CN102177232B - Microcapsules in surfactant-containing compositions - Google Patents
Microcapsules in surfactant-containing compositions Download PDFInfo
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- CN102177232B CN102177232B CN200980140032.9A CN200980140032A CN102177232B CN 102177232 B CN102177232 B CN 102177232B CN 200980140032 A CN200980140032 A CN 200980140032A CN 102177232 B CN102177232 B CN 102177232B
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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
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Abstract
A composition comprising, 1-99%wt of surfactant and at least one micro-particle having a diameter of 100nm-2mm, said micro-particle comprising: i) a core comprising a hydrophobic benefit agent (preferably a perfume or a dye), and, ii) a shell comprising an uncharged hydrophobically-modified, water-soluble film-forming polymer (preferably a modified PVOH), whereby the film remains substantially intact in the presence of surfactant but dissolves when the concentration of surfactant is reduced, thereby releasing the benefit agent. The invention provides a process for treatment of surfaces comprising the step of contacting a composition according to the invention with fabric, hair, or living tissue. The invention also provides a method for preparing compositions according to claims 1-13 which comprises the steps of: a) providing an aqueous solution of uncharged, hydrophobically-modified, film forming polymer having a hydrophobic benefit agent dispersed therein, b) forming a layer of the uncharged, hydrophobically-modified, film forming polymer around the dispersed hydrophobic benefit agent, and c) stabilizing said layer with surfactant.
Description
Technical field
The present invention relates to comprise the composition that contains tensio-active agent and its purposes of the particle that contains useful reagent, especially as detergent for washing clothes or fabric conditioner product.The present invention also is applicable to as being suitable for using at fur and crust those of other product that contains tensio-active agent.
Background technology
The present invention will be that perfume compound, dyestuff and cats product are described with reference to beneficial agent especially.
Perfume compound is that laundry detergent composition contains the important and expensive component of the product of tensio-active agent with other.Importantly guarantee during the processing of composition or do not lose perfume compound during storage and they are deposited on the article and surface that are washed.Because volatility, perfume compound is easy to evaporate from composition, if when said composition is subject to high temperature especially.The method that deposits fragrance components and other beneficial agent from the composition that contains tensio-active agent is different and perfume compound usually is incorporated in carrier or other delivery system.The carrier system of perfume compound is typically based on perfume compound is encapsulated or is trapped in the matrix.Perfume compound can be by simply emulsification, usually is inefficient and can occurs keeping or the problem of poor stability but deposit on substrate such as fabric, skin or the hair.By being diffused into, perfume compound prepares the substrate deposition that material may lock into preparation reservation complicated, for a long time diffusion, the difference of perfume compound in matrix and difference subsequently in the carrier.
As the method that addresses these problems, advised the perfume compound encapsulation.EP 332175 (Lion, 1988) disclose the method for producing the water-insoluble microcapsule, comprised mixing (i) aqueous dispersion, it comprises capsule, this capsule has the wall film, comprises PVOH and contains the electrolytical aqueous solution and the step that (ii) comprises the linking agent of aldehyde.Ionogen is stablized until the wall film is crosslinked capsule.These particles are for washing and being stable in aqueous dispersion.
Commercially available perfume compound encapsulant based on the aminoplastics material and can with the cationic materials modification improve the surface such as the deposition on the textiles.If use in comprising the environment of anion surfactant as capsule, these charged capsules suffer that difficulty and tensio-active agent will interact.
Polyvinyl alcohol (PVOH) has been used to form water-soluble pouch, and it comprises cats product.WO 2004/031271 discloses polyvinyl alcohol (PVOH) pouch of modification, and it is that the film of 50-500 micron centers on by preferred mean thickness.Pouch preferably comprises the material of 0.5ml-100ml such as the laundry amendment.
GB 0803165.0 (applying date is on February 8th, 2008) discloses a kind of microcapsule, its diameter is less than 2mm, comprise: (a) beneficial agent (such as perfume compound), and (b) with the water-soluble polymers film forming material of hydrophobic grouping and the first charged deriveding group modification.Film: in the presence of tensio-active agent, basically keep complete, and when the concentration of tensio-active agent fully reduces, decompose, thus releasing beneficial reagent.
Dyestuff is many another useful components that contain the composition of tensio-active agent.For example, in laundry composition, dyestuff can be used as " shading " or " toning " agent.Dyestuff may reside in the hair products in order to make coloring hairs.As perfume compound, dyestuff is difficult to deposit from surfactant composition, because tensio-active agent has auxiliary article or surperficial tendency of removing dyestuff from just being washed.The situation of many other beneficial agents also is the same.
Summary of the invention
We have determined hydrophobically modified polymers (especially modified polyvinyl alcohol (mPVOH)), it does not have the charged deriveding group that is required by GB 0803165.0, can be used for applying the microparticle and these particles that comprise beneficial agent, although stable under the high surface agent concentration, releasing beneficial reagent under low surfactant concentration.These microparticles are much smaller than the pouch of WO 2004/031271 and be different from crosslinked, the water-insoluble particle of EP 332175, do not need to pulverize to discharge its content.
Therefore, a first aspect of the present invention provides a kind of composition, and it comprises that the tensio-active agent of 1-99wt% and at least a diameter are the microparticle of 100nm-2mm, and described microparticle comprises:
I) comprise the core of hydrophobic benefit reagent, and,
Ii) comprise shell uncharged hydrophobically modified, water miscible film-forming polymer, wherein film keeps complete basically in the presence of tensio-active agent, but dissolves when the concentration of tensio-active agent reduces, thus releasing beneficial reagent.
Preferably, the diameter of microparticle is the 1-1000 micron, more preferably 1-100 micron, most preferably 1-50 micron.
According to a further aspect of the present invention, provide a kind of for the preparation of the method according to composition of the present invention, it is made of following step:
A) provide the aqueous solution of the film-forming polymer of uncharged, hydrophobically modified, have the hydrophobic benefit reagent that is dispersed in wherein,
B) around the hydrophobic benefit reagent that disperses, form the layer of the film-forming polymer of uncharged, hydrophobically modified, and
C) stablize described layer with tensio-active agent.
In scope of the present invention, the ClogP of hydrophobic benefit reagent is greater than 0.5, is preferably more than 1 and more preferably greater than 2.Be not intended to be bound by theory, it is believed that when core and polymkeric substance compile, hydrophobic parts causes that polymkeric substance assembles at the interface at water-core.In particularly preferred embodiments, when the temperature of solution is enhanced the lower bound critical solution temperature (LCST that is higher than polymkeric substance, lower critical solution temperature) time, this coating crystallization becomes a part water insoluble and the formation shell.When adding suitable tensio-active agent, form other layer by the interaction between the hydrophobic parts on tensio-active agent and the polymkeric substance, produce thus the shell around core.When temperature drops to when being lower than LCST, it is stable that the surfactant and polymer shell keeps, and condition is to have enough tensio-active agents.In containing the product of tensio-active agent, shell is stable.Yet when diluted product, shell becomes unstable and beneficial agent is released.
