WO2010015493A1 - Microcapsules dans des compositions contenant un tensioactif - Google Patents

Microcapsules dans des compositions contenant un tensioactif Download PDF

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Publication number
WO2010015493A1
WO2010015493A1 PCT/EP2009/059046 EP2009059046W WO2010015493A1 WO 2010015493 A1 WO2010015493 A1 WO 2010015493A1 EP 2009059046 W EP2009059046 W EP 2009059046W WO 2010015493 A1 WO2010015493 A1 WO 2010015493A1
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WIPO (PCT)
Prior art keywords
surfactant
composition according
modified
benefit agent
hydrophobic
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PCT/EP2009/059046
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English (en)
Inventor
Stuart Anthony Barnett
Craig Warren Jones
Andrew Philip Parker
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Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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Application filed by Unilever Plc, Unilever N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to ES09780617T priority Critical patent/ES2402486T3/es
Priority to BRPI0917442A priority patent/BRPI0917442A2/pt
Priority to CN200980140032.9A priority patent/CN102177232B/zh
Priority to EP09780617A priority patent/EP2307536B1/fr
Publication of WO2010015493A1 publication Critical patent/WO2010015493A1/fr
Priority to ZA2011/00600A priority patent/ZA201100600B/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to surfactant-containing compositions which include particles comprising a benefit agent and their use, particularly as laundry detergent or fabric conditioner products.
  • the invention is also applicable to other surfactant-containing products such as those suitable for use on skin and hair and on hard surfaces.
  • the invention will be particularly described with reference to the benefit agents being perfumes, dyes and cationic surfactants.
  • Perfumes are important and expensive components of laundry detergent compositions and other surfactant containing products. It is important to ensure that perfumes are not lost during processing or on storage of the compositions and that they deposit onto articles and surfaces being washed. Being volatile, perfumes are prone to evaporate from a composition, especially if the composition is subjected to elevated temperatures. Methods for deposition of perfume components and other benefit agents from surfactant-containing compositions are diverse and perfume is often incorporated into a carrier or other delivery system. Carrier systems for perfumes are typically based on encapsulation or entrapment of the perfume within a matrix. The perfume may simply be emulsified but deposition onto a substrate, such as fabric, skin or hair, is often inefficient and problems with poor retention or stability may be found. Preparation of materials by diffusion of the perfume into a carrier can suffer from complex preparation, long times of diffusion, poor retention of the perfume in the matrix and subsequent poor substrate deposition.
  • EP 332175 discloses a method of producing water- insoluble microcapsules comprising the steps of mixing (i) an aqueous dispersion containing capsules having a wall-membrane containing PVOH and an aqueous solution containing an electrolyte and (ii) a cross-linking agent comprising an aldehyde.
  • the electrolyte stabilises the capsules until the wall-membrane has been cross-linked.
  • perfume encapsulates are based on aminoplast materials and may be modified with cationic materials to improve deposition on surfaces such as textiles. These charged capsules encounter difficulties if used in an environment which contains anionic surfactants as the capsules and the surfactant will interact.
  • Poly-vinyl alcohol has been used to form water-soluble sachets containing cationic surfactants.
  • WO 2004/031271 discloses modified poly-vinyl alcohol (PVOH) sachets which are surrounded by films with a preferred average thickness of from 50 to 500 microns.
  • the sachets preferably contain from 0.5 ml to 100 ml of a material such as a laundry conditioner.
  • GB 0803165.0 discloses a microcapsule, having a diameter of less than 2mm comprising: (a) a benefit agent (such as perfume), and (b) a water soluble polymeric film-forming material modified with both a hydrophobic group and a first charged, dehvatising group(s).
  • the film remains substantially intact in the presence of a surfactant, and disintegrates when the concentration of the surfactant reduces sufficiently, thereby releasing the benefit agent.
  • Dyes are another useful component of many surfactant-containing compositions.
  • dyes can be used as "shading” or "hueing” agents.
  • Dyes may be present in hair products to colour the hair.
  • perfumes dyes are difficult to deposit from surfactant compositions as the surfactant has a tendency to assist removal of the dye from the article or surface being washed. The same is true of many other benefit agents.
  • a hydrophobically modified polymer which does not have the charged dehvatising group required by GB 0803165.0 can be used to coat micro-particles which comprise a benefit agent and that these particles, while stable at high surfactant concentrations, release the benefit agent at low surfactant concentrations.
  • micro-particles are far smaller than the sachets of WO 2004/031271 and unlike the cross-linked, water-insoluble particles of EP 332175, do not need to be crushed to release their contents.
  • the first aspect of the invention provides a composition comprising, 1 -99%wt of surfactant and at least one micro-particle having a diameter of 100nm-2mm, said micro-particle comprising:
  • a core comprising a hydrophobic benefit agent
  • a shell comprising an uncharged hydrophobically-modified, water-soluble film-forming polymer, whereby the film remains substantially intact in the - A -
  • the micro-particles have a diameter of 1 -1000 microns, more preferably 1 -100 microns, most preferably 1 -50 microns.
