [0040] [0040] The starting notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]). Well-known examples of starting notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. The starting notes typically comprise from 15 to 25% by weight of a perfume composition, and in embodiments of the invention that contain a higher level of starting notes it is anticipated that at least 20% by weight may be present in the particle.
    [0041] [0041] Typical perfume components which have an advantageous use in the embodiments of the present invention include those with a relatively low boiling point, preferably those with a boiling point below 300, preferably between 100 and 250 degrees Celsius.
    [0042] [0042] It is also advantageous to encapsulate perfume components that have a low LogP (that is, those that will be partitioned in water), preferably with a LogP less than 3.0. These relatively low boiling point and relatively low LogP materials have been called "delayed flowering" perfume ingredients and include the following materials:
    [0043] [0043] Allil Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisol, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Format, Benzyl Iso Valerate, Benzyl Propionate, Beta Hexenol Range, Camphor Gum, Laevo-Carvona , d-Carvona, Cinnamic Alcohol, Cinamil Formate, Cis-Jasmona, Cis-3-Hexenyl Acetate, Cumínic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Acet Acetate, Ethyl Amyl Ketone , Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenylacetate, Eucalyptol, Eugenol, Fenchil Acetate, Flower Acetate (Decenyl Acetate Tricycle), Fructene (Decenyl Propionate Tricycle), Geraniol, Hexenol, Hexenyl Acetate, Acetate Hexyl Forma, Hydrotropic Alcohol, Hydroxycitronal, Indone, Isoamyl Alcohol, Iso Mentona, Isopulegyl Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Format, Menthol, Methyl Acetphenone, Methyl Amyl Ketone, Methyl Amyl Ketone, Methyl Amyl Ketone Methyl nzoate, Methyl-Benzylic Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptin Carbonate, Methyl Heptyl Ketone, Methyl Hexyl Ketone, Methyl-Phenyl-Carbinyl Acetate, Methyl Salicylate, Methyl-N-Methyl Anthranylate, Nerol , Octalactone, Octyl Alcohol, p-Cresol, Methyl Ether p-Cresol, p-Methoxy Acetophenone, p-Methyl Acetophenone, Phenoxy Ethanol, Phenyl Acetaldehyde, Phenylethyl Acetate, Phenylethyl Alcohol, Phenyl Ethyl Dimethyl Carbinyl, Pren Acetate Propyl Bornate, Pulegona, Rosa Oxide, Safrole, 4-Terpinenol, Alpha-Terpinenol, and / or Viridine.
    [0044] [0044] It is common for a plurality of perfume components to be present in a formulation. In the encapsulates of the present invention, it is envisaged that there may be four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components from the given list of delayed-flowering perfumes indicated above in the particles.
    [0045] [0045] Another group of perfumes with which the present invention can be applied is that of the so-called "aromatherapy" materials. They include many components used also in perfumery, which include the components of essential oils, such as sage, eucalyptus, geranium, lavender, apple extract, neroli, nutmeg, mint, sweet violet and valerian leaves. By means of the present invention, these materials can be transferred to textile articles that will be used or will otherwise come into contact with the human body (such as scarves and bedding). The inner casing
    [0046] [0046] The inner shell comprises a polyamide which comprises an aromatic group.
    [0047] [0047] The polyamide polymer can comprise at least one water-miscible monomer and one water-immiscible organic monomer.
    [0048] [0048] The water-miscible monomer can comprise a material selected from the group consisting of a diamine, a triamine and mixtures thereof. The diamines and triamines themselves can be selected from the group consisting of diethylene triamine, hexamethylene diamine, ethylene diamine and mixtures thereof.
    [0049] [0049] The water-immiscible organic monomer can be selected from the group consisting of diacyl chlorides, triacyl chlorides and their mixtures. Diacila chlorides can be selected from the group consisting of sebacoyl dichloride, adipoyl dichloride, and mixtures thereof, and said triacyl chlorides can be selected from the group consisting of teraftaloyl chloride, trimesoyl chloride, acetyl chloride, benzoyl chloride, 1, 3, 5-benzentricarbonyl chloride and mixtures thereof.
    [0050] [0050] In one embodiment, said polyamide polymer can comprise two or more water-miscible monomers. The outer casing
    [0051] [0051] The outer shell comprises a dextran aldehyde (also referred to herein as the "first dextran aldehyde") with a molecular weight of 2,000 to 2,000,000 Da, preferably 5,000 to 1,000,000 Da, even more preferably 10,000 to 500,000 Da, even more preferably from 15,000 to 250,000 Da.
    [0052] [0052] In a preferred embodiment, the outer shell further comprises a second dextran aldehyde with a molecular weight of more than 50,000 to 2,000,000 Da, preferably from 75,000 to 1,000,000 Da, still more preferably from 100,000 to 500,000 Da, still more preferably 150,000 to 300,000 Da, more preferably 200,000 Da. In this embodiment, it is preferred that the first dextran aldehyde has a molecular weight of 2,000 to 50,000 Da, preferably 5,000 to 30,000 Da, even more preferably 10,000 to 25,000 Da, still more preferably 15,000 to 22,000 Da, more preferably 20,000 Da. In this embodiment, the preferred weight / weight ratio of the second dextran aldehyde to the first dextran aldehyde is suitably in the range of 0.1 to 10, preferably 0.5 to 5 , and more preferably from 1 to 2.
    [0053] [0053] Dextran is a glucan linked to α-D-1,6-glucose with side chains 1-3 attached to the units of the main structure of dextran. Typically, the degree of branching is approximately 5%. The branches are mainly 1 to 2 glucose units in length. It is surprising that an alpha 1-6 polysaccharide must show any affinity for both cellulose and polyester.
    [0054] [0054] Dextran aldehyde materials must contain 2 or more aldehyde groups, in order to form cross-linked.
    [0055] [0055] Dextran aldehyde is advantageously used in an amount of 2.0 to 5.0% by weight, preferably from 2.8 to 3.0% by weight, which results in regular and uniform capsules.
    [0056] [0056] The total amount of dextran aldehyde is preferably from 0.5 to 5.0% by weight, more preferably from 1.0 to 3.5% by weight, more preferably from 2.0 to 3.0% by weight weight, by total particle weight. MPVOH (modified polyvinyl alcohol)
    [0057] [0057] It has been found that the amount of mPVOH influences the preparation of the capsule. Uniform and regular capsules can only be obtained in adequate concentrations of mPVOH.
    [0058] [0058] The preferred concentration of mPVOH for the preparation of the capsules of the present invention is in the range of 0.01 to 3% by weight, more preferably from 0.05 to 2% by weight, more preferably from 0.4 to 0, 6% by weight, by weight of the mPVOH solution.
    [0059] [0059] Below this amount, the drop of perfume has not been fully emulsified. In amounts greater than this, the resulting capsules became aggregated due to the greater likelihood of cross-linking between the capsules.