Preferably, polymer-modified have:
A) in comprising greater than the water of one or more anionic/nonionic of the concentration of 1 grams per liter or cats product 20 ℃ solubleness or dispersiveness: less than 0.5 Grams Per Hour, and,
When b) concentration in water is less than 1 grams per liter when anionic/nonionic or cats product, solubleness or dispersiveness: greater than 0.5 Grams Per Hour.
When being applied to the beneficial agent of oily material such as the drop of free perfume oil, or even comprise the particle of pre-packaged perfume compound, carbamate or aminoplastics encapsulant (comprise especially, melamine-formaldehyde encapsulant) and during polyolefine encapsulant (comprise based on poly-(methyl) acrylate those), the present invention finds special practicality.Other oily materials that are fit to comprise having the oil-soluble colourant that are dispersed in wherein, or the oil of other beneficial agent.In preferred embodiments, the solubleness (at 20 ℃) of beneficial agent in water is less than 600mg/L, preferably less than 200mg/L.
The present invention can also be used for encapsulating charged material, and preferably cationic materials so that they can be added to the solution of the material that contains opposite charges, and does not cause flocculation/unstable.
Preferably, the hydrophobic deriveding group of polymkeric substance stems from ClogP greater than 0.5 fertile material.According to a further aspect of the present invention, provide a kind of method for the treatment of fabric, it comprises makes according to the step of composition of the present invention (with form pure or dilution) with clothing in contact.Should be noted in the discussion above that purposes of the present invention is not limited to laundry applications and can be used in other surface as on hair or the living tissue surface.The present invention can be used for stable and sends from any significantly hydrophobic benefit reagent of the system that contains tensio-active agent of dilution that will experience during use.Therefore, the present invention further provides a kind ofly for the surface-treated method, it comprises makes according to composition of the present invention (with form pure or dilution) and the step of Surface Contact.
Embodiment
In order further to understand the present invention, below described with particular reference to the preferred feature of specific factor of the present invention.
Polymkeric substance
The all or part of polymkeric substance of main chain that is suitable for use as the water-soluble polymers of hydrophobically modified preferably is selected from polyvinyl alcohol, polyvinyl acetate, ether of cellulose, polyoxyethylene, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene-maleic anhydride, Natvosol, methylcellulose gum, polyoxyethylene glycol, Cellulose,ether with glycolic acid, polyacrylate, alginate esters or salt, acrylamide copolymer, guar gum, casein, ethene-maleic anhydride resin series, polymine, Type 3U, ethylmethylcellulose and hydroxyethylmethyl-cellulose.Copolymer mixture derived from the polymkeric substance of above-mentioned main chain also is suitable.Preferably, water-soluble polymers has the main chain that comprises pendant hydroxyl group.
The most preferred main chain of water-soluble polymers comprises polyvinyl alcohol (PVAc), and preferably molecular-weight average is 10kD to 300kD, preferably 20kD to 200kD, most preferably 75kD to 175kD.
Polyvinyl alcohol (PVOH) can provide with the form that comprises a certain amount of polyvinyl acetate (PVAc), and wherein the hydroxyl (OH) of the PVOH material of certain level is replaced by acetate moiety group (OCOCH3).The hydrolysis of PVAc is the common methods for the preparation of PVOH.Yet, realize that completely hydrolysis is only at the most about 99% hydrolysis of material high price and typical.Therefore, PVOH used herein generally includes some PVAc.PVOH material (hydrophobic modified before or after) can comprise 0.01 to 40%PVAc, preferably 0.01 to 20%, more preferably 0.1 to 15%, most preferably 0.5 to 10%, and based on the per-cent of the sum of the monomer that consists of polymkeric substance.As used in this article, term PVOH comprises the PVOH compound of the PVAc level that has as defined above.In this respect, referring to material is that the uncharged PVOH of referring to comprises uncharged deriveding group, as being needed by GB 0803165.0, is not that it does not contain remaining PVAc.
Preferably, polymer-modified average hydrolysis degree is 70-99%.Preferably, polymer-modified have according to DIN 53 015 measure 20 ℃ 1 to 100mPa.s viscosity, by 4% solution.
As mentioned above, water-soluble polymers is modified and comprises hydrophobic substituent.Preferred hydrophobicity deriveding group comprises based on those of the precursor group that is selected from acetal, aldehyde, ketal, ester, fluorinated organic compounds, ether, alkane, alkene and aromatic substance.Highly preferred hydrophobic substituent is the hydrocarbyl group of C4 to C22 carbon chain lengths.These hydrocarbyl groups can be based on alkyl or alkenyl, and it can be straight chain, branching or comprise ring; It also can or alternatively introduce the aromatics part.
More preferably, hydrocarbyl group has C4 to C20, C4 to C15 more preferably, and C4 to C10 most preferably, for example, the carbon chain lengths of C4 to C8.
Hydrocarbyl chain length greater than C22 is undesirable, because react relatively poor or reaction by the fertile material that wherein obtains deriveding group and main polymer chain.The hydrocarbyl group that is shorter than C4 provides inappreciable other hydrophobicity.
The particularly preferred material that is applicable to the hydrophobicity deriveding group is incorporated on the water-soluble polymers is aldehyde such as butyraldehyde, octanal, dodecyl aldehyde, 2-ethyl hexanal, hexanaphthene formaldehyde, citral and 4-amino butyraldehyde dimethyl acetal (4-aminobutyraldehyde dimethyl acetal).
Based on the gross weight of polymkeric substance, hydrophobic material is preferably with 0.1 to 40wt%, and more preferably 2 to 30%, most preferably 5 to 15% level is present in the polymkeric substance.
When wherein main polymer chain was based on polyvinyl alcohol, the hydrophobicity derived material preferably existed with such level, so that the right number ratio of the free hydroxyl group on hydrophobic grouping and the main chain is 1:3 to 1:30, and more preferably 1:4 to 1:20, most preferably 1:7 to 1:15.
The variation of the level of deriving of polymkeric substance makes it possible to the performance of modification shell so that shell will discharge the material in the core under the especially level of tensio-active agent.Therefore, can prepare shell, it is stable in containing the product of tensio-active agent, but that the level of the tensio-active agent that it exists in washings becomes is unstable (for example, its in the main washing of laundry processes or become during with this product treatment skin or hair in the presence of the water unsettled).Such system can help the stability at the beneficial agent of product memory period.In alternatives, shell can be stable washings, but during processed surface or article flushing washings, become unstable.Therefore, can form particle, it is releasing beneficial reagent during flushing process, and reduce the trend that beneficial agent is removed by tensio-active agent.May reside in more than one type particle and to prevent for example interaction of opalizer (itself otherwise may interact) of component in the given product.
Other film composition
For water-soluble film, maybe advantageously provided by the material with partial cross-linked polymer architecture.Yet crosslinked level should be held low in order to avoid forming insoluble material.Preferably, the material of making film is not crosslinked at all.