  • hydrophobic benefit agents have a ClogP greater than 0.5, preferably greater than 1 and more preferably greater than 2.
  • ClogP critical solution temperature
  • the surfactant-polymer shell When the temperature is dropped below the LCST, the surfactant-polymer shell remains stable, provided that sufficient surfactant is present.
  • the shell is stable in a surfactant containing product. However, upon dilution of the product the shell becomes unstable and the benefit agent is released.
  • the modified polymer has:
  • a solubility or dispersibility at 2O 0 C in water which contains a concentration of one or more anionic/non-ionic or cationic surfactants of greater than 1g/L of less than 0.5 g per hour, and,
  • the invention finds particular utility when applied to benefit agents which are droplets of oily material such as free perfume oil or even to particles which comprise pre-encapsulated perfumes, in particular to urethane or aminoplast encapsulates, (including, melamine-formaldehyde) encapsulates and to poly- olefinic encapsulates (including those based on poly(meth)acrylates).
  • oily materials include oils having oil-soluble dyes, or other benefit agents dispersed therein.
  • the benefit agent has a solubility in water (at 20 Celcius) of less than 600mg/L, preferably less than 200mg/L.
  • the invention can also be used to encapsulate charged species, preferably cationic materials, so that they can be added to a solution containing materials of the opposite charge without causing flocculation/instability.
  • the hydrophobic dehvatising group of the polymer is derived from a parent material having a ClogP of greater than 0.5.
  • a process for treatment of fabrics comprising the step of contacting a composition according the present invention, in neat or dilute form, with fabric.
  • the use of the invention is not limited to laundry applications and can be used on other surfaces such as that of hair or living tissue.
  • the present invention can be used to stabilize and deliver hydrophobic benefit agents from any surfactant-containing system which will undergo significant dilution during use.
  • the invention further provides a process for the treatment of a surface comprising the step of contacting a composition according the present invention, in neat or dilute form, with the surface.
  • Polymers suitable for use as whole or part of the backbone of the hydrophobically modified water soluble polymer are preferably selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, cellulose ethers, polyethylene oxide, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene maleic anhydride, hydroxyethylcellulose, methylcellulose, polyethylene glycols, carboxymethylcellulose, polyacrylic acid salts, alginates, acrylamide copolymers, guar gum, casein, ethylene-maleic anhydride resin series, polyethyleneimine, ethyl hydroxyethylcellulose, ethyl methylcellulose and hydroxyethyl methylcellulose.
  • Copolymeric mixtures of polymers derived from the aforementioned backbones are also suitable.
  • the water soluble polymer has a backbone comprising side chain hydroxyl groups
  • the most preferred backbone for the water soluble polymer comprises polyvinyl alcohol (PVAc), preferably with an average a molecular weight of from 10kD to 30OkD preferably from 2OkD to 20OkD most preferably from 75kD to 175kD. .
  • PVAc polyvinyl alcohol
  • Polyvinyl alcohol can be supplied in a form comprising a certain amount of polyvinyl acetate (PVAc), in that a level of the hydroxyl groups (OH) of the PVOH material is substituted with acetate groups (OCOCH 3 ).
  • Hydrolysis of PVAc is a common way to make PVOH. However, to achieve complete hydrolysis is expensive and typical materials are only up to around 99% hydrolysed. Thus the PVOH used herein generally comprise at some PVAc.
  • the PVOH materials may comprise from 0.01 to 40% PVAc, preferably from 0.01 to 20%, more preferably from 0.1 to 15%, most preferably 0.5 to 10%, based on the % of the total number of monomers making up the polymer.
  • PVOH includes PVOH compounds with a PVAc level as previously defined.
  • the reference to the material being uncharged means that the PVOH comprises no charged derivatising group as required by GB 0803165.0, not that it is free of residual PVAc.
  • the modified polymer has an average degree of hydrolysis within the range from 70 to 99%.
  • the modified polymer has a viscosity as a 4% solution at 20 0 C measured according to DIN 53 015 within the range 1 to 100 mPa.s.
  • the water-soluble polymer is modified to comprise hydrophobic substituents.
  • Preferred hydrophobic derivatisation groups include those based on parent groups selected from acetals, aldehydes, ketals, esters, fluorinated organic compounds, ethers, alkanes, alkenes and aromatics.
  • Highly preferred hydrophobic substituents are hydrocarbyl groups of C 4 to C22 carbon chain length. These hydrocarbyl groups may be alkyl or alkenyl based, which can be straight chain, branched or comprise rings; it may also or alternatively incorporate aromatic moieties.
  • the hydrocarbyl group has a carbon chain length of from C 4 to C20, even more preferably from C 4 to C15, most preferably from C 4 to C10, for example, from C 4 to C 8 .
  • Hydrocarbyl chain lengths greater than C22 are undesirable as the parent material from which the dehvatising group is obtained reacts poorly or not at all with the polymeric backbone. Hydrocarbyl groups shorter than C4 provide negligible additional hydrophobicity.
  • aldehydes such as butyraldehyde, octyl aldehyde, dodecyl aldehyde, 2-ethyl hexanal, cyclohexane carboxy-aldehyde, citral and 4-aminobutyraldehyde dimethyl acetal.