    [0060] [0060] PVOH (precursor material), which has a degree of hydrolysis of 60 to 99%, reacts first with a derivatization material, such as butyraldehyde, to give rise to mPVOH.
    [0061] [0061] mPVOH comprises an alkyl chain, generally between C3 and C18. Hydrocarbon chains longer than 22 are undesirable, since the precursor material from which the derivatization group is obtained reacts poorly or does not react with the polymeric backbone.
    [0062] [0062] The hydrocarbyl chain length of the original function in the precursor material from which the derivatization group is obtained is preferably from 4 to 22, more preferably from 5 to 20.
    [0063] [0063] In this context, the number of carbon atoms in the hydrocarbyl group includes any carbon in the chain attached to any other functional group within the derivatization material. For example, butyraldehyde has a hydrocarbyl chain length of 4.
    [0064] [0064] The derivatization material is preferably present in the polymer at a level of 0.1 to 40% by weight, based on the total weight of the polymer, more preferably from 2 to 30%, more preferably from 5 to 15%, for example, 8 to 12%.
    [0065] [0065] When the polymeric main structure is based on PVOH, the derivatization material is preferably present at a level such that the numerical ratio between the derived groups and the free hydroxyl pairs in the main structure is from 1: 3 to 1: 30, more preferably from 1: 4 to 1:20, more preferably from 1: 7 to 1:15, for example, from 1: 8 to 1:13.
    [0066] The preferred polyvinyl alcohol-based polymers for use here have an average molecular weight of 1,000 to 300,000, preferably 2,000 to 100,000, and more preferably 2,000 to 75,000. Hydrolysis, or alcohololysis, is defined as the percentage of reaction complexion in which the acetate groups in the resin are replaced by the hydroxyl groups, -OH. A hydrolysis range of 60 to 99% PVOH-based film-forming resin is preferred, while a more preferred hydrolysis range is about 88 to 99%. As used in this application, the term "PVOH" includes polyvinyl acetate compounds with the levels of hydrolysis disclosed herein.
    [0067] [0067] Preferred PVOH polymers preferably have an average degree of saponification in the range of 70 to 99%, and a viscosity as a 7% solution in the range of 100 to 5000 mPa.s at room temperature, measured in a shear rate of 20s-1.
    [0068] [0068] All of the above polymers include the polymer classes mentioned above, either as simple polymers or as copolymers formed by monomeric units or as copolymers formed by monomeric units derived from the specified class or as copolymers in which the monomeric units are copolymerized with one or more comonomer units.
    [0069] [0069] A particularly preferred polymer for use in the present invention is represented by the formula:
    [0070] [0070] More preferably, R is an alkyl group with 3 to 6 carbon atoms. Most preferably, R is C3H7. Deposition aids:
    [0071] [0071] The particle optionally comprises a deposition aid. In particularly preferred embodiments, the deposition aid is substantive to surfaces of proteinaceous material, cellulose, polyester, lipid or polyamide. By using said deposition aid, the efficiency of distribution to a specific substrate can be enhanced.
    [0072] [0072] The deposition aids modify the properties of the particle's exterior. A particular benefit that can be obtained with these materials is to leave the particles more substantive for a desired substrate. The desired substrates include cellulosic materials (including cotton), polyesters (including those used in the manufacture of polyester fabrics) and substrates that contain proteins (such as skin and hair). The deposition aids are preferably selected from substantive polymers to the non-hydrolyzable substrate, substantive polymers to the hydrolyzable substrate and substantive polyester polymers.
    [0073] [0073] Preferred polysaccharide polymers, whether hydrolyzable or not, can be derived from a wide variety of polysaccharides. Preferably, the polysaccharide is selected from the group consisting of: tamarind gum (preferably consisting of xyloglucan polymers), guar gum, locust bean gum (preferably consisting of galactomannan polymers), and other industrial gums and polymers which include, among others, Tara, fenugreek, aloe, chia, flaxseed, Psyllium seed, quince seed, xanthan, gelano, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophilan, chitin, hydroxyalkylcellulose, arabinan ( preferably beet), debranched arabinan (preferably beet), arabinoxylan (preferably rye and wheat flour), galactan (preferably lupine and potatoes), pectic galactan (preferably potato), galactomannan (preferably locust bean, and even low and high viscosities), glucomannan, lichen (preferably Icelandic moss), mannan (preferably ivory nuts), pachyman, ramnogalacturonan, acacia gum, agar, alginates, carrageenan, chitosan, clavan, hyaluronic acid, heparin, inulin, cellodextrins, cellulose, cellulose derivatives and mixtures thereof.
    [0074] Preferred non-hydrolyzable substantive deposition aids to the substrate include non-hydrolyzable polysaccharides. The preferred polysaccharide for cotton substantivity has, for example, a main structure with ß-1,4 bond.
    [0075] [0075] Preferably, the polysaccharide is a cellulose, a cellulose derivative, or other ß-1,4 linked polysaccharide with affinity for cellulose, such as polymanane, polyglucan, polyglucomann, polyoxyloglucan and polygalactomannan, or a mixture thereof. More preferably, the polysaccharide is selected from the group consisting of polyoxyloglucan and polygalactomannan. More preferably, the deposition aid is locust bean gum, xyloglucan, guar gum or mixtures thereof.
    [0076] Preferred substantive deposition aids to the hydrolyzable substrate include hydrolyzable polysaccharides. They comprise a polysaccharide that has been modified to become more soluble in water by means of a group covalently linked to the polysaccharide by means of hydrolyzable bond. Preferred groups can, for example, be selected independently of one or more from the groups acetate, propanoate, trifluoroacetate, 2- (2-hydroxy-1-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate, cinnamate, format , salicylate, carbamate, methylcarbamate, benzoate, gluconate, methanesulfonate, toluene, sulfonate, and hemiester groups of fumaric acid, malonic acid, itaconic acid, oxalic acid, maleic acid, succinic acid, tartaric acid, aspartic acid, glutamic acid, and malic acid.
    [0077] [0077] Mono-cellulose acetate is preferred among the so-called hydrolyzable deposition aids for the substantivity of cotton.
    [0078] Suitable and preferred substantive polyester deposition aids include phthalate-containing polymers, more preferably a polymer with one or more non-ionic hydrophilic components comprising oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene segments, and one or more hydrophobic components that comprise the terephthalate segments. Typically, the oxyalkylene segments of these deposition aids will have a degree of polymerization from 1 to about 400, although higher levels can be used, preferably from 100 to about 350, more preferably from 200 to about 300.
    [0079] [0079] A preferred type of deposition aid is a copolymer with random blocks of ethylene terephthalate and polyethylene oxide terephthalate.