Specially suitable linking agent comprises formaldehyde; Polyester; Epoxide, amido amine, acid anhydrides, phenol; Isocyanic ester; Vinyl ester; Carbamate; Polyimide; Acrylic acid or the like; Two (methacryloxy (methacrylkoxy) propyl group) tetramethyl-silica alkane (vinylbenzene, β-dimethyl-aminoethylmethacrylate (ethylmethacrylate)); N-diazonium pyruvate; Phenyl-boron dihydroxide (phenyboronic acids); Cis-platinum; Vinylstyrene; Polymeric amide; Dialdehyde; Triallyl cyanurate; N-(2-ethane alkylsulfonyl ethyl) pyridinium halide; Tetralkyl titanate (tetraalkyltitanate); The mixture of titanate and borate or zirconate; Cr, Zr, the polyvalent ion of Ti; Dialdehyde, diketone; The alcohol complex of organic titanate/salt, zirconate/ester (zircoates) and borate/ester and copper (II) complex compound.For PVOH type film, preferred linking agent is quasi-metal oxide such as borate, tellurate, arsenate and its precursor.Other known linking agent comprises vanadyl (vanadyl) ion, the titanium ion of positive trivalent, or high manganese ion (being disclosed among the patent US 3,518,242).Alternative linking agent provides in Books: Polyvinylalcohol-Properties and applications, Chapter 9 by CA. Finch (John Wiley; Sons, New York, 1973).
Film can be in conjunction with softening agent and/or degree of crystallinity disrupting agent.Should will be appreciated that term " softening agent " and phrase " degree of crystallinity disrupting agent " are interchangeable, so that mention that one is that implicit expression is mentioned another.
For the mPVOH film, water itself is suitable softening agent, but other common softening agent comprises: polyol, glycerine for example, TriMethylolPropane(TMP), glycol ether, triglycol, Sorbitol Powder, dipropylene glycol, polyoxyethylene glycol; Starch, starch ethers for example, esterification starch, Sumstar 190 and from the starch of potato, cassava and wheat; Mierocrystalline cellulose/carbohydrate, for example amylopectin, dextrin, carboxymethyl-Mierocrystalline cellulose and pectin.Amine is particularly preferred softening agent.
For mPVP type film, suitable softening agent can be selected from lower one or more: phosphoric acid ester is tri-2-ethylhexyl phosphate for example, p isopropylbenzoic acid base diphenyl ester, tributyloxyethyl phosphate (tributoxyethylphosphate); Polyvalent alcohol is glycerine for example, Sorbitol Powder, two n-nonanoic acid glycol ether esters (diethylene glycol diperlargonate), poly-two-2 ethyl hexanoic acid glycol ester, dibutyl tartrate; Polyol ester is the polycaprolactone of hydroxyl for example, the PLLA of hydroxyl; Rudimentary phthalic ester is dimethyl phthalate for example, diethyl phthalate, dibutyl phthalate; With sulphonamide toluol sulfonamide for example, N-ethyltoluene sulphonamide.
For mPEO type film, suitable softening agent can be selected from lower one or more: phosphoric acid ester is tri-2-ethylhexyl phosphate for example, p isopropylbenzoic acid base diphenyl ester, tributyloxyethyl phosphate (tributoxyethylphosphate); Polyvalent alcohol is glycerine for example, Sorbitol Powder, two n-nonanoic acid glycol ether esters (diethylene glycol diperlargonate), poly-two-2 ethyl hexanoic acid glycol ester, dibutyl tartrate; Rudimentary phthalic ester is dimethyl phthalate for example, diethyl phthalate, dibutyl phthalate; With sulphonamide toluol sulfonamide for example, N-ethyltoluene sulphonamide.
The package surface promoting agent
The tensio-active agent that is used for forming the gel barrier with film is anionic preferably, although nonionic or cats product can use.Be used for detergent for washing clothes such as fruit granule, used tensio-active agent preferentially is negatively charged ion or non-ionic.The negatively charged ion product also typically is used for hair and/or skin-cleaning composition.Be used for the rinsing clothes amendment such as fruit granule, so tensio-active agent positively charged ion or non-ionic preferably.Equally, cats product typically is used for the hair-conditioning product.
Suitable anion surfactant is: linear alkylbenzene sulfonate (LAS, linear alkyl benzene sulphonate), primary alkyl sulfuric acid (PAS, primary alkyl sulphate), fatty ether sulfuric acid (LES, fatty ether sulphates), secondary paraffin sulfonate (secondary alkane sulphonate), sulfonated α-olefin (α-olefin sulphonate), alpha-sulfo fatty acid methyl ester (α-sulphonic fatty acid methyl ester), methyl ester sulfonate (MES, methyl ester sulphonates).Preferred tensio-active agent is LAS, PAS, LES, and its mixture.Preferred material comprises fatty alcohol sulphuric acid ester sodium salt (sodium fatty alcohol sulphate), fatty alcohol sulphuric acid ester ammonium salt (ammonium fatty alcohol sulphate), alcohol ether sulfuric ester ammonium salt (ammonium alcohol ether sulphate), aliphatic ether sulfuric ester sodium salt (sodium fatty ether sulphate), alcohol ether carboxylate (alcohol ether carboxylate) and nonylphenol polyoxy ethyleneether carboxylate salt (nonylphenol polyoxyethylene ether carboxylate).The most preferred tensio-active agent that is used for laundry composition is LAS.
Suitable ionic surfactant pack is drawn together straight chain and the branched-chain alcoho of ethoxylation, the alkylphenol of ethoxylation, fatty acid ester, amine and amide derivatives, APG, Pluronic PE 6800, polyvalent alcohol and ethoxylation polyvalent alcohol.
For hair and skin products, existing tensio-active agent preferably has 8-14 carbon, more preferably 10-12 and the most preferably anion surfactant of 12 carbon.More preferably, these carbon are present in the single alkyl.For hair and skin products, preferred anion surfactant comprises alkyl sulfuric ester an alkali metal salt (alkali metal alkyl sulphate), more preferably alkyl ether sulphate salts (alkyl ether sulphate).Particularly preferred negatively charged ion clean surface promoting agent comprises lauryl ether sulfuric ester sodium salt (sodium lauryl ether sulphate).Typically, the cleaning phase of hair or skin products (that is, except any conditioning or humidification mutually) comprises 27-70wt%, the clean surface promoting agent of 35-50wt% preferably, by composition.
In hair and skin condition product, preferred cats product has following formula: N
+(R
1) (R
2) (R
3) (R
4), R wherein
1, R
2, R
3And R
4(C16-C30) alkyl or benzyl independently.Preferably, R
1, R
2, R
3And R
4In 1,2 or 3 be (C16-C30) alkyl and other R independently
1, R
2, R
3And R
4Group is (C1-C6) alkyl or benzyl.Randomly, in alkyl chain, alkyl can comprise one or more esters (OCO-or-COO-) and/or ether (O-) key.Alkyl can randomly be replaced by one or more hydroxyls.Alkyl can be straight or branched and, for the alkyl with 3 or more carbon atoms, can be ring-type.Alkyl can be the saturated one or more carbon-to-carbon double bonds (for example oil base) that maybe can comprise.Alkyl randomly on alkyl chain by the ethoxylation of one or more ethyleneoxy group group.