  • the hydrophobic material is preferably present in the polymer at a level from 0.1 to 40% by weight, based on the total weight of the polymer, more preferably from 2 to 30%, most preferably from 5 to 15%.
  • the hydrophobic dehvatisation material is preferably present at a level such that the number ratio of the hydrophobic groups to the free hydroxyl pairs on the backbone is from 1 :3 to 1 :30, more preferably from 1 :4 to 1 :20, most preferably 1 :7 to 1 :15.
  • Variation of the level of derivatisation of the polymer enables the properties of the shell to be modified such that the shell will release the materials in the core at a particular level of surfactant.
  • shells can be made which are stable in the surfactant-containing product but which become unstable at the level of surfactant found in a wash-liquor (for example, which become unstable in the main-wash of a laundry process or during skin or hair treatment with the product in the presence of water).
  • Such systems can assist in the stability of the benefit agent during product storage.
  • shells may be stable a wash liquor, but become unstable during rinsing of the wash-liquor from the surface or article being treated.
  • particles can be formed which release the benefit agent during a rinsing process, and reduce the tendency of the benefit agent to be removed by the surfactant. More than one type of particle may be present in a given product to prevent interaction of components, for example sunscreens, which might otherwise interact.
  • the water soluble film can be provided from a material which has a partly cross-linked polymeric structure.
  • the level of cross- linking should be kept low so as to avoid the formation of an insoluble material. It is preferable that the material from which the film is made is not cross-linked at all.
  • cross-linking agents include formaldehyde; polyesters; epoxides, amidoamines, anhydrides, phenols; isocyanates; vinyl esters; urethanes; polyimides; acrylics; bis(methacrylkoxypropyl) tetramethylsiloxane (styrenes, ethylmethacrylates); n-diazopyruvates; phenyboronic acids; cis-platin; divinylbenzene; polyamides; dialdehydes; thallyl cyanurates; N-(-2- ethanesulfonylethyl)pyhdinium halides; tetraalkyltitanates; mixtures of titanates and borates or zirconates; polyvalent ions of Cr, Zr, Ti; dialdehydes, diketones; alcohol complexes of organotitanates, zircoates and borates and copper (II) complex
  • the preferred cross-linking agent is a metalloid oxide such as borate, tellurate, arsenate, and precursors thereof.
  • Other known cross-linkers include the vanadyl ion, titanium ion in the plus three valence state, or a permanganate ion (disclosed in patent US 3,518,242).
  • Alternative cross-linkers are given in the book: Polyvinylalcohol - Properties and applications, Chapter 9 by CA. Finch (John Wiley & Sons, New York, 1973).
  • the film may incorporate a plasticiser and/or crystallinity disruptor. It is to be understood that the term “plasticiser” and phrase “crystallinity disruptor” are interchangeable such that a reference to one is an implicit reference to the other.
  • Water itself is a suitable plasticizer for mPVOH films but other common plasticizers include: Polyhydroxy compounds, e.g. glycerol, thmethylolpropane, diethylene glycol, triethylene glycol, sorbitol, dipropylene glycol, polyethylene glycol; starches, e.g. starch ether, estehficated starch, oxidized starch and starches from potato, tapioca and wheat; cellulosics/carbohydrates, e.g. amylopectin, dextrin, carboxymethyl-cellulose and pectin. Amines are particularly preferred plasticisers.
  • Polyhydroxy compounds e.g. glycerol, thmethylolpropane, diethylene glycol, triethylene glycol, sorbitol, dipropylene glycol, polyethylene glycol
  • starches e.g. starch ether, estehficated starch, oxidized starch and starches from potato, tapioca and wheat
  • Suitable plasticisers for mPVP-based films may be chosen from one or more of: phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenyl phosphate, tributoxyethylphosphate; polyols e.g. glycerol, sorbitol, diethylene glycol diperlargonate, polyethylene glycol di-2-ethylhexanoate, dibutyl tartrate; polyol esters e.g. hydroxy containing polycaprolactones, hydroxy containing poly-L- lactide; lower phthalates e.g.
  • phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenyl phosphate, tributoxyethylphosphate
  • polyols e.g. glycerol, sorbitol, diethylene glycol diperlargonate, poly
  • Suitable plasticizers for mPEO-based films may be selected from one or more of: phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenyl phosphate, tributoxyethylphosphate; polyols e.g. glycerol, sorbitol, diethylene glycol diperlargonate, polyethylene glycol di-2-ethylhexanoate, dibutyl tartrate; lower phthalates e.g. dimethyl phthalate, diethyl phthalate, dibutyl phthalate; and sulphonamides e.g. toluene sulphonamide, N-ethyltoluene sulphonamide.
  • phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenyl phosphate, tributoxyethylphosphate
  • polyols
  • the surfactant used to form the gel barrier with the film is preferably anionic, although nonionic or cationic surfactants can be used. If the particle is for use within a laundry detergent, the surfactant used is preferentially anionic or nonionic.
  • Anionic products are also typically used in hair and/or skin cleaning compositions.