    [0080] [0080] Another preferred polymeric deposition aid is polyester with repeated units of ethylene terephthalate units which contain 10 to 15% by weight of ethylene terephthalate units with 90 to 80% by weight of polyoxyethylene terephthalate units, derived from an average molecular weight polyethylene glycol from 0.2kD to 40kD. Examples of this class of polymer include the commercially available materials ZELCON 5126 (from DuPont) and MILEASE T (from ICI). Examples of related polymers can be found in US 4702857.
    [0081] Another preferred polymeric deposition aid is a sulfonated product of a substantially linear ester oligomer comprising a terephthaloyl oligomer ester backbone and oxyalkyleneoxy repeating units and terminal fractions covalently attached to the backbone. These dirt release agents are fully described in US 4968451. Other suitable polymeric dirt release agents include the terephthalate polyesters of US 4711730, the anionic treated oligomeric esters of US 4721580 and the block polyester oligomeric compounds of US 4702857.
    [0082] [0082] Preferred polymeric deposition aids also include the dirt release agents of US 4877896, which discloses anionic treated terephthalate esters, especially sulfoarolyl.
    [0083] [0083] Yet another preferred deposition aid is an oligomer with repeated units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form the main structure of the oligomer and are preferably terminated with treated modified isethionate. A particularly preferred deposition aid of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethylenoxy and oxy-1,2-propylenoxy units in a ratio of about 1.7 to about 1.8, and two treated units of 2- Sodium (2-hydroxyethoxy) -ethanesulfonate. Said dirt release agent also comprises from about 0.5% to about 20% by weight of the oligomer, of a crystalline reduction stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures.
    [0084] [0084] The deposition aid can be linear or branched. The preferred molecular weight of the polymeric deposition aid is in the range of about 5 kD to about 500 kD, preferably 10 kD to 500 kD, more preferably 20 kD to 300 kD.
    [0085] [0085] Preferably, the auxiliary deposition polymer is present at levels such that the solids of polymeric particles are in the range of 1: 500 to 3: 1, preferably 1: 200 to 1: 3. PREPARATION METHODS:
    [0086] [0086] The beneficial agent can be present in the reaction mixture at one level to give the levels of the beneficial agent in the resulting particles at the levels revealed above, although it is also possible to form "empty" particles (with or without an agent carrier) of benefit, for example, wax) and subsequently expose them to a benefit agent that can be adsorbed in the inner region.
    [0087] [0087] Deposition aids are usually added to the aqueous phase at the end of the process, in which, for example, other monomers can be added to form yet another shell material and bond additional materials to the exterior of the particle.
    [0088] [0088] The deposition aid can be added at the end of the later phase (preferably after cooling) when, for example, other shell forming material (for example, an acrylate monomer) is also added to turn on the deposition aid. deposition on the external surface of the particle by the formation of another wrapping material that retains a portion of the deposition aid and leads to a "hairy" particle in which the "hair" comprises the deposition aid.
    [0089] [0089] For single core-coating particles, the core that excludes the beneficial agent is less than or equal to 95% by weight, and the wrapper is generally 5% by weight or more of the particle mass. Particularly preferred achievements:
    [0090] [0090] It is particularly preferred that the above particle comprises a fragrance contained in the core, surrounded by an envelope and / or adsorbed on a carrier material, for example, a mineral oil, which is surrounded by the envelope and / or a deposition aid. polysaccharide external to the shell. Particularly preferred particles have a particle size of 5 to 50 microns. Use in products:
    [0091] [0091] The final product compositions of the invention can be in any physical form, for example, a solid such as a powder or granules, a tablet, a solid bar, a paste, a gel or liquid and, especially, a base liquid watery.
    [0092] [0092] The particles of the invention can advantageously be incorporated into compositions containing a surfactant and, in particular, into laundry and personal care compositions. The particles are normally included in said compositions at levels of 0.001% to 10%, preferably between 0.005% and 7.55%, more preferably from 0.01% to 5% by weight of the total composition.
    [0093] [0093] For laundry applications, an active ingredient in the compositions is preferably a surfactant or a fabric conditioning agent.
    [0094] [0094] More than one active ingredient can be included. For some applications, a mixture of active ingredients can be used.
    [0095] [0095] Preferably, at least one, for example, from 2 to 4 surfactants selected from anionic, cationic, non-ionic and zwitterionic surfactants is present.
    [0096] [0096] Compositions formulated which comprise the particles of the invention may contain a surfactant compound (surfactant) that can be chosen from anionic, cationic, non-ionic, amphoteric, zwitterionic and non-soap surfactants and mixtures thereof. Many suitable surfactant compounds are available and are fully described in the literature, for example, in “Surface-Active Agents and Detergents”, Volumes I and II, by Schwartz, Perry and Berch. The preferred surfactant compounds that can be used are anionic and non-ionic soap and non-synthetic soap compounds.
    [0097] [0097] The compositions of the invention may contain linear alkylbenzene sulfonate, in particular linear alkylbenzene sulfonates with an alkyl chain length of C8 to C15. It is preferred that the linear alkylbenzene sulfonate level is from 0% by weight to 30% by weight, more preferably from 1% by weight to 25% by weight, more preferably from 2% by weight to 15% by weight of the total composition.
    [0098] [0098] The compositions may contain other anionic surfactants in quantities in addition to the percentages mentioned above. Suitable anionic surfactants are well known to those skilled in the art. Examples include primary and secondary alkyl sulfates, in particular primary C8 to C15 alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and sulfonates of fatty acid esters. Sodium salts are generally preferred.
    [0099] [0099] The compositions can also contain non-ionic surfactant. Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, in particular ethoxylated C8 to C20 aliphatic alcohols with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially those primary and secondary C10 to C15 ethoxylated aliphatic alcohols with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide).
    [0100] [0100] It is preferred that the level of nonionic surfactant is from 0% by weight to 30% by weight, preferably from 1% by weight to 25% by weight, more preferably from 2% by weight to 15% by weight , by weight of a fully formulated composition comprising the particles of the invention.
    [0101] [0101] Any conventional tissue conditioning agent can be used. Conditioning agents can be cationic or non-ionic. If the fabric conditioning compound is used in a main washing detergent composition, the compound will typically be non-ionic. For use in the rinse phase, they will normally be cationic. They can be used, for example, in amounts from 0.5% by weight to 35% by weight, preferably from 1% by weight to 30% by weight, more preferably from 3% by weight to 25% by weight of a fully formulated composition comprising the particles of the invention.
    [0102] [0102] Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials that comprise a single long alkyl or alkenyl chain with an average chain length equal to or greater than C20 or, more preferably, compounds comprising a polar head group and two alkyl or alkenyl chains with an average chain length equal to or greater than C14. Preferably, the fabric softening compounds have two long chain alkyl or alkenyl chains, each having an average chain length greater than or equal to C16. More preferably, at least 50% of the long chain alkyl or alkenyl groups have a chain length of C18 or greater. It is preferred that the alkyl or alkenyl long chain groups of the fabric softening compound are predominantly linear.