Be used for comprising palmityl trimethyl ammonium chloride according to the suitable cats product of conditioner composition of the present invention, INCROQUAT TMC-80, pyrisept, tetramethyl ammonium chloride, etamon chloride, stearyl dimethyl benzyl ammonium chloride, cocoyl trimethyl ammonium chloride (cocotrimethylammonium chloride), PEG-2-ole ammonium chloride and its corresponding oxyhydroxide.Other suitable cats product comprises those materials with CTFA name Quaternium-5, Quaternium-31 and Quaternium-18.The mixture of any above-mentioned materials also may be suitable.The useful especially cats product that is used for according to amendment of the present invention is palmityl trimethyl ammonium chloride, the commercially available for example GENAMIN CTAG that derives from, Hoechst Gelanese.Another the useful especially cats product that is used for according to amendment of the present invention is INCROQUAT TMC-80, commercially available deriving from, for example, GENAMIN KDMP, Clariant.
One class is used for another example of suitable cats product of the present invention, randomly individually or with the form of mixing of one or more other cationic conditioning tensio-active agents, be amido amine.Useful preferred amido amine comprises SAPDMA in this article, the stearamide propyl diethylamide, stearylamide ethyl diethylamide, stearylamide ethyl dimethyl amine, the palmitic amide propyl-dimethyl amine, palmitic amide propyl group diethylamide, palmitic amide ethyl diethylamide, palmitic amide ethyl dimethyl amine, mountain Yu amido propyl dimethyl amine, mountain Yu amido propyl diethylamide, mountain Yu acid amides ethyl diethylamide, mountain Yu acid amides ethyl dimethyl amine, peanut amido propyl dimethyl amine, peanut amido propyl diethylamide, peanut acid amides ethyl diethylamide, peanut acid amides ethyl dimethyl amine, and its mixture.
Useful particularly preferred amido amine is SAPDMA in this article, stearylamide ethyl diethylamide, and its mixture.
Useful commercially available amido amine comprises in this article: SAPDMA, commodity are called LEXAMINE S-13, can be available from Inolex (Philadelphia Pennsylvania, the U.S.) and AMIDOAMINE MSP, can be available from Nikko (Tokyo, Japan), stearylamide ethyl diethylamide, commodity are called AMIDOAMINE S, can be available from Nikko, mountain Yu amido propyl dimethyl amine, commodity are called INCROMINE BB, can be available from Croda (North Humberside, Britain), and various amido amine, commodity SCHERCODINE series by name, can be available from Scher (Clifton New Jersey, USA).
The level of cats product will be generally 0.01-10% in the hair-conditioning product, 0.02-7.5% more preferably, and 0.05-5% most preferably is by the gross weight of cats product, based on the gross weight of composition.
Beneficial agent
Use the present invention, can introduce various beneficial agents.Preferred beneficial agent comprises perfume compound, lubricant, any other oily material.Particularly preferred beneficial agent includes but not limited to, below:
A) silicone oil, resin, and its variant such as straight chain and X 2-1401, amino-modification, allyl group (allcyl), aryl and alkylaryl silicone oil, it preferably has the viscosity greater than 50,000cst;
B) fragrance components comprises spices (fragrance), essence (perfumery) and volatile oil, and resin;
C) sensitive materials, comprise dyestuff and pigment, comprise and have hydrophobically modified surface and/or be dispersed in mineral compound in oil or the hydrophobic liquid, also comprise fluorescent agent: for example: in laundry product, be used for fabric (such as cotton, nylon, polyester cotton (polycotton) or polyester) on 2, two (2-benzoxazolyl) thiophene of 5-; UV protective material: such as opalizer for example: OMC (octyl methoxycinnamate) (Parsol MCX), butyl methoxydibenzoylmethise (Parsol 1789) and BP-3 (Uvinul M-40), and forulic acid (ferulic acid), organic sunscreen activity thing, for example, OMC (octylmethoxy cinnamate);
D) biocide, for example, 2-hydroxyl-4,2,4-three chlorodiphenyl ethers; Antidandruff agent: for example: oxygen mercaptopyridine zinc (zinc pyrithione);
E) skin lightening agent, for example 4-ethyl resorcinol;
F) ester solvent; For example, Isopropyl myristate;
G) lipid and lipid material, for example, cholesterol; Fish and vegetables oil, the hydrophobicity plant milk extract; Wax;
H) hydrocarbon such as paraffin, vaseline and mineral oil
I) pre-packaged material, for example perfume compound encapsulant;
J) with the tensio-active agent of package surface promoting agent opposite charges;
K) other medicinal and other bioactive compounds is such as biocides and agrochemicals.
Fragrance components is in most preferred beneficial agent.Fragrance components comprises fragrance materials and front fragrant material, no matter whether encapsulates.As the oily material (being that quantity is less than the carrier of 50wt%) of the carrier of the oil soluble beneficial agent of small amount also in preferred beneficial agent.Such oil soluble beneficial agent comprises hydrophobic dye and other hydrophobic active thing such as agrochemicals.
Front perfume (or spice) can for example be the food lipid.The food lipid is oily material and typically comprises and have remarkable hydrophobic structural unit.Most of lipid stems from lipid acid.In these " acyl group " lipids, lipid acid mainly exists and comprises list, two, triacylglycerol with the form of ester, phosphatide, glycolipid, glycol lipid, wax, sterol ester and tocopherol.In their state of nature, vegetable lipid comprises antioxidant in order to prevent its oxidation.Although these may be removed at least in part during separating oil from plant, some antioxidants may remain.These antioxidants also may be front perfume (or spice).Especially, carotenoid and relevant compound, comprise that vitamin A, Vogan-Neu, retinene, vitamin A acid and provitamin A can be converted into aromatoising substance, comprise ionone, trans-Damascenone (damascones) and damascone (damscenones).Fragrant food lipid comprises sweet oil, plam oil, Canola oil, squalene, wunflower seed oil, wheat germ oil, Prunus amygdalus oil, Oleum Cocois, wine stone oil, rapeseed oil, Viscotrol C, Semen Maydis oil, oleum gossypii seminis, Thistle oil, peanut oil, poppyseed oil, plam oil, Rice pollard oil, sesame oil, soybean oil, pumpkin-seed oil, Jojoba oil and tori seed oil before preferred.As further describing in detail below the fragrance components of fragrance materials.
Perfume compound as beneficial agent:
Perfume compound typically exists with following quantity, 10-85%, and by the gross weight of particle, preferably 20 to 75%, by the gross weight of particle.Perfume compound suitably has 50 to 500 molecular weight.