  • the surfactant is preferably cationic or nonionic. Similarly, cationic surfactants are typically used in hair conditioning products.
  • Suitable anionic surfactants are: linear alkyl benzene sulphonate (LAS), primary alkyl sulphate (PAS), fatty ether sulphates (LES), secondary alkane sulphonate, ⁇ -olefin sulphonate, ⁇ -sulphonic fatty acid methyl ester, methyl ester sulphonates (MES).
  • the preferred surfactants are LAS, PAS, LES, and mixtures [hereof.
  • Preferred materials include including sodium fatty alcohol sulphate, ammonium fatty alcohol sulphate, ammonium alcohol ether sulphate, sodium fatty ether sulphate, alcohol ether carboxylate and nonylphenol polyoxyethylene ether carboxylate.
  • the most preferred surfactant for laundry compositions is LAS.
  • Suitable non-ionic surfactants include ethoxylated linear and branched alcohols, ethoxyiated alkyl phenols, fatty acid esters, amine and amide derivatives, aikylpoiygiycosides, EO/PO block copolymers, polyalcohols and ethoxyiated poiyaicohois.
  • the surfactant present is preferably an anionic surfactant has from 8 to 14 carbons, more preferably from 10 Io 12 and most preferably 12 carbons. More preferably, these carbons are present in a single alkyi group.
  • Preferred anionic surfactants for hair and skin products comprise include alkali metal alky!
  • the cleansing phase of a hair or skin product comprises from 27 to 70% by weight cleansing surfactant, preferably from 35 to 50% by weight of the composition.
  • preferred cationic surfactants have the formula N+(R 1 )(R-)(R 3 )(R "1 ), wherein R 1 , R 2 , R 3 and R A are independently (C 18 to C30) alkyi or benzyl.
  • R 1 , R 2 , R 3 and R A are independently (C 18 to C30) alkyi or benzyl.
  • R 1 , R' : , R :i and R 4 are independently (C18 to C30) aikyl and the other R 1 .
  • R 2 , R 3 and R " group or groups are ⁇ C1-C6) alkyi or benzyl.
  • the alkyi groups may comprise one or more ester (-OGO- or -GOO-) and/or ether (-O-) linkages within the alkyi chain.
  • Aikyl groups may optionally be substituted with one or more hydroxyl groups.
  • Aikyl groups may be straight chain or branched and, for aikyl groups having 3 or more carbon atoms, cyclic.
  • the aikyl groups may be saturated or may contain one or more carbon-carbon double bonds (e.g., oleyl).
  • Alkyi groups are optionally ethoxyiated on the aikyl chain with one or more ethyleneoxy groups.
  • Suitable cationic surfactants for use in conditioner compositions according to the invention include cetylt ⁇ methylamrnomurn chloride, behenyltrimethylammo ⁇ ium chloride, cetyipyridinium chloride, tetramethylammonium chloride. tetraethylammonium chloride, stearyldirnethylbe ⁇ zylarnmo ⁇ ium chloride, cocot ⁇ methyiammonlum chloride, PEG-2-oleammon ⁇ um chloride and the corresponding hydroxides thereof.
  • Further suitable cationic surfactants include those materials having the CTFA designations Guaternium-5. Quatemium-31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable.
  • a particularly useful cationic surfactant for use in conditioners according to the invention is cetyit ⁇ methyiammonium chloride, available commercially, for example as GENAMIN CTAG. ex Hoechst Gelanese.
  • Another particularly useful cationic surfactant for use in conditioners according to the invention is behenyltrimethylammonium chloride, available commercially, for example as GENAMIN KDMP, ex Ciariant
  • amidoammes Another example of a class of suitable cationic surfactants for use in the invention, either alone or in admixture with one or more other cationic conditioning surfactants, are amidoammes.
  • Preferred amidoammes useful herein include sfearamido-propyidimethylamine, stearamidopropyidielhyiamine, stearamidoethyldiethylamine, stearamidoethyldimethyiamine, palmitamido- propyidimelhyiamsne. palmit-amidopropyidiethylamine, palmitamidoethyldiethylamine, palmitamido-ethyldimethylamine.
  • behenamidopropyldimethylarnine behenamido-propyldiethylmine, behenamidoethyidiethyiamine, behenamidoethyidimethylamine, arachidamidopropyidimethylamine, arachidamidopropyldiethylamine, arachid- amidoethyidielhyiamine, arachidamidoelhyidimethyiami ⁇ e, and mixtures thereof.
  • amsdoamsnes useful herein are stearamidopropyidimethylamine. stearamidoethyldiethylamine, and mixtures thereof.
  • amidoammes useful herein include: stearamidopropyidimethylamine with tradenames LEXAMiNE S-13 available from Index (Philadelphia Pennsylvania, USA) and AMiDOAMINE MSP available from Nikko (Tokyo, Japan), sfearamidoethyidiethyiamine with a tradename AMSDOAMSNE S available from Nikko, behenamidopropyldimethylamine with a lradename INCROMINE BB available from Croda (North Humberside, England), and various amidoamines with tradenames SCHERCODINE series available from Scher (Ciiflon New Jersey, USA).
