EP1657299A1 - Microcapsules - Google Patents

Microcapsules Download PDF

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Publication number
EP1657299A1
EP1657299A1 EP04026980A EP04026980A EP1657299A1 EP 1657299 A1 EP1657299 A1 EP 1657299A1 EP 04026980 A EP04026980 A EP 04026980A EP 04026980 A EP04026980 A EP 04026980A EP 1657299 A1 EP1657299 A1 EP 1657299A1
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Prior art keywords
acid
preparations according
alcohol
microcapsules
anionic
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German (de)
English (en)
Inventor
Josep-Lluis Viladot Petit
Nuria Dr. Bonastre Gilabert
Agustin Sanchez
Maria Dr. De Moragas
Juan-Antonio Dr. Asensio
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/384—Animal products

Definitions

  • the invention is in the field of detergents, dishwashing detergents and cleaners and relates to aqueous preparations containing active ingredients enclosed in defined microcapsules and the finishing of textiles and utility papers with these microcapsules.
  • microcapsule or “nanocapsule” is understood by those skilled spherical aggregates having a diameter in the range of about 0.0001 to about 5 and preferably 0.005 to 0.5 mm, containing at least one solid or liquid core, of at least enclosed in a continuous envelope. More specifically, it is finely dispersed liquid or solid phases coated with film-forming polymers, in the preparation of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. According to another method, molten waxes are taken up in a matrix (“microsponge”), which may additionally be enveloped as microparticles with film-forming polymers.
  • microsponge a matrix
  • particles are coated alternately with polyelectrolytes of different charge ("layer-by-layer” method).
  • the microscopic capsules can be dried like powder.
  • mononuclear microcapsules multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material.
  • Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath.
  • the shell may be made of natural, semi-synthetic or synthetic materials.
  • Natural shell materials are, for example, gum arabic, agar-agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or Dextran, polypeptides, protein hydrolysates, sucrose and waxes.
  • Semisynthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, eg cellulose acetate, Ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, as well as starch derivatives, especially starch ethers and esters.
  • Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • microcapsules of the prior art are the following commercial products (in parentheses is the shell material): Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (marine collagen), Lipotec Millicapseln (alginic acid, agar-agar), Induchem Unispheres (lactose , microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar-agar) and Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (chitosan, alginates) and Primasys (phospholipids) ,
  • EP 0937496 A2 Unilever
  • microcapsules which are obtained by pH-induced coacervation of gelatin and special CMC and subsequent crosslinking with glutaraldehyde.
  • the capsules are added to food preparations and have the task to release certain aromas delayed.
  • Microcapsules of similar composition are known from the documents EP 0833732 A1 and WO 98/020612 (Tastemaker) and FR 2732240 A1 . These documents are not related to detergents, dishwashing detergents and cleaning agents nor do they contain an indication of the surfactant compatibility of the systems.
  • microcapsules have the task of separating constituents of formulations which would otherwise undergo chemical reactions spontaneously or over time, on the other hand, certain active substances are to be delayed or released under controlled conditions.
  • Another background may be to add colored microcapsules to certain preparations to give them an attractive appearance.
  • the active substances are dyes or fragrances which would not be stable in the presence of surfactants or other optionally aggressive constituents (think only of hypochlorite or hydrogen peroxide).
  • fragrances when using fragrances there is still the need to release them delayed, especially when fibers, textiles or even utility papers should first be equipped with the encapsulated active ingredients.
  • the object of the present invention has thus been to provide new color and / or scent capsules which, compared to surfactants in general and cationic surfactants in particular, have improved resistance, in particular under pressure and temperature stress.
  • microcapsules of the abovementioned type have sufficient stability to surface-active substances in general and cationic surfactants, especially so-called ester quats, in particular, even when they are exposed to higher temperatures.
  • Microcapsules with dyes and / or fragrances, which are enclosed in a matrix of gelatin and a shell of carboxymethylcellulose, have proven to be particularly durable.
  • the color and scent capsules according to the invention also prove to be sufficiently elastic so that they can be used by way of forced application for finishing fibers, textiles and utility papers.
  • the preparations according to the invention may contain anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants in quantities of typically from 1 to 50, preferably from 5 to 40 and in particular from 10 to 25,% by weight.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino
  • anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using alkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl ester sulfonates and mixtures thereof.