The useful component of perfume compound comprises the material in natural and synthetic source.They comprise individualized compound and mixture.The specific example of such component is found in the current literature, for example, and Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 author M. B. Jacobs, editor Van Nostrand; Or Perfume and Flavour Chemicals author S. Arctander 1969, Montclair, N.J. (USA).These materials are to make consuming product fragrance, add flavor and/or sweetening treatment, namely give smell and/or fragrance or taste to convention by the consuming product of fragrance or perfuming, or it is well-known to change the technician in field of the smell of described consuming product and/or taste.
Perfume compound not only refers to the product spices (fragrance) prepared fully in this respect, but also refers to the selected component of this spices (fragrance), and those that are easy to especially lose are such as so-called " head fragrant (tope notes) ".
Head is fragrant by following document definition: Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]).The fragrant example of well-known head comprises citrus oil, linalool, Linalyl acetate, lavender, dihydromyrcenol, rose oxide and suitable-3-hexanol.Head is fragrant typically to be accounted for the 15-25wt% of perfume composition and in those embodiments of the present invention that contain the head perfume that improves content, estimates that 20wt% will be present in the encapsulant at least.
Typical fragrance components, wherein advantageously with its encapsulation, comprise have more lower boiling those, preferably boiling point less than 300, those of 100-250 degree centigrade preferably.
Encapsulation has the fragrance components (that is, will being assigned in the water those) of low LogP also advantageously, preferably wherein LogP less than 3.0.These materials, than lower boiling and low LogP, be called as " postponing floating loose (delayed blooming) " perfume compound composition and comprise following material:
Pineapple aldehyde, amyl acetate-n, amyl propionate, aubepine, methyl-phenoxide, phenyl aldehyde, jasmal, benzyl acetone, phenylcarbinol, benzyl formate, benzyl isovalerate, benzyl propionate, β γ hexenol, camphor glue, L-CARVONE, the d-Karvon, styryl carbinol, formic acid cinnamyl (cinamyl) ester, suitable-jasmone, suitable-acetic acid 3-hexenyl ester, cuminyl alcohol, ligustral, dimethyl benzyl carbinol, dimethyl benzyl carbinyl acetate, ethyl acetate, methyl aceto acetate, EAK, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, the acetic acid ethyl phenyl ester, eucalyptol, allylguaiacol (eugenol), acetic acid fenchyl ester, Flor acetic ester (tricyclodecenyl acetate), Frutene (propionic acid tricyclodecenyl ester), Geraniol, hexenol, acetic acid hexenyl ester, hexyl acetate, hexyl formate, black nightshade alcohol, laurine, indone, primary isoamyl alcohol, isomenthone, isopulegyl acetate, isoquinolines, ligustral, linalool, Linalool oxide, any ester in the formic acid, piperitone, menthyl phenyl methyl ketone (acetphenone), Methyl amyl ketone, methyl o-aminobenzoate, methyl benzoate, acetic acid methyl-benzyl ester (methyl benyl acetate), methyleugenol (eugenol), Sulcatone, methylheptine carbonate (methyl heptine carbonate), methyl heptyl ketone, methyl hexyl ketone, styroyl acetate, wintergreen oil, N-methyl methyl o-aminobenzoate, vernol, caprylolactone, octanol, p-cresol, the p-cresol methyl ether, p-methoxyacetophenone, p-methyl acetophenone, phenoxyethyl alcohol, phenyl acetaldehyde, ethyl phenyl acetate, phenylethyl alcohol, dimethyl phenylethyl carbinol, prenyl acetate, tripropoxy-boron (propyl bornate), pulegone, rose oxide, safrole, the 4-terpinenol, α-terpinenol and/or 1,1-dimethoxy-2-phenylethane (viridine).
Usually, multiple fragrance components is present in the preparation.In encapsulant of the present invention, expectation will exist 4 kinds or more kinds of, preferably 5 kinds or more kinds of, more preferably 6 kinds or more kinds of, or even the fragrance components of the given tabulation of 7 kinds or more kinds of different floating loose perfume compound of delay from providing more than in the perfume compound that is present in encapsulation.
Can be applicable to another group perfume compound of the present invention is so-called " aromatherapy " material.These comprise many same components that are used for essence (perfumery), comprise the component of volatile oil such as Salvia sclarea (Clary Sage), folium eucalypti (Eucalyptus), Flos Pelargonii (Geranium), lavender (Lavender), Semen Myristicae (Mace) extract, orange flower oil (Neroli), Semen Myristicae (Nutmeg), Mentha viridis L (Spearmint), Viola odorata leaf (Sweet Violet Leaf) and valerian (Valerian).By the present invention, these materials can be transferred to textiles, and the latter will be worn or otherwise contact with human body (such as handkerchief and bed linen).
As mentioned above, the core of particle of the present invention can itself be the perfume compound of encapsulation, such as melamine/urea/formaldehyde encapsulant.By adding the other layer that not affected by perfume compound, the present invention can be used for " improvement " seepage capsule.In use, in cleaning process, remove other layer (PVOH and tensio-active agent).Within for some time, and/or in the situation of laundry, pledging clothes is worn and capsule when crushed, so capsule can discharge perfume compound.
As illustrational below with reference to specific embodiment, the present invention can be used in the pre-packaged beneficial agent (such as perfume compound) of encapsulation, and the latter has had the positively charged ion capsule when it encapsulates for the first time.Such positively charged ion capsule it is believed that to demonstrate than not charged capsule and is for example better depositing on the cloth.Yet they demonstrate the negative interaction with anion surfactant.By further encapsulate these capsules according to the present invention, can reduce these undesirable interactions.
Dyestuff as beneficial agent
As the alternatives of perfume compound or except perfume compound, dyestuff is the beneficial agent that possible be present in the particle.Dyestuff is typically so that the level that they are effective as toning (shading) dyestuff exists.Dope dye is preferably blue or purple.Suitable and preferred dope dye is WO05/003274, WO06/032327, WO06/032397, EP08167033, WO06/045375, those described in WO06/053598 and the WO08/017570.Can use the mixture of dope dye.
The dope dye of preferred kind is positively charged ion thiazole (thiazolium) dyestuff, positively charged ion isothiazole (isothiazolium) dyestuff, positively charged ion azines, positively charged ion pyridine/pyridazine dyes, acid azines, hydrophobic anthraquinone dye and hydrophobicity azoic dyestuff.Most preferred dope dye is to be selected from following those: directly purple 9; Direct purple 35; Direct purple 51; Direct purple 99; Acid violet 50; 63 ,DIS,PER,SE ,Vio,let, 63 28 Hes, solvent violet 13.In the packed situation of some other beneficial agents according to the present invention, dyestuff can be present in the capsule with other appendicular form or in the product ontology.
Tensio-active agent as beneficial agent
Beneficial agent may itself be that tensio-active agent maybe may comprise tensio-active agent.In laundry product, for example, beneficial agent can be cats product, its by the shell that forms around its prevent with product ontology in anion surfactant interact.For laundry product, suitable such cats product is the water-soluble cationic material, and it has at least one alkyl or alkenyl chain.Preferably the length summation of alkyl chain is less than 20.Preferred cats product is: the quaternary ammonium compound with single long-chain aliphatic group.Palmityl trimethyl ammonium chloride is particularly preferred.