  • the level of cahonic surfaclant in hair conditioning products will generally range from 0.01 to 10%, more preferably 0.02 to 7.5%, most preferably 0.05 to 5% by total weight of cationic surfactant based on the total weight of the composition.
  • benefit agents can be incorporated using this invention.
  • Preferred benefit agents include perfumes, lubricants any other oily materials.
  • Particularly preferred benefit agents include, but not limited to, the following:
  • silicone oils resins, and modifications thereof such as linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 cst;
  • perfume components including fragrance, perfumery, and essential oils and resins
  • photo-active materials including dyes and pigments, including inorganic compounds with hydrophobically-modified surface and/or dispersed in an oil or a hydrophobic liquid, also including fluorescing agents: for example: 2,5-bis(2-benzoxazolyl) thiophene for use on fabrics (such as cotton, nylon, polycotton or polyester) in laundry products; UV protecting agents: such as sunscreens for example: octyl methoxycinnamate (Parsol MCX), butyl methoxydibenzoylmethane (Parsol 1789) and benzophenone-3 (Uvinul M- 40), and ferulic acid, organic sunscreen actives, for example, octylmethoxy cinnamate; d) antimicrobial agents, for example, 2-hydroxy-4,2,4-trichlorodiphenylether; antidandruff agents: for example: zinc pyhthione;
  • ester solvents for example, isopropyl myristate
  • lipids and lipid like substance for example, cholesterol; fish and vegetable oils, hydrophobic plant extracts; waxes;
  • hydrocarbons such as paraffins, petrolatum, and mineral oil
  • pre-encapsulated materials e.g. perfume encapsulates
  • perfume components include both odiferous materials and pro-fragrance materials whether encapsulated or not.
  • oily materials used as carriers for minor amounts of oil-soluble benefit agents, i.e. in amounts of less than 50%wt of the carrier.
  • oil soluble benefit agents include hydrophobic dyes and other hydrophobic actives such as agrochemicals.
  • the pro-fragrance can, for example, be a food lipid.
  • Food lipids are oily materials and typically contain structural units with pronounced hydrophobicity. The majority of lipids are derived from fatty acids. In these 'acyl' lipids the fatty acids are predominantly present as esters and include mono-, di-, triacyl glycerols, phospholipids, glycolipids, diol lipids, waxes, sterol esters and tocopherols.
  • plant lipids comprise antioxidants to prevent their oxidation. While these may be at least in part removed during the isolation of oils from plants some antioxidants may remain. These antioxidants can also be pro-fragrances.
  • the carotenoids and related compounds including vitamin A, retinol, retinal, retinoic acid and provitamin A are capable of being converted into fragrant species including the ionones, damascones and damscenones.
  • Preferred pro- fragrance food lipids include olive oil, palm oil, canola oil, squalene, sunflower seed oil, wheat germ oil, almond oil, coconut oil, grape seed oil, rapeseed oil, castor oil, corn oil, cottonseed oil, safflower oil, groundnut oil, poppy seed oil, palm kernel oil, rice bran oil, sesame oil, soybean oil, pumpkin seed oil, jojoba oil and mustard seed oil.
  • Perfume components which are odiferous materials are described in further detail below.
  • the perfume is typically present in an amount of from 10-85% by total weight of the particle, preferably from 20 to 75% by total weight of the particle.
  • the perfume suitably has a molecular weight of from 50 to 500.
  • Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by
  • perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
  • Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
  • Typical perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius.
  • perfume components which have a low LogP (i.e. those which will be partitioned into water), preferably with a LogP of less than 3.0.
  • materials, of relatively low boiling point and relatively low LogP have been called the "delayed blooming" perfume ingredients and include the following materials:
  • AIIyI Caproate Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisole,
  • perfume components it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the encapsulated perfume.
  • perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. By means of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed linen). As noted above the core of the particles of the present invention can itself be an encapsulated perfume such a melamine/urea/formaldehyde encapsulate.
  • the present invention can be used to "improve" leaky capsules by adding a further layer which is impervious to the perfume.
  • the further layer PVOH and surfactant
  • the capsules can then release perfume over a period of time and/or, in the case of laundry, when garments are worn and the capsules are crushed.
  • the present invention can be employed to encapsulate pre-encapsulated benefit agents (such as perfumes) which have been, in their first encapsulation, provided with a cationic capsule.
  • cationic capsules are believed to show better deposition on, for example, cloth than uncharged capsules. However, they show negative interactions with anionic surfactants. By further encapsulating these capsules according to the present invention these unwanted interactions can be reduced.
  • Dyes are a benefit agent which may be present in the particles as an alternative to or in addition to perfumes. Dyes are typically present at levels which make them effective as hueing (shading) dye.
  • the hueing dye is preferably blue or violet. Suitable and preferred hueing dyes are those described in WO05/003274, WO06/032327, WO 06/032397, EP08167033, WO 06/045375, WO 06/053598 and WO 08/017570. Mixtures of hueing dyes may be used.