    [0103] [0103] Quaternary ammonium compounds with two long chain aliphatic groups, for example, distearyldimethyl ammonium chloride and di (hydrogenated tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioning compositions. Other examples of these cationic compounds are found in "Surfactants Science Series" Volume 34 ed. Richmond 1990, Volume 37 ed. Rubingh 1991 and volume 53 eds. Cross and Singer 1994, Marcel Dekker Inc. New York ".
    [0104] [0104] Fabric softening compounds are preferably compounds that provide excellent softening and are characterized by a chain that melts Lβ to La at a transition temperature above 25 degrees Celsius, preferably above 35 degrees Celsius, more preferably above 45 degrees Celsius. This transition from Lβ to La can be measured by differential scanning calorimetry, as defined in "Handbook of Lipid Bilayers", D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337).
    [0105] [0105] Fabric softening compounds substantially insoluble in water are defined as fabric softening compounds with a solubility of less than 1 x 10-3% by weight in demineralized water at 20 degrees Celsius. Preferably, the fabric softening compounds have a solubility of less than 1 x 10-4% by weight, more preferably less than 1 x 10-8 to 1 x 10-6% by weight.
    [0106] [0106] Especially preferred are cationic fabric softening compounds which are water-insoluble quaternary ammonium materials with two C12-22 alkyl or alkenyl groups attached to the molecule via at least one ester bond, preferably two ester bonds. Di (oxyloxyethyl tallow) dimethyl ammonium chloride and / or its hardened tallow analog is an especially preferred compound of this class.
    [0107] [0107] A second preferred type comprises those derivatives of triethanolamine (referred to herein as "TEA quats”), as described, for example, in US 3915867. Suitable materials are, for example, N-methyl silicate diester. N, N, N-triethanolamine or quaternary hardened silk diester chloride or methosulfate Examples of commercially available TEA quats include Rewoquat WE18 and Rewoquat WE20, both partially unsaturated (eg WITCO), Tetranyl AOT-1, completely saturated (for example, KAO) and Stepantex VP 85, completely saturated (for example, Stepan).
    [0108] [0108] It is advantageous that the quaternary ammonium material is biologically biodegradable.
    [0109] [0109] It is also possible to include certain monoalkyl cationic surfactants that can be used in main wash compositions for fabrics. The cationic surfactants that can be used include the quaternary ammonium salts of the general formula R1R2R3R4N + X-, where the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter- ion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C12-C14 or C8-C10 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
    [0110] [0110] The choice of surfactant compound (surfactant) and the amount present will depend on the intended use of the detergent composition. In fabric washing compositions, different surfactant systems can be chosen, as is well known to the person skilled in the art, for manual washing products and for products intended for use in different types of washing machine.
    [0111] [0111] The total amount of surfactant present also depends on the intended end use and can, in fully formulated products, be as high as 60% by weight, for example, in a composition for manual washing of fabrics. In machine wash compositions, an amount of 5 to 40% by weight is generally suitable. Typically, the compositions comprise at least 2% by weight of surfactant, for example, from 2 to 60%, preferably from 15 to 40%, more preferably from 25 to 35% by weight.
    [0112] [0112] Detergent compositions suitable for use in most automatic washing machines generally contain non-anionic surfactant, or non-ionic surfactant, or combinations of the two in any suitable proportion, optionally with soap.
    [0113] [0113] The compositions, when used as the main fabric washing compositions, usually also contain one or more detergency builders. The total amount of detergency builders in the compositions will typically be in the range of 5 to 80% by weight, preferably 10 to 60% by weight, by weight of the composition.
    [0114] [0114] Inorganic activators that may be present include sodium carbonate, if desired in combination with a crystallization seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites, as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates, as disclosed in GB 1 473 202 (Henkel), and mixed crystalline / amorphous aluminosilicates, as described in GB 1 470 250 (Procter &Gamble); and layered silicates, as disclosed in EP 164 514B (Hoechst). Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
    [0115] [0115] The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates, in general, can be incorporated in formulations of final products in amounts of 10 to 70% by weight (anhydrous base), preferably from 25 to 50% by weight.
    [0116] [0116] Alkali metal aluminosilicate can be crystalline or amorphous or mixtures thereof, with the general formula: 0.8-1.5 Na2O. Al2O3. 0.8-6 SiO2.
    [0117] [0117] These minerals contain some bound water, and are needed to have a calcium ion exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5 to 3.5 units of SiO2 (in the formula above). Both amorphous and crystalline materials can be readily prepared by reaction between sodium silicate and sodium aluminate, as widely described in the literature. Suitable crystalline sodium aluminosilicate ion exchange detergent builders are described, for example, in GB 1 429 143 (Procter & Gamble). Preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X and mixtures thereof.
    [0118] [0118] Zeolite may be the commercially available zeolite 4A widely used today in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is a maximum aluminum zeolite P (MAP zeolite), as described and claimed in EP 384 070A (Unilever). MAP zeolite defined as an alkali metal aluminosilicate of the zeolite P type with a weight ratio of silicon to aluminum that does not exceed 1.33, preferably within the range of 0.90 to 1.33 and, more preferably, within the range from 0.90 to 1.20.
    [0119] [0119] Especially preferred is MAP zeolite with a silicon to aluminum weight ratio of not more than 1.07, more preferably about 1.00. The calcium-binding capacity of MAP zeolite is generally at least 150 mg of CaO per g of anhydrous material.
    [0120] [0120] Organic builders that may be present include polycarboxylate polymers, such as polyacrylates, acrylic / maleic copolymers and acrylic phosphinates; monomeric polycarboxylates, such as citrates, gluconates, oxisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxy succinates, carboxymethyloxylates, dipicolinates, hydroxyethyliminodiacetates, alkyl and alkenylmalonates and succinates; and salts of sulfonated fatty acids. This list is not meant to be exhaustive.
    [0121] [0121] The most preferred organic builders are citrates, used appropriately in compositions fully formulated in quantities of 5 to 30% by weight, preferably from 10 to 25% by weight; and acrylic polymers, more particularly acrylic / maleic copolymers, used suitably in amounts of 0.5 to 15% by weight, preferably 1 to 10% by weight.
    [0122] [0122] Builders, both inorganic and organic, are preferably present in the form of alkali metal salt, especially the sodium salt.
    [0123] [0123] The compositions comprising the particles according to the invention can also suitably contain a bleaching system. Fabric washing compositions may desirably contain peroxy bleaching compounds, for example, inorganic persals or organic peroxyacids, capable of producing hydrogen peroxide in aqueous solution.