Other beneficial agent
Beneficial agent can comprise siloxanes, preferably as adjusting agent, is used for being applicable to especially the product of hair and skin products.Alternatively or in addition, the siloxanes adjusting agent may reside in the composition body.Particularly preferred siloxanes adjusting agent is as being formed by siloxanes those of silicone emulsion, such as polydiorganosiloxane, the polydimethylsiloxane of CTFA called after dimethicone especially, the polydimethylsiloxane with hydroxyl end groups of CTFA called after dimethiconol, and the polydimethylsiloxane of amino-sense of CTFA called after amodimethicone.
Also suitable is such silicone emulsion, and wherein the surfactivity segmented copolymer of the high molecular of some type has mixed with the silicone emulsion drop, as for example describing among the WO03/094874.In such material, the silicone emulsion drop is preferably formed by described above those of polydiorganosiloxane.A kind of surfactivity segmented copolymer of preferred form is according to following formula:
Wherein the mean value of x be 4 or larger and mean value y be 25 or larger.
The surfactivity segmented copolymer of another preferred form is according to following formula:
Wherein the mean value of a be 2 or larger and mean value b be 6 or larger.
Also can use the mixture of any above-mentioned silicone emulsion.
Above-described siloxanes will be usually in composition of the present invention with 0.05-15%, preferably the level of 0.5-12% exists, by the gross weight of siloxanes, based on the gross weight of composition.
Can estimate other hydrophobic benefit reagent.Many agrochemicals materials are hydrophobic and perhaps in use are potentially dangerouss.Such material can exist with the form of the solution in oily material, and it has formed the core according to particle of the present invention.Existence around the stable shell of the tensio-active agent of these cores it is believed that the release that has postponed these materials until composition is diluted, and preferably exactly before use, has therefore reduced undesirable exposure.
Estimate that these materials can prepare as described in this manual.
Manufacture method (polymkeric substance)
The modification of polymkeric substance can realize by a series of known methods.For example, in making the PVOH of modification, the acidic solution of PVOH (preferably be higher than form under 80 degrees centigrade the temperature) about 70 degrees centigrade with aldehyde/aldolization (preferably dripping).After adding component, reaction is carried out a few hours under normal temperature-pressure.Yet suitable polymer materials is commercially available and comprises Mowiflex LPFX 416 (Kuraray).
Particularly preferred embodiment of the present invention is the main washing detergent composition that comprises anion surfactant.Tensio-active agent preferably is present in the composition with the level of 1wt% to 60wt%.Suitable anion surfactant is that those skilled in the art are well-known and comprise alkylbenzene sulfonate (alkyl benzene sulphonate), primary and secondary alkyl sulfuric ester salt (primary and secondary alkyl sulphates), especially C8-C15 primary alkyl sulfuric acid (primary alkyl sulphates); Alkyl ether sulphate salts (alkyl ether sulphates); Alkene sulfonate (olefin sulphonates); Alkylxylene sulfonate (alkyl xylene sulphonate), dialkyl sulfosuccinate succinate salt (dialkyl sulphosuccinate); Ether carboxylate (ether carboxylate); Isethionate (isethionates); Sarcosinate (sarcosinates); Fatty sulfonate (fatty acid ester sulphonates) and its mixture.Usually, sodium salt is preferred.When being included in wherein, composition comprises about 1%-about 50% usually, the anion surfactant of 10wt%-40wt% preferably, based on fabric treatment composition, such as linear alkylbenzene sulfonate (linear alkylbenzenesulfonate), sulfonated α-olefin (α-olefinsulfonate), alkyl sulfuric ester salt (alkyl sulfate) (fatty alcohol sulfate salt (fatty alcohol sulfate)), alcohol ethoxy sulfuric acid (alcohol ethoxysulfate), secondary alkyl sulfonate (secondary alkanesulfonate), alpha-sulfo fatty acid methyl ester (alpha-sulfo fatty acid methyl ester), alkyl or alkenyl succsinic acid or soap.Preferred tensio-active agent is the blend of alkyl ether sulphate salts (alkyl ether sulphate) and oxyalkylated alkyl nonionogenic tenside and alkylsulfonate (alkyl sulphonate) or alkyl ether sulphate salts (alkyl ether sulphate).Preferred alkyl ether sulphate salts is C8-C15 alkyl and the ethoxylation (ethoxlation) with 2-10 mole.Preferred alkyl sulfuric ester salt (alkyl sulphates) is alkylbenzene sulfonate (alkylbenzene sulphonates), has especially the linear alkylbenzene sulfonate of C8-C15 alkyl chain length.The counter ion of anion surfactant are sodium typically, although other counter ion such as TEA or ammonium can be used.Suitable anion surfactant material can get in market, as ' Genapol', from Clariant.In these preferred embodiments, beneficial agent is selected from:
A) perfume compound itself;
B) packed perfume compound; With,
C) cats product.
For can be further and understand better the present invention, be illustrated referring to specific embodiment.
Granulometry
Use two kinds of methods to measure granularity.
1. use the Olympus BX-41 opticmicroscope that digital camera is housed, the particle in the solution is carried out imaging.Catch image, use Olympus Cell P software, it allows to measure granularity.
2. the particle dry air is carried out imaging to the nonabsorbable surface and in Hitachi-TM 1000 desk type scanning electronic microscopes.Use is determined granularity by the length scales that related software adds in the image.
Embodiment:
Embodiment 1: perfume compound and dyestuff are as beneficial agent
1a) do not contain the contrast solution of polymkeric substance:
The 30ml demineralized water
500 μ l AKK* perfume compound+5 μ l oil red EGN (* type 15-component perfume compound)
Use high speed agitator, mix perfume compound, water and oil red EGN20 minute (1200rpm, Jiffy agitator).Then, use water-bath, temperature is elevated to 55 ℃, and other 10 minutes of mix products.Add 20% living solution of the linear alkylbenzene sulfonate (LAS) of 10ml.Other 10 minutes of 800rpm mix products, then stir under 20 minutes at 800rpm and make it be cooled to room temperature.
1b) the solution of polymkeric substance-modification:
10ml Mowiflex LPFX 416 (5% active mPVOH, Kuraray)
500 μ l AKK* perfume compound+5 μ l oil red EGN (* type 15-component perfume compound)
The 20ml demineralized water
Use high speed agitator, mix perfume compound, water and oil red EGN10 minute (1200rpm, Jiffy agitator).Add Mowiflex LPFX 416 and continue and stirred other 10 minutes.Then, use water-bath, temperature is elevated to 55 ℃, and continue to mix other 10 minutes.Add 10ml linear alkylbenzene sulfonate (LAS) 20% living solution and continue to mix other 10 minutes at 800rpm.Under stirring 20 minutes, 800rpm make product be cooled to room temperature.
After 24 hours, contrast solution (1a) has the significant red color layer of free perfume compound and dyestuff.The solution that contains Mowiflex (1b) remains uniform.