  • Preferred alkylbenzenesulfonates follow the formula (I) , R 1 -Ph-SO 3 X (I) in which R 1 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • R 1 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph is a phenyl radical
  • X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • dodecylbenzenesulfonates tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the
  • Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary and / or secondary alcohols, which preferably follow the formula ( II ) , R 2 O-SO 3 X (II) in which R 2 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from the Roelen oxo synthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • branched primary alcohols are oxo alcohols, as they are accessible, for example by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
  • oxo alcohols as obtained by the classical oxo process of Enichema or the Condea by addition of carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of highly branched alcohols.
  • Such alcohol mixtures are commercially available under the trade name Lial®.
  • Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
  • Alkyl and / or alkenyl ether sulfates which are also frequently referred to as fatty alcohol ether sulfates, are the sulfation products of alkylene oxide addition products of primary and / or secondary alcohols, which preferably follow formula (III) , R 3 O (CH 2 CHR 4 O) n -SO 3 X (III) in the R 3 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 4 is hydrogen or methyl, n is from 1 to 20 and X is an alkali metal and / or or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • the starting materials are again the same alcohols, which have already been enumerated in the section alkyl sulfates.
  • R 7 CO-OX (IV) Under soaps are further fatty acid salts of the formula (IV) to understand R 7 CO-OX (IV) in which R 7 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and in turn X is alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • coconut or palm kernel fatty acids are used in the form of their sodium or potassium salts.
  • nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.
  • the preferred fatty alcohol polyglycol ethers follow the formula (V), R 8 O (CH 2 CHR 9 O) n 1 H (V) in which R 8 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 9 is hydrogen or methyl and n 1 is a number from 1 to 20.
  • Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) , R 10 CO (OCH 2 CHR 11) n 2 OR 12 (VI) in the R 10 CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 11 for hydrogen or methyl, R 12 for linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 for numbers from 1 to 20 stands.
  • Typical examples are the formal charge products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof.
  • the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite.
  • catalysts such as, for example, calcined hydrotalcite.
  • Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettklamethylestern.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VII), R 13 O- [G] p (VII) in which R 13 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or Alkenyloligoglykoside are thus alkyl and / or Alkenyloligo glucoside.
  • alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 13 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
  • Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 13 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
  • cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyl distearyl ammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or esterquats.
  • R 15 and R 16 are each independently hydrogen or R 14 CO
  • R 15 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H Group
  • ml, m2 and m3 in total is 0 or numbers from 1 to 12
  • m4 is numbers from 1 to 12
  • Y is halide, alkylsulfate or alkyl phosphate.
  • esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils.
  • the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used.
  • an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm oil fatty acid (iodine value 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proved to be particularly advantageous, in which R 14 is CO for an acyl radical having 16 to 18 carbon atoms, R 15 is R 15 CO, R 16 is hydrogen, R 17 is a methyl group, ml , m2 and m3 are 0 and Y is methylsulfate.
  • suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX), in the R 18 CO for an acyl radical having 6 to 22 carbon atoms, R 19 is hydrogen or R 18 CO, R 20 and R 21 are independently alkyl radicals having 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate.
  • R 22 CO for an acyl radical having 6 to 22 carbon atoms
  • R 23 is hydrogen or R 22 CO
  • R 24 , R 25 and R 26 are independently alkyl radicals having 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12
  • X again represents halide, alkyl sulfate or alkyl phosphate.
  • suitable esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine, in which R 27 is CO for an acyl radical having 6 to 22 carbon atoms, R 28 is hydrogen or R 27 CO, R 29 and R 30 are independently alkyl radicals having 1 to 4 carbon atoms and Y is again halide, alkyl sulfate or alkyl phosphate.
  • Such Amidesterquats are available for example under the brand Incroquat® (Croda) in the market.
  • alkylbetaines examples include alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII) , R 31 is alkyl and / or alkenyl radicals having from 6 to 22 carbon atoms, R 32 is hydrogen or alkyl radicals having from 1 to 4 carbon atoms, R 33 is alkyl radicals having from 1 to 4 carbon atoms, q 1 is from 1 to 6, and Z is from 1 to 6 Alkali and / or alkaline earth metal or Ammonium stands.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C 16/18 tallowalkyldimethylamine, and technical mixtures thereof.