    [0124] [0124] Suitable peroxide bleaching compounds include organic peroxides such as urea peroxide, and inorganic persals, such as alkali metal perborates, percarbonates, phosphates, persilicates and persulfates. Preferred inorganic persals are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
    [0125] [0125] Especially preferred is sodium percarbonate with a protective coating against moisture destabilization. Sodium percarbonate with a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044b (Kao).
    [0126] [0126] The peroxide bleaching compound is suitably present in a fully formulated product in an amount of 0.1 to 35% by weight, preferably from 0.5 to 25% by weight. The peroxide bleaching compound can be used in conjunction with a bleach activator (bleach precursor) to improve the bleaching action at low washing temperatures. The bleach precursor is suitably present in an amount of 0.1 to 8% by weight, preferably from 0.5 to 5% by weight.
    [0127] [0127] The preferred bleach precursors are the precursors of peroxycarboxylic acids, more especially the precursors of peracetic acid and the precursors of pernoanoic acid. Especially preferred bleach precursors suitable for use in the present invention are N, N, N ', N', tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulfonate (SNOBS). The new bleach precursors of quaternary ammonium and phosphonium disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever), and the cationic bleach precursors revealed in EP 284 292A and EP 303 520A ( Kao) are also of interest.
    [0128] [0128] The bleaching system can be supplemented with or replaced with a peroxyacid. Examples of said peracids can be found in US 4 686 063 and US 5 397 501 (Unilever). A preferred example is the class of peroxycarboxylic imido peracids described in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325 289. A particularly preferred example is peroxy caproxy acid (PAP). Said peracids are suitably present from 0.1 to 12% by weight, preferably from 0.5 to 10% by weight.
    [0129] [0129] A bleach stabilizer (transition metal scavenger) may also be present in fully formulated products. Suitable bleach stabilizers include ethylenediamine tetraacetate (EDTA), polyphosphonates like Dequest (Trademark) and non-phosphate stabilizers like EDDS (ethylene diamine di succinic acid). These bleach stabilizers are also useful for removing stains, especially in final products that contain low levels of bleach species or no bleach species.
    [0130] [0130] An especially preferred bleaching system comprises a bleaching peroxide compound (preferably sodium percarbonate, optionally with a bleaching activator), and a bleaching transition metal catalyst, as described and claimed in EP 458 397A, EP 458 398A and EP 509 787a (Unilever).
    [0131] [0131] Advantageously, in the compositions of the invention, the benefit agents and in particular the perfume components can be used because they are sensitive to bleaches, since the encapsulation of the perfume component, for example, inside the particles, will provide some degree of protection to the perfume component or other beneficial agent.
    [0132] [0132] Fully formulated compositions can also contain one or more enzymes.
    [0133] [0133] Suitable enzymes include proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation into detergent compositions. Preferred proteolytic enzymes (proteases) are catalytically active protein materials that degrade or alter the types of stain proteins when present, such as in tissue stains in a hydrolysis reaction. They can be of any suitable origin, such as vegetable, animal, bacterial or yeast.
    [0134] [0134] Proteolytic enzymes or proteases of various qualities and origins and with activity in various pH ranges from 4 to 12 are available and can be used in the present invention. Examples of suitable proteolytic enzymes are subtilisins which are obtained from particular strains of B. Subtilis, B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Genencor International NV, Delft, The Netherlands, and Alcalase (Trademark), such as that provided by Novozymes Industri A / S, Copenhagen, Denmark.
    [0135] [0135] Particularly suitable is a protease obtained from a strain of Bacillus with a maximum activity over the pH range of 8 to 12, being commercially available, for example, by Novozymes Industri A / S under the registered trade names Esperase (Trademark) Trademark) and Savinase (Trademark). The preparation of these enzymes and analogous enzymes is described in GB 1 243 785. Other commercial proteases are Kazusase (Trademark obtained from Showa Denko in Japan), Optimase (Trademark of Miles Kali Chemie, Hannover, West Germany), and Superase (Trademark obtained from Pfizer USA).
    [0136] [0136] Detergent enzymes are commonly used in products fully formulated in granular form in amounts of about 0.1 to about 3.0% by weight in the product. However, any suitable physical form of enzyme can be used. Advantageously, in the compositions of the invention, benefit agents, for example, perfume components can be employed because they are sensitive to enzymes, since the encapsulation of the perfume component (or other benefit agent) within the particles will provide some degree of protection to the perfume component (or other beneficial agent).
    [0137] [0137] The compositions of the invention may contain an alkali metal, preferably sodium carbonate, in order to increase detergency and facilitate processing. Sodium carbonate may be suitably present in fully formulated products in amounts ranging from 1 to 60% by weight, preferably from 2 to 40% by weight. However, compositions containing little or no sodium carbonate are also within the scope of the invention.
    [0138] [0138] The fully formulated detergent composition, when diluted in the wash solution (during a topical wash cycle) will typically result in a wash solution pH of 7 to 10.5 for a main wash detergent.
    [0139] [0139] Particulate detergent compositions are prepared appropriately by spray drying a slurry with compatible heat insensitive ingredients, and then sprayed or post-dosed on the unsuitable ingredients for processing through the slurry. The expert detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not. It is particularly useful to add the perfume particles of the present invention by means of post-dosing.
    [0140] [0140] Particulate detergent compositions preferably have a bulk density of at least 400 g / liter, more preferably at least 500 g / liter. Especially preferred compositions have bulk densities of at least 650 g / liter, more preferably at least 700 g / liter.
    [0141] [0141] Said powders can be prepared by tower densification of spray dried powder column or by totally non-tower methods, such as dry mixing and granulation. In both cases, a high speed of the mixer / granulator can be advantageously used. The processes using the high speed mixer / granulator are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
    [0142] [0142] Liquid detergent compositions can be prepared by mixing the essential ingredients and their optional ingredients in any desired order to provide compositions that contain the components in the required concentrations. The liquid compositions according to the present invention can also be in compact form, which means that they will contain a lower water level compared to a conventional liquid detergent.
    [0143] [0143] So that the present invention can still be better understood and put into practice, it will still be described with reference to the following examples: EXAMPLES Materials used
    [0144] [0144] The raw materials used in the following examples are summarized in Table 1. Table 1: Name, supplier and description of the materials used in these examples.
    [0145] [0145] A 10% by weight solution of PVOH in water was prepared by placing 100 g of PVOH (Mowiol 20-98 (trade name), ex Kuraray Specialties) and 900 g of demineralized water in a flask and heating to 70 ° C. For this, 10 ml of hydrochloric acid (36% aqueous solution) were added to catalyze the reaction, and then butyraldehyde was added in an amount of 10% based on the total weight of the polymer. The mixture was then stirred at 70 ° C for 5 hours under an inert atmosphere, after which heating was stopped and stirring was continued for another 20 hours at room temperature. The reaction mixture was then brought to pH 7 using sodium hydroxide solution.