Embodiment 2: perfume compound and dyestuff are as beneficial agent
The Solution Dispersion of the preparation in embodiment (1b) of 1ml is formed product (2a) at the non-aromatic detergent base of 19ml five equilibrium, and also the solution for preparing among embodiment (1b) with 1ml is dissolved in the demineralized water of 19ml and forms product (2b).
Two solution are placed cuvette, seal and at room temperature left standstill 24 hours.After during this period of time, estimate the existence of perfume compound in the headspace of two samples.
In the situation of (2a), do not detect perfume compound.In (2b), detect perfume compound.
Embodiment 3: cats product is as beneficial agent
(3a) there is not the contrast encapsulant of polymkeric substance
At 50 ℃, the Praepagen TQ (trolamine diester quat methosulphate, Clariant) of 1.75g is dispersed in the demineralized water of 46.5ml.Then solution is cooled to 20 ℃ and add the AKK type perfume compound of 0.5ml.Then use high speed agitator, stirred solution 10 minutes.Then make solution be warming up to 60 ℃ and stirred other 10 minutes.Then added 20% linear alkylbenzene sulfonate (LAS) solution of 1.25ml and stirred solution other 10 minutes.Then solution is cooled to 20 ℃ and stirred other 20 minutes.
(3b) has modification PVOH
Use the demineralized water of 42.75ml, 1.75gPraepagen TQ, (Mowiflex LPFX 416 Kuraray), repeats identical process to the 5% modified poly ethylene alcoholic solution of the AKK type perfume compound of 0.5ml and 3.75ml.
When (3a), when adding LAS, observe extensive flocculation at the preparation contrast solution, this show as expected between LAS and Praepagen TQ, formed insoluble complex.
Yet, when preparation contains the solution (3b) of modification PVOH, do not observe flocculation, this shows the shell by Mowiflex, protection perfume compound/Praepagen TQ drop is not subjected to the impact of anion surfactant.
Embodiment 4: the perfume compound encapsulant is as beneficial agent
In embodiment 3, but Praepagen TQ replaces with cation-modified perfume compound capsule (encaps) (Coolwear, Firmenich).
After finishing, the solution that contains modification PVOH is translucent, and wherein the clear encapsulant that disperses is visible under opticmicroscope.Contrast solution is opaque, has few encapsulant.After 24 hours, contrast solution demonstrates sedimentation (sedimentation) and creaming (creaming), and the two is not present in the solution that contains modification PVOH.
In embodiment 3, the existence of modification PVOH shields cationic charge and the anion surfactant on (screen) encapsulant effectively, therefore makes it stable in the Betengent product of negatively charged ion-enrichment.
Embodiment 5: the dyestuff as beneficial agent is product scope
In these embodiments, selected beneficial agent is solvent violet 13, a kind of cosmetic level hydrophobic dye, and it is suitable as the fabric opalizer.The mineral oil (white, lightweight, Sigma Aldrich, CAS No. 8042-47-5) of mixing colouring agent (0.1g) and 10ml is until fully dissolving.
Following acquisition comprises the product sample of the SV13 of encapsulation: use the Jiffy agitator under 1200rpm and 10 minutes, oil/SV13 of 500ul is dispersed in the demineralized water of 50ml.Then solution is heated to 50 ℃, adds the 20% LAS solution of 10ml and stirring velocity is dropped to 800rpm.After 3 minutes, under 800rpm stirs, solution is cooled to 20 ℃.
Following acquisition comprises the product sample of the SV13 of encapsulation: use the Jiffy agitator under 1200rpm and 5 minutes, oil/SV13 of 500ul is dispersed in the demineralized water of 32ml.Then added 5% solution of Mowiflex LPFX416 of 18ml and stirred solution other 5 minutes.Then solution is heated to 50 ℃, adds the 20% LAS solution of 10ml and stirring velocity is dropped to 800rpm.After 3 minutes, under 800rpm stirs, solution is cooled to 20 ℃.
For whether test dye is successfully encapsulated, in the commercially available product that contains tensio-active agent that adds each solution of 3ml to 10ml.Then measure the reflection spectrum of solution by following manner: fill 1 centimetre of PMMA cuvette with solution, cover three sides with blank sheet of paper, the slit that then blank face is butted on mutually Color 17 spectrophotometers (6mm slit plate, minute surface is got rid of, the UV eliminating) is placed.Larger-b* value shows that more dyestuff is released in the product.
| ? | Product | B* before interpolation | B* with SV13 | B* with SV13+Mowiflex |
| 5a | The Small-and-Mighty detergent for washing clothes | 6.94 | -10.17 | -0.49 |
| 5b | Dettol antimicrobial surface sanitising agent | -1.69 | -7.52 | -5.37 |
| 5c | Pantene Pro-V ices bright shampoo | -0.23 | -6.43 | -5.19 |
| 5d | The pleasant shower Gel of Simple mile | -0.63 | -5.26 | -4.33 |
| 5e | The Boots bathing is revealed | -7.19 | -10.92 | -9.94 |
| 5f | Palmolive Aquarium Gel Liquid soap | -2.35 | -7.18 | -5.89 |
All can find out that the encapsulation of dyestuff reduces the degree of dyeing product ontology significantly among the embodiment 5a-5f.
Claims (15)
1. composition, it comprises that the tensio-active agent of 1-99wt% and at least a diameter are the microparticle of 100nm-2mm, described microparticle comprises:
I) comprise the core of hydrophobic benefit reagent, its ClogP is greater than 0.5, and,
Ii) comprise shell uncharged hydrophobically modified, water-soluble, film-forming polymers, wherein film keeps basically complete in the presence of tensio-active agent, but dissolves when reducing the concentration of tensio-active agent, thus releasing beneficial reagent.
2. according to claim 1 composition, the diameter of wherein said particle or each particle is the 1-100 micron.
3. according to claim 1 composition, wherein the main chain of film-forming polymer is selected from: polyvinyl alcohol, polyvinyl acetate, ether of cellulose, polyoxyethylene, starch, polyvinylpyrrolidone, polyacrylamide, polyvinyl methyl ether-maleic anhydride, polymaleic anhydride, styrene-maleic anhydride, polyoxyethylene glycol, polyacrylate, alginic acid ester or salt, acrylamide copolymer, guar gum, casein, ethene-maleic anhydride resin series, polymine, and its mixture.
4. according to claim 3 composition, wherein film-forming polymer comprises ether of cellulose, and it is selected from Natvosol, methylcellulose gum, carboxymethyl cellulose, Type 3U, ethylmethylcellulose, hydroxyethylmethyl-cellulose, and its mixture.
5. according to claim 1 composition, wherein the pre-reaction by film-forming polymer and acetal or aldehyde obtains hydrophobic modified.
6. according to claim 1 composition, wherein the polymkeric substance of modification has:
A) in comprising greater than the water of one or more anionic/nonionic of the concentration of 1 grams per liter or cats product 20 ℃ solubleness or dispersiveness: less than 0.5 Grams Per Hour, and,
When b) concentration in water is less than 1 grams per liter when anionic/nonionic or cats product, solubleness or dispersiveness: greater than 0.5 Grams Per Hour.