  • hueing dyes are cationic thiazolium dyes, cationic isothiazolium dyes, cationic azine dyes, cationic pyridine/pyridazine dyes, acid azine dyes, hydrophobic anthraquinone dyes and hydrophobic azo dyes.
  • the most preferred hueing dyes are those selected from: Direct Violet 9; Direct Violet 35; Direct Violet 51 ; Direct Violet 99; Acid Violet 50; Disperse Violet 28 and, Solvent Violet 13.
  • the dyes may be present as an additional adjunct either within the capsule or in the bulk of the product.
  • the benefit agent may itself be a surfactant or may include a surfactant.
  • the benefit agent may be a cationic surfactant which is prevented from interacting with anionic surfactant in the bulk of the product by the shell formed around it.
  • suitable such cationic surfactants are water soluble cationic species having at least one alkyl or alkenyl chain. It is preferable that the sum of the length of the alkyl chains is less than 20.
  • Preferred cationic surfactants are: quaternary ammonium compounds having single long-chain aliphatic groups. Cetylthmethylammonium chloride is particularly preferred.
  • the benefit agent may comprise a silicone, preferably as a conditioning agent, especially for products suitable for use in hair and skin products.
  • silicone conditioning agents may be present in the bulk of the composition.
  • Particularly preferred silicone conditioning agents are silicone emulsions such as those formed from silicones such as polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone, polydimethyl siloxanes having hydroxyl end groups which have the CTFA designation dimethiconol, and amino-functional polydimethyl siloxanes which have the CTFA designation amodimethicone.
  • silicone emulsions in which certain types of surface active block copolymers of a high molecular weight have been blended with the silicone emulsion droplets, as described for example in WO03/094874.
  • the silicone emulsion droplets are preferably formed from polydiorganosiloxanes such as those described above.
  • One preferred form of the surface active block copolymer is according to the following formula:
  • the above-described silicone will generally be present in a composition of the invention at levels of from 0.05 to 15%, preferably from 0.5 to 12% by total weight of silicone based on the total weight of the composition.
  • hydrophobic benefit agents can be envisaged.
  • Many agrochemical materials are hydrophobic and maybe potentially hazardous in use. Such materials can be present as a solution in an oily material which forms the core of the particles according to the present invention. The presence of the surfactant stabilized shell around these cores is believed to retard the release of these materials until the composition is diluted, preferably just prior to use, thus reducing unwanted exposure.
  • Specific water-insoluble agrochemical materials with a solubility of less than or equal to 200mg/L include: Gamma-cyhalothrin, Deltamethrin, Fluvalinate, Fenvalerate, Esfenvalerate, Flucycloxuron, Cyfluthhn, Metaflumizone, Clofentezine, Bifenthrin, Novaluron, Alpha-cypermethrin, Flufenoxuron, Lambda- cyhalothrin, Acequinocyl, Cypermethrin, Zeta-cypermethhn, Ethalfluralin, Teflubenzuron, Pyhdaben, Cyflufenamid, Fenbutatin oxide, Tefluthrin, Chlorfluazuron, Acrinathrin, Etofenprox, Fenpyroximate, Hexaflumuron, Cyflumetofen, Flubendiamide, Bisthfluron, Dimethomorph, Th
  • the modification of the polymer can be accomplished by a range of known processes. For example in the manufacture of modified PVOH, an acidic solution of PVOH (preferably formed at a temperature of above 80 Celsius) is reacted at around 70 Celsius with an aldehyde/acetal (preferably added dropwise). After the addition of the components the reaction is allowed to proceed for several hours at STP.
  • suitable polymer materials are commercially available and include MowiflexTM LPFX 416 (ex Kuraray).
  • Particularly preferred embodiments of the present invention are main wash detergent compositions comprising an anionic surfactant.
  • the surfactants are preferably present in the composition at a level of from 1 % to 60% by weight.
  • Suitable anionic surfactants are well known to the person skilled in the art and include alkyl benzene sulphonate, primary and secondary alkyl sulphates, particularly C 8 -Ci 5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl sulphosuccinates; ether carboxylates; isethionates; sarcosinates; fatty acid ester sulphonates and mixtures thereof.
  • the sodium salts are generally preferred.
  • the composition usually contains from about 1 % to about 50%, preferably 10 wt%-40 wt% based on the fabric treatment composition of an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
  • an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
  • Preferred surfactants are alkyl ether sulphates and blends of alkoxylated alkyl nonionic surfactants with either alkyl sulphonates or alkyl ether sulphates.
  • Preferred alkyl ether sulphates are C8-C15 alkyl and have 2-10 moles of ethoxlation.
  • Preferred alkyl sulphates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of Cs-Ci 5 .
  • the counter ion for anionic surfactants is typically sodium, although other counter-ions such as TEA or ammonium can be used. Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'TM range from Clariant. In these preferred embodiments the benefit agent is selected from:
  • the particles in solution were imaged using a Olympus BX-41 optical microscope fitted with a digital camera. Images were captured using the Olympus Cell P software which allows particle sizes to be measured. 2. The particles were air-dried onto a non-absorbent surface and imaged in a Hitachi TM-1000 desktop scanning electron microscope. The particle size was determined using the length scale added to the image by the associated software.