    [0146] [0146] The resulting solution was precipitated in acetone to produce the acetalysed PVOH polymer and washed repeatedly with acetone (500 ml) and then water (50 ml). Then, it was vacuum dried at 70 ° C overnight to produce a white polymer.
    [0147] [0147] The following capsules have been prepared: Hybrid Capsule 1 - hybrid polyamide-mPVOH capsule. Hybrid Capsule 2 - hybrid polyamide-mPVOH capsule made according to the invention. Comparative Capsule A - a polyamide perfume capsule Comparative Capsule B - dextran crosslinked mPVOH capsule
    [0148] [0148] The following methods were used to prepare the capsules for use in these examples: I) Preparation of the polyamide perfume capsule (Comparative Capsule A)
    [0149] [0149] Comparative Capsule A, which comprises the perfume Limonene, was prepared using the following method: Step 1: - The following liquids have been prepared: Liquid A: 2.4 ml of perfume (Limonene) and 0.27 g of terephthaloyl chloride were mixed until the terephthaloyl chloride was dissolved to obtain an oily liquid. Aqueous solution B: 30 ml of deionized water containing 1% by weight of PVA (5-88) were prepared, and the pH was adjusted to the desired value with the use of 1M NaOH. Aqueous solution C: 3.9 ml of DETA were dissolved in 6 ml of deionized water. Step 2: - Liquid A was then added to solution B under homogenization at 6000 rpm, and the mixture was emulsified for 5 min. Solution C was then added dropwise to the emulsion, and homogenization was continued for 10 min. The resulting suspension of polyamide capsules, called "Comparative Capsule A", was left to age for 24 h to obtain the capsule slurry for use in the examples below. II) Preparation of the dextran crosslinked mPVOH capsule (Comparative Capsule B) Preparation of dextran crosslinking agent
    [0150] [0150] An dextran derived from aldehyde was first prepared as follows:
    [0151] [0151] 50 ml of a 4% aqueous solution of sodium periodate (NaIO4) was prepared in a flask. The pH of the solution was adjusted to about 3.5 with the addition of 0.5 ml of 1M HCl, and the solution was then protected from light by covering the flask with aluminum foil. 1.5 g dextran (MWt 20,000) was added to the flask and dissolved. The resulting mixture was heated to 40 ° C with stirring for 3 h. The mixture was then dialyzed using a dialysis tube with a 7000 MWt cut for 48 h. The resulting material was then ready to be used as a crosslinking agent.
    [0152] • 32 g de solução de mPVOH 0,5% foram misturados a 480μΙ de perfume Limoneno em um balão de uma boca de modo que uma proporção final de perfume para mPVOH de 3:1 foi alcançada. • A mistura foi então emulsificada por homogeneização em 6000 rpm durante 5 min. O balão foi então colocado em um banho de água e aquecido até 50°C em uma taxa de cerca de 1°C/min com agitação suave, e a mistura foi mantida em 50°C durante 5 min. • 0,4 ml de agente de reticulação de dextrano, como preparado acima, (ou seja, solução de dextrano derivado de aldeído (20k) (a concentração CHO era de 0,2 mol/L)) foi adicionado ao balão, e a mistura foi mantida em 50 °C durante mais 1,5 h. • 500 μL de HCl 1M foram então adicionados para ajustar o pH para 2-3, e a mistura resultante foi agitada durante mais 4,5 h em 50°C. • O balão foi então removido e as cápsulas de perfume, designadas "Cápsula Comparativa B”, foram formadas na mistura. [0152] Comparative Capsule B, which comprises the perfume Limonene, was prepared using the following method: • 32 g of 0.5% mPVOH solution was mixed with 480μΙ of Limonene perfume in a one-mouth flask so that a final perfume to mPVOH ratio of 3: 1 was achieved. • The mixture was then emulsified by homogenization at 6000 rpm for 5 min. The flask was then placed in a water bath and heated to 50 ° C at a rate of about 1 ° C / min with gentle agitation, and the mixture was maintained at 50 ° C for 5 min. • 0.4 ml dextran cross-linking agent, as prepared above, (ie, dextran solution derived from aldehyde (20k) (CHO concentration was 0.2 mol / L)) was added to the flask, and the The mixture was maintained at 50 ° C for an additional 1.5 h. • 500 μL of 1M HCl was then added to adjust the pH to 2-3, and the resulting mixture was stirred for an additional 4.5 h at 50 ° C. • The flask was then removed and the perfume capsules, designated "Comparative Capsule B", were formed in the mixture.
    [0153] [0153] A polyamide perfume capsule comprising the Limonene perfume was first prepared in the same way as described above for the preparation of Comparative Capsule A.
    [0154] • A suspensão foi centrifugada durante 10 min em 1000 rpm. 28 ml de água limpa no fundo do tubo foram então removidos com a utilização de um injetor de agulha longa. • A pasta fluida remanescente foi diluída para 42 ml com água deionizada. • As etapas de centrifugação e diluição acima foram repetidas 6 vezes. • O pH da pasta fluida de poliamida final foi ajustado para 7 com a utilização de HCl. [0154] The following steps were then followed in order to remove any unreacted DETA from the resulting polyamide capsule slurry. • The suspension was centrifuged for 10 min at 1000 rpm. 28 ml of clean water at the bottom of the tube was then removed using a long needle injector. • The remaining slurry was diluted to 42 ml with deionized water. • The above centrifugation and dilution steps were repeated 6 times. • The pH of the final polyamide slurry was adjusted to 7 using HCl.