7. according to claim 1 composition, wherein the polymkeric substance of modification stems from the polyvinyl alcohol that molecular weight is 10kD to 300kD.
8. according to claim 1 composition, wherein the polymkeric substance of modification stems from the polyvinyl alcohol that the hydrolysis scope is 60-99%.
9. according to claim 1 composition, wherein the polymkeric substance of modification stem from polyvinyl alcohol and have according to DIN 53 015 measure 20 ℃ 1 to 100mPa.s viscosity, by 4% solution.
10. according to claim 1 composition, wherein polymkeric substance is with hydrophobic deriveding group modification, and described hydrophobic deriveding group stems from ClogP greater than 0.5 fertile material.
11. composition according to claim 10, wherein the fertile material of hydrophobic deriveding group is selected from the group that comprises butyraldehyde, octanal, dodecyl aldehyde, 2-ethyl hexanal, hexanaphthene formaldehyde, citral, propionic aldehyde, (2-methoxy ethoxy) dimethylacetal ((2-methoxyethoxy) acetaldehyde dimethylacetal) and phenyl aldehyde.
12. composition according to claim 1, wherein tensio-active agent is selected from anionic detersive surfactant or cats product, and it is the softening actives of conditioning.
13. composition according to claim 1, wherein beneficial agent comprises perfume compound.
14. the method for the treatment of the surface, it comprises the steps: to make according to claim 1, and each composition contacts with fabric, hair or living tissue in-13.
15. one kind prepares according to claim 1-13 each the methods of composition, it comprises the steps:
A) provide the aqueous solution of the film-forming polymer of uncharged, hydrophobically modified, have the hydrophobic benefit reagent that is dispersed in wherein,
B) around the hydrophobic benefit reagent that disperses, form the layer of the film-forming polymer of uncharged, hydrophobically modified, and
C) stablize described layer with tensio-active agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0814423A GB0814423D0 (en) | 2008-08-08 | 2008-08-08 | Improvements relating to surfactant-containing compositions |
| GB0814423.0 | 2008-08-08 | ||
| PCT/EP2009/059046 WO2010015493A1 (en) | 2008-08-08 | 2009-07-15 | Microcapsules in surfactant-containing compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102177232A CN102177232A (en) | 2011-09-07 |
| CN102177232B true CN102177232B (en) | 2013-03-27 |
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| CN200980140032.9A Expired - Fee Related CN102177232B (en) | 2008-08-08 | 2009-07-15 | Microcapsules in surfactant-containing compositions |
Country Status (9)
| Country | Link |
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| EP (1) | EP2307536B1 (en) |
| CN (1) | CN102177232B (en) |
| AR (1) | AR072921A1 (en) |
| BR (1) | BRPI0917442A2 (en) |
| ES (1) | ES2402486T3 (en) |
| GB (1) | GB0814423D0 (en) |
| TW (1) | TW201012542A (en) |
| WO (1) | WO2010015493A1 (en) |
| ZA (1) | ZA201100600B (en) |
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| CN102198117B (en) * | 2011-06-17 | 2013-02-27 | 中国林业科学研究院林产化学工业研究所 | Thermosensitive polymeric microcapsules and preparation method and use thereof |
| EP2920290B1 (en) | 2012-11-19 | 2016-09-21 | Unilever PLC, a company registered in England and Wales under company no. 41424 | Improvements relating to encapsulated benefit agents |
| EP3027303B1 (en) * | 2013-07-30 | 2016-09-28 | Unilever N.V. | Improvements relating to encapsulated benefit agents |
| WO2015048266A1 (en) | 2013-09-27 | 2015-04-02 | Rohm And Haas Chemicals Llc | Water dispersible films for packaging high water containing formulations |
| EP3033385B1 (en) | 2013-09-27 | 2017-05-31 | Rohm and Haas Company | Ionic strength triggered disintegration of films and particulates |
| CA2922987C (en) | 2013-10-04 | 2020-07-21 | The Procter & Gamble Company | Benefit agent containing delivery particle |
| CN110225967A (en) * | 2017-02-06 | 2019-09-10 | 宝洁公司 | Laundry detergent compositions piece with microcapsules |
| CN112280401A (en) * | 2020-10-30 | 2021-01-29 | 湖南圣人防水材料有限公司 | Preparation method of reinforced waterproof coating with mildew inhibition effect |
| CN115110094A (en) * | 2021-03-18 | 2022-09-27 | 江苏筑磊电子科技有限公司 | Method for treating metal surface of dipropylene glycol after fire |
| CN113693078A (en) * | 2021-10-28 | 2021-11-26 | 潍坊新绿化工有限公司 | Herbicide containing anilofos, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0332175A2 (en) * | 1988-03-10 | 1989-09-13 | Lion Corporation | Method of producing microcapsule |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799421B2 (en) * | 2002-02-14 | 2010-09-21 | Akzo Nobel N.V. | Controlled release materials |
| US7053034B2 (en) * | 2002-04-10 | 2006-05-30 | Salvona, Llc | Targeted controlled delivery compositions activated by changes in pH or salt concentration |
| GB0222964D0 (en) * | 2002-10-03 | 2002-11-13 | Unilever Plc | Polymeric film for water soluble package |
| GB0803165D0 (en) * | 2008-02-21 | 2008-04-02 | Unilever Plc | Encapsulated benefit agent |
-
2008
- 2008-08-08 GB GB0814423A patent/GB0814423D0/en not_active Ceased
-
2009
- 2009-07-15 CN CN200980140032.9A patent/CN102177232B/en not_active Expired - Fee Related
- 2009-07-15 WO PCT/EP2009/059046 patent/WO2010015493A1/en active Application Filing
- 2009-07-15 BR BRPI0917442A patent/BRPI0917442A2/en not_active IP Right Cessation
- 2009-07-15 EP EP09780617A patent/EP2307536B1/en not_active Revoked
- 2009-07-15 ES ES09780617T patent/ES2402486T3/en active Active
- 2009-07-16 TW TW98124143A patent/TW201012542A/en unknown
- 2009-08-06 AR ARP090103010 patent/AR072921A1/en not_active Application Discontinuation
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- 2011-01-24 ZA ZA2011/00600A patent/ZA201100600B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0332175A2 (en) * | 1988-03-10 | 1989-09-13 | Lion Corporation | Method of producing microcapsule |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201012542A (en) | 2010-04-01 |
| CN102177232A (en) | 2011-09-07 |
| AR072921A1 (en) | 2010-09-29 |
| WO2010015493A1 (en) | 2010-02-11 |
| ZA201100600B (en) | 2012-05-01 |
| BRPI0917442A2 (en) | 2015-12-01 |
| EP2307536A1 (en) | 2011-04-13 |
| GB0814423D0 (en) | 2008-09-10 |
| EP2307536B1 (en) | 2013-02-13 |
| ES2402486T3 (en) | 2013-05-06 |
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