  • the perfume, water and Oil Red EGN are mixed using a high-speed stirrer for 20 minutes (1200rpm, Jiffy® stirrer). The temperature is then elevated to 55°C using a water bath and the product is mixed for a further 10 minutes. 10ml of a 20% active solution of linear alkyl benzene sulphonate (LAS) are added. The product is mixed for a further 10 minutes @ 800rpm then allowed to cool to room temperature with stirring over a period of 20 minutes @ 800 rpm.
  • LAS linear alkyl benzene sulphonate
  • the perfume, water and Oil Red EGN are mixed using high-speed stirrer for 10 minutes (1200rpm, Jiffy® stirrer).
  • the Mowiflex LPFX 416 is added and stirring continued for a further 10 minutes.
  • the temperature is then elevated to 55°C using a water bath and mixing continued for a further 10 minutes.
  • 10ml of a 20% active solution of linear alkyl benzene sulphonate (LAS) is added and mixing continued for a further 10 minutes @ 800 rpm.
  • the product is allowed to cool to room temperature with stirring over 20 minutes @ 800 rpm.
  • control solution (1a) had a pronounced red layer of free perfume and dye.
  • the solution containing Mowiflex (1 b) was still homogeneous.
  • Clariant was dispersed in 46.5ml of demin water at 50 0 C. The solution was then cooled to 20 0 C and 0.5ml of AKK model perfume added. The solution was then stirred using a high-speed stirrer for 10 minutes. The solution was then warmed to 60°C and stirred for a further 10 minutes. 1.25ml of a 20% linear alkyl benzene sulphonate (LAS) solution was then added and the solution stirrer for a further 10 minutes. The solution was then cooled to 20 0 C and stirred over a further 20 minutes.
  • LAS linear alkyl benzene sulphonate
  • the solution containing the modified PVOH was translucent with clearly dispersed encapsulates visible under light microscopy.
  • the control solution was opaque with few encaps. After 24 hours, the control solution exhibited both sedimentation and creaming, neither of which was present in the solution containing the modified PVOH.
  • the presence of the modified PVOH effectively screens the cationic charge on the encapsulate from the anionic surfactant, thus making it stable in anionic-hch detergent products.
  • Example 5 Dye as Benefit Agent is a Range of Products
  • the benefit agent selected was Solvent Violet 13, a cosmetic grade hydrophobic dye, which is suitable for use as a fabric shading agent.
  • the dye (0.1 g) was mixed with 10ml of mineral oil (white, light, ex Sigma Aldrich, CAS No. 8042-47-5) until fully dissolved.
  • Product samples comprising encapsulated SV13 were obtained as follows: 50OuI of oil/SV13 was dispersed in 50ml of demin water using a Jiffy stirrer @ 1200rpm for 10 minutes. The solution was then heated to 50 0 C, 10ml of 20% LAS solution was added and the stirring speed reduced to 800rpm. After 3 minutes, the solution was cooled to 20 0 C with stirring at 800rpm.
  • Product samples comprising encapsulated SV13 were obtained as follows: 50OuI of oil/SV13 was dispersed in 32ml of demin water using a Jiffy stirrer @ 1200rpm for 5 minutes.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

L'invention porte sur une composition comprenant 1-99 % en poids de tensioactif et au moins une microparticule ayant un diamètre de 100 nm-2 mm, ladite microparticule comprenant : i) un cœur comprenant un agent bénéfique hydrophobe (de préférence un parfum ou un colorant) et ii) une enveloppe comprenant un polymère filmogène hydrosoluble modifié de façon hydrophobe non chargé (de préférence un PVOH modifié), le film restant pratiquement intact en présence de tensioactif mais se dissolvant lorsque la concentration de tensioactif est réduite, ce qui libère de cette manière l'agent bénéfique. L'invention porte sur un procédé pour le traitement de surfaces comprenant l'étape consistant à mettre en contact une composition selon l'invention avec un tissu, des cheveux ou un tissu vivant. L'invention porte également sur un procédé pour la fabrication de compositions selon les revendications 1-13 qui comprend les étapes consistant à : a) se procurer une solution aqueuse de polymère filmogène modifié de façon hydrophobe non chargé ayant un agent bénéfique hydrophobe dispersé dans celui-ci, b) former une couche du polymère filmogène modifié de façon hydrophobe non chargé autour de l'agent bénéfique hydrophobe dispersé et c) stabiliser ladite couche avec un tensioactif.