    [0155] • 21 ml de pasta fluida de cápsula de poliamida lavada foram combinados com 32 g de solução de mPVOH 0,5% em um balão de uma boca com agitação. • O balão foi então colocado em um banho de água e aquecido até 50°C em uma taxa de cerca de 1°C/min com agitação suave, e a mistura foi mantida em 50°C durante 5 min. • 0,4 ml de agente de reticulação de dextrano, como preparado acima, (ou seja, solução de dextrano derivado de aldeído (20k) (a concentração CHO era de 0,2 mol/L)) foi adicionado ao balão, e a mistura foi mantida em 50 °C durante mais 1,5 h. • 500 μL de HCl 1M foram então adicionados para ajustar o pH para 2-3, e a mistura resultante foi agitada durante mais 4,5 h em 50°C. • O balão foi então removido, e as cápsulas híbridas foram encontradas formadas na mistura. IV) Preparação de poliamida-mPVOH híbrida (Cápsula Híbrida 2) • 1,2 ml de perfume (Limoneno) e 0,135 g de cloreto de tereftaloílo foram misturados até que o cloreto de tereftaloílo fosse dissolvido para a obtenção de um líquido oleoso. • O líquido oleoso assim obtido foi então adicionado a 32 g de solução de mPVOH 0,5% em um frasco de uma boca sob agitação. • A mistura foi então emulsificada por homogeneização em 6000 rpm durante 2 min. • 0,4 ml de agente de reticulação de dextrano, como preparado acima, (ou seja, solução de dextrano derivado de aldeído (20k) (a concentração CHO era de 0,2 mol/L)) foi adicionado à emulsão, e a mistura foi homogenizada em 6000 rpm durante 3 min. • O balão foi então colocado em um banho de água e aquecido até 50°C em uma taxa de cerca de 1°C/min com agitação suave. • 500 μL de 1M HCl foram então adicionados para ajustar o pH para 2-3, e a mistura resultante foi agitada durante mais 1 h em 50°C. • 1,95 ml de DETA foram dissolvidos em 3 ml de água deionizada e adicionados gota a gota à emulsão. • A mistura resultante foi agitada durante mais 2 h em 50 °C. • O balão foi então removido, e as cápsulas híbridas foram encontradas formadas na mistura. [0155] The hybrid capsule was then prepared as follows, using the washed polyamide capsule as a seed. • 21 ml of washed polyamide capsule slurry was combined with 32 g of 0.5% mPVOH solution in a shaking mouth flask. • The flask was then placed in a water bath and heated to 50 ° C at a rate of about 1 ° C / min with gentle agitation, and the mixture was kept at 50 ° C for 5 min. • 0.4 ml dextran cross-linking agent, as prepared above, (ie, dextran solution derived from aldehyde (20k) (CHO concentration was 0.2 mol / L)) was added to the flask, and the The mixture was maintained at 50 ° C for an additional 1.5 h. • 500 μL of 1M HCl was then added to adjust the pH to 2-3, and the resulting mixture was stirred for an additional 4.5 h at 50 ° C. • The flask was then removed, and hybrid capsules were found to be formed in the mixture. IV) Preparation of hybrid polyamide-mPVOH (Hybrid Capsule 2) • 1.2 ml of perfume (Limonene) and 0.135 g of terephthaloyl chloride were mixed until the terephthaloyl chloride was dissolved to obtain an oily liquid. • The oily liquid thus obtained was then added to 32 g of 0.5% mPVOH solution in a vial from a mouth under agitation. • The mixture was then emulsified by homogenization at 6000 rpm for 2 min. • 0.4 ml of dextran crosslinking agent, as prepared above, (ie, dextran solution derived from aldehyde (20k) (CHO concentration was 0.2 mol / L)) was added to the emulsion, and the The mixture was homogenized at 6000 rpm for 3 min. • The flask was then placed in a water bath and heated to 50 ° C at a rate of about 1 ° C / min with gentle agitation. • 500 μL of 1M HCl was then added to adjust the pH to 2-3, and the resulting mixture was stirred for another 1 h at 50 ° C. • 1.95 ml of DETA were dissolved in 3 ml of deionized water and added dropwise to the emulsion. • The resulting mixture was stirred for an additional 2 h at 50 ° C. • The flask was then removed, and hybrid capsules were found to be formed in the mixture.
    [0156] [0156] Hybrid Capsules 1 and 2 were stored at room temperature for a period of 1 month.
    [0157] [0157] The capsules were observed under an optical microscope (Hirox KH7700 3D microscope) before and after storage, in order to assess the levels of rupture and aggregation. Table 2: Appearance of the capsule before and after storage.
    [0158] [0158] Hybrid Capsules 2 were found to have superior storage stability compared to Hybrid Capsules 1. Example 3: Effect of drying on Hybrid Capsules 2, Comparative Capsule A and Comparative Capsule B
    [0159] [0159] Hybrid Capsule 2, Comparative Capsule A and Comparative Capsule B were subjected to a drying process, in which a drop of slurry from the capsule was dripped onto a glass slide, and then allowed to dry naturally for 20 min. room temperature.
    [0160] [0160] The capsules were observed under an optical microscope (Hirox KH7700 3D microscope) after drying, in order to assess the level of rupture induced by the drying process. Table 3: Appearance of the capsule after drying.
    [0161] [0161] It will be seen that Hybrid Capsules 2 had a good resistance to drying. Example 4: Evaluation of perfume leakage from Hybrid Capsule 2, Comparative Capsule A and Comparative Capsule B
    [0162] [0162] The following method was used to assess the leakage of perfume from Hybrid Capsule 2, Comparative Capsule A and Comparative Capsule B
    [0163] [0163] The capsules (in an amount containing 15 mg of perfume) were added to 2 g of Lux Body Wash, formulation from the United States, commercially available from January to February 2011, in a glass bottle and the bottle was sealed. The mixture was then incubated at 37 ° C for 10 days prior to the evaluation of SPME-GC-MS for the perfume leak.
    [0164] [0164] 2 g Body Wash formulation containing 15 mg free perfume were prepared as the calibration standard corresponding to 100% leakage. Likewise, a logarithmic scale of target concentrations such as calibration standards was prepared corresponding to 1.0, 1.8, 3.2, 5.6, 10, 18, 32, 56% leakage.
    [0165] [0165] Calibrations, samples and control were all preferably measured within the same timeframe.
    [0166] [0166] The leakage of the perfume capsule in the Body Wash formulation was obtained by comparing the corresponding peak of absorption and that of the calibrations. The details of the SPME-GC-MS method are presented below. SPME-GC-MS method: Equipment: Agilent 6890 GC equipped with Agilent 5975B MS and PAL CTC sampler Incubation time: 300s Incubation temperature: 30 ° C Extraction time: 10s Desorption time: 60s Oven: 50 ° C keep for 1min, 20 ° C / min at 180 ° C, 40 ° C / min at 280 ° C and keep for 2 min, 80 ° C / min at 200 ° C, 60 ° C / min in 140 ° C, 40 ° C / min at 100 ° C, Runtime: 15min Input: 250 ° C, splitless Conveyor: He, 1.0 mL / min Column: DB-5MS, J&W 122-5532 Acquisition mode: YES, m / z 71, 136, 150 Table 4: Perfume leakage from Hybrid Capsule 2, Comparative Capsule A and Comparative Capsule B in the Body Wash formulation
    [0167] [0167] 2 g Body Wash formulation containing 15 mg free perfume were prepared as the calibration standard corresponding to 100% leakage.
    [0168] [0168] It will be seen that Hybrid Capsules 2 leak less than Comparative Capsule A.
    [0169] [0169] In general, the capsules of the invention exhibit a unique combination of storage stability, robustness to drying and low leakage of perfume. Example 5: Evaluation of the long-lasting freshness of Hybrid Capsule 2, and Comparative without perfume
    [0170] [0170] 1.2 ml of limonene perfume and 37.7 ml of 0.01% mPVOH solution were homogenized, and the resulting mixture was designated Comparative without perfume.