PCT/EP2009/059046 2008-08-08 2009-07-15 Microcapsules dans des compositions contenant un tensioactif WO2010015493A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES09780617T ES2402486T3 (es) 2008-08-08 2009-07-15 Microcápsulas en composiciones que contienen tensioactivos
BRPI0917442A BRPI0917442A2 (pt) 2008-08-08 2009-07-15 composições compreendendo tensoativo e microcápsulas, processo para o tratamento de superfícies, e, método para preparar composições
CN200980140032.9A CN102177232B (zh) 2008-08-08 2009-07-15 含表面活性剂的组合物中的微胶囊
EP09780617A EP2307536B1 (fr) 2008-08-08 2009-07-15 Microcapsules dans des compositions contenant un tensioactif
ZA2011/00600A ZA201100600B (en) 2008-08-08 2011-01-24 Microcapsules in surfactant-containing compositions

Applications Claiming Priority (2)

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GB0814423.0 2008-08-08
GB0814423A GB0814423D0 (en) 2008-08-08 2008-08-08 Improvements relating to surfactant-containing compositions

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CN (1) CN102177232B (fr)
AR (1) AR072921A1 (fr)
BR (1) BRPI0917442A2 (fr)
ES (1) ES2402486T3 (fr)
GB (1) GB0814423D0 (fr)
TW (1) TW201012542A (fr)
WO (1) WO2010015493A1 (fr)
ZA (1) ZA201100600B (fr)

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CN102198117A (zh) * 2011-06-17 2011-09-28 中国林业科学研究院林产化学工业研究所 一种温敏性高分子微胶囊及其制备方法和应用
WO2014075956A1 (fr) * 2012-11-19 2014-05-22 Unilever Plc Améliorations se rapportant à des agents bénéficiants encapsulés
WO2015014792A1 (fr) * 2013-07-30 2015-02-05 Unilever N.V. Améliorations concernant des agents avantageux encapsulés
US10047329B2 (en) 2013-09-27 2018-08-14 Rohm And Haas Chemicals Llc Water dispersible films for packaging high water containing formulations
US10400114B2 (en) 2013-09-27 2019-09-03 Rohm And Haas Company Ionic strength triggered disintegration of films and particulates
US10881593B2 (en) 2013-10-04 2021-01-05 The Procter & Gamble Company Benefit agent containing delivery particle
CN113693078A (zh) * 2021-10-28 2021-11-26 潍坊新绿化工有限公司 一种含莎稗磷的除草剂、制备方法及其应用
US11680232B2 (en) 2017-02-06 2023-06-20 The Procter & Gamble Company Laundry detergent sheet with microcapsules

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CN112280401A (zh) * 2020-10-30 2021-01-29 湖南圣人防水材料有限公司 一种具抑霉作用的加强型防水涂料的制备方法
CN115110094A (zh) * 2021-03-18 2022-09-27 江苏筑磊电子科技有限公司 一缩二丙二醇在火灾后金属表面处理的方法

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WO2003068852A1 (fr) * 2002-02-14 2003-08-21 National Starch And Chemical Investment Holding Coporation Matériaux à libération contrôlée
WO2003087287A1 (fr) * 2002-04-10 2003-10-23 Salvona L.L.C. Compositions a liberation controlee ciblee activees par des modifications du ph ou de la concentration en sel
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CN102198117B (zh) * 2011-06-17 2013-02-27 中国林业科学研究院林产化学工业研究所 一种温敏性高分子微胶囊及其制备方法和应用
CN102198117A (zh) * 2011-06-17 2011-09-28 中国林业科学研究院林产化学工业研究所 一种温敏性高分子微胶囊及其制备方法和应用
US9321987B2 (en) 2012-11-19 2016-04-26 Conopco, Inc. Encapsulated benefit agents
WO2014075956A1 (fr) * 2012-11-19 2014-05-22 Unilever Plc Améliorations se rapportant à des agents bénéficiants encapsulés
JP2016532546A (ja) * 2013-07-30 2016-10-20 ユニリーバー・ナームローゼ・ベンノートシヤープ カプセル封入有益剤に関する改良
CN105408016A (zh) * 2013-07-30 2016-03-16 荷兰联合利华有限公司 与包封的有益剂相关的改善
WO2015014792A1 (fr) * 2013-07-30 2015-02-05 Unilever N.V. Améliorations concernant des agents avantageux encapsulés
US10117815B2 (en) 2013-07-30 2018-11-06 Conopco, Inc. Improvements relating to encapsulated benefit agents
US10047329B2 (en) 2013-09-27 2018-08-14 Rohm And Haas Chemicals Llc Water dispersible films for packaging high water containing formulations
US10400114B2 (en) 2013-09-27 2019-09-03 Rohm And Haas Company Ionic strength triggered disintegration of films and particulates
US10881593B2 (en) 2013-10-04 2021-01-05 The Procter & Gamble Company Benefit agent containing delivery particle
US11680232B2 (en) 2017-02-06 2023-06-20 The Procter & Gamble Company Laundry detergent sheet with microcapsules
CN113693078A (zh) * 2021-10-28 2021-11-26 潍坊新绿化工有限公司 一种含莎稗磷的除草剂、制备方法及其应用

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CN102177232B (zh) 2013-03-27
GB0814423D0 (en) 2008-09-10
EP2307536B1 (fr) 2013-02-13
EP2307536A1 (fr) 2011-04-13
TW201012542A (en) 2010-04-01
ES2402486T3 (es) 2013-05-06
CN102177232A (zh) 2011-09-07
AR072921A1 (es) 2010-09-29
ZA201100600B (en) 2012-05-01
BRPI0917442A2 (pt) 2015-12-01

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