    [0171] [0171] The following method was used to evaluate the long-lasting freshness of the Hybrid Capsule 2 and the Comparative without perfume:
    [0172] [0172] 0.5 ml of Hybrid Capsule 2 (in an amount containing 13 mg of perfume) or 0.5 ml of Comparative without perfume (in an amount containing 13 mg of perfume) was dripped onto a piece (6x6 cm) of mesh sheet of polyester fabric. The tissue sheet was hung and dried naturally at room temperature for periods of 10 min, 20 min, 30 min, 40 min or 120 min. Then, the tissue was placed in 10ml of acetone and sonified for 90s (circulatory pulse mode that includes 2 seconds of operation and 5 seconds of suspension). The amount of perfume in acetone was then assessed using GC-FID. GC-FID method: Device: HP 6890 plus + Oven: initial 40 ° C, keep for 1min, 10 ° C / min at 200 ° C and keep for 2min Runtime: 19min Inlet: 220 ° C Division ratio: 50: 1 Detector: 230 ° C Column: Agilent 19091S-133, HP-INNOWax, Polyethylene Glycol Conveyor: Helium Flow rate: 1.0ml / min Table 5: Long-lasting freshness of Hybrid Capsule 2, and Comparative without perfume
    [0173] [0173] It can be seen that the Hybrid Capsule 2 showed better long-lasting freshness than the Comparative without perfume.
    权利要求:
    Claims (17)
    [0001]
    PROCESS FOR THE PREPARATION OF A PARTICLE, characterized by the particle comprising: (a) a core that comprises a hydrophobic beneficial agent; (b) an external crosslinked wrapper comprising a hydrophobically modified crosslinked polyvinyl alcohol, comprising a crosslinking agent, comprising a first dextran aldehyde with a molecular weight of 2,000 to 2,000,000 Da; and (c) an inner polyamide shell, the shell comprising a polyamide, and the polyamide comprising an aromatic group; wherein the outer crosslinked wrapper is formed prior to the formation of the inner polyamide wrapper.
    [0002]
    PROCESS, according to claim 1, characterized by comprising the steps of: i) formation of an emulsion comprising a) an oily phase comprising the hydrophobic benefiting agent and a reactive monomer comprising an aromatic group; and b) an aqueous phase comprising a hydrophobically modified polyvinyl alcohol; ii) addition of the first dextran aldehyde with a molecular weight of 2,000 to 2,000,000 Da, so that the crosslinking of the hydrophobically modified polyvinyl alcohol occurs to form the outer crosslinked shell; and iii) addition of a reactive amine, so that the reactive monomer in the oil phase is subjected to polymerization to form the internal polyamide shell.
    [0003]
    PROCESS according to claim 1 or 2, characterized in that the first dextran aldehyde has a molecular weight of 2,000 to 50,000 Da and the outer crosslinked shell further comprises a second dextran aldehyde with a molecular weight of more than 50,000 to 2,000,000 Da.
    [0004]
    PROCESS according to claim 3, characterized in that the w / w ratio (weight / weight) of the second dextran aldehyde to the first dextran aldehyde is in the range of 0.1 to 10.
    [0005]
    PROCESS according to any one of claims 1 to 4, characterized in that the particle comprises a deposition aid.
    [0006]
    PROCESS, according to claim 5, characterized in that the deposition aid is a polysaccharide.
    [0007]
    PROCESS, according to claim 6, characterized in that the deposition aid is a non-ionic polysaccharide.
    [0008]
    PROCESS according to any one of claims 1 to 7, characterized in that the particle has an average diameter of 5 to 50 micrometers.
    [0009]
    PROCESS according to any one of claims 1 to 8, characterized in that the beneficial agent is a fragrance, an antimicrobial compound or a mixture thereof.
    [0010]
    PROCESS according to any one of claims 1 to 9, characterized in that the polyamide comprises at least one water-miscible monomer and one water-immiscible organic monomer.
    [0011]
    PROCESS according to any one of claims 1 to 10, characterized in that the hydrophobically modified polyvinyl alcohol is modified with butyraldehyde.
    [0012]
    PARTICLE OBTAINED FROM THE PROCESS, as defined in any one of claims 1 to 11, characterized by comprising: (a) a core that comprises a hydrophobic beneficial agent; (b) an external crosslinked wrapper comprising a hydrophobically modified crosslinked polyvinyl alcohol, comprising a crosslinking agent, comprising a first dextran aldehyde with a molecular weight of 2,000 to 2,000,000 Da; and (c) an inner polyamide shell, the shell comprising a polyamide, and the polyamide comprising an aromatic group; wherein the outer crosslinked wrapper is formed prior to the formation of the inner polyamide wrapper.
    [0013]
    NET COMPOSITION, characterized by comprising the particle, as defined in claim 12, and which further comprises: a) at least one surfactant selected from anionic, cationic, non-ionic and zwitterionic surfactants; and b) a solvent.
    [0014]
    NET COMPOSITION, according to claim 13, characterized in that the composition comprises water.
    [0015]
    COMPOSITION FOR DOMESTIC CARE OR PERSONAL CARE, characterized by comprising at least one particle, as defined in claim 12.
    [0016]
    COMPOSITION FOR DOMESTIC CARE OR PERSONAL CARE, as defined in claim 13, characterized by the composition being a laundry detergent, laundry conditioner, deodorant, antiperspirant, shampoo, hair conditioner or skin care product or skin cleanser.
    [0017]
    METHOD OF TREATING A SUBSTRATE, characterized in that the substrate is selected from skin, hair and / or textile material, which includes the stage of treating the substrate with a composition comprising the particles, as defined in claim 12.
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    同族专利:
    公开号 | 公开日
    BR112016001974A8|2019-10-01|
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    JP6577948B2|2019-09-18|
    ES2609237T3|2017-04-19|
    BR112016001974A2|2017-08-01|
    JP2016532546A|2016-10-20|
    US10117815B2|2018-11-06|
    WO2015014792A1|2015-02-05|
    MX2016000803A|2016-04-27|
    EP3027303A1|2016-06-08|
    US20160193125A1|2016-07-07|
    CN105408016A|2016-03-16|
    MX356983B|2018-06-22|
    CN105408016B|2017-10-13|
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    法律状态:
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: B01J 13/14 (2006.01) |
    2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-06| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    2021-03-16| B09A| Decision: intention to grant|
    2021-04-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CNPCT/CN2013/080412|2013-07-30|
    CN2013080412|2013-07-30|
    EP13189102|2013-10-17|
    EP13189102.0|2013-10-17|
    PCT/EP2014/066175|WO2015014792A1|2013-07-30|2014-07-28|Improvements relating to encapsulated benefit agents|
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