  • R 34 CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • R 35 is hydrogen or alkyl radicals having 1 to 4 carbon atoms
  • R 36 is alkyl radicals having 1 to 4 carbon atoms
  • q 2 is from 1 to 4 6
  • q3 represents numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
  • imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the object of the present invention has been to provide color and fragrance capsules available.
  • the selection of the active ingredients is not critical. Specifically, this means that in principle completely different active principles, such as plant extracts, cosmetic oils, UV filters, antioxidants can be used, especially since the encapsulation material would also allow oral applications.
  • the dyes suitable for cosmetic purposes, and authorized substances may be used as they are, for example, compiled in the publication "Cosmetic Colourants” Commission of the Irish Klasscher, Verlag Chemie, Weinheim, 1984, S.81-106. Examples are Kochillerot A (CI 16255), Patent Blue V (CI42051), Indigotin (CI73015), Chlorophyllin (CI75810), Quinoline Yellow (CI47005), Titanium Dioxide (CI77891), Indanthrene Blue RS (CI 69800) and Krapplack (CI58000). As a luminescent dye and luminol may be included. These dyes are usually used in concentrations of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 wt .-%, based on the capsule weight.
  • Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal to the ketones such as the ionone, ⁇ -isomethylionone and methylatedryl ketone to the alcohols
  • Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, among the hydrocarbons are mainly the terpenes and balms.
  • fragrance oils are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, ⁇ -damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irot
  • Suitable flavors are, for example, peppermint oil, spearmint oil, aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, citron oil, wintergreen oil, clove oil, menthol and the like.
  • These fragrances are usually used in concentrations of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 wt .-%, based on the capsule weight.
  • alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:
  • the average molecular weight of the alginic acids or alginates is in the range of 150,000 to 250,000.
  • Salts of alginic acid are to be understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and, preferably, the sodium alginate ("algin") as well as the ammonium and alkaline earth salts. especially preferred are mixed alginates, e.g. Sodium / magnesium or sodium / calcium alginates.
  • anionic chitosan derivatives e.g. Carboxylation and especially Succinylmaschines.
  • poly (meth) acrylates having average molecular weights in the range of 5,000 to 50,000 daltons come into consideration.
  • Chitosan is used for the cationization.
  • Chitosans are biopolymers and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins of different molecular weight containing the following - idealized - monomer unit:
  • chitosans are cationic biopolymers under these conditions.
  • the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used.
  • chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities.
  • the chitin is thereby used in a process first described by Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum.
  • the chitosans are generally used in the form of their salts, preferably as glycolates.
  • the preparation it has been found advisable to raise the pH back to 6.5 (for example, by adding caustic soda) and to add a small amount of a suitable thickening agent (eg xanthan gum) to sediment the microcapsules which are typical have a diameter of 1 to 500 and in particular 10 to 100 micras, to prevent.
  • a suitable thickening agent eg xanthan gum
  • the diameter of the capsules can be significantly influenced, with high stirring speeds favoring small diameters.
  • the preparations were added 0.5 wt .-% of a 50 wt .-% aqueous solution of glutaraldehyde. After a reaction time of 4 h at 25 ° C., the capsules were treated with 7.5% by weight of an aqueous solution of a cationic surfactant (Dehyquart® AU 46) and then filtered off using a Buchner funnel. The average particle diameter was 12.8 ⁇ m.
  • the formulations were added 0.5 wt .-% of a 50 wt .-% aqueous solution of formaldehyde. After a reaction time of 4 h at 25 ° C., the capsules were treated with 7.5% by weight of an aqueous solution of a cationic surfactant (Dehyquart® AU 46) and then filtered off using a Buchner funnel. The average particle diameter was 45.5 ⁇ m.
  • a cationic surfactant (Dehyquart® AU 46, Cognis) were heated to 50 ° C, so that a liquid phase was obtained. This was mixed with 930 ml of water (30 ° C) and then mixed with vigorous stirring with 15 g of microcapsules according to Preparation Example 3.
  • the blue-colored capsules obtained according to Inventive Example 1 and Comparative Example C1 were used in an amount of 1.5% by weight in a test formulation (12% by weight sodium lauryl sulfate, 5% by weight cocamidopropyl betaine, 5% by weight). % Coco Glucosides, ad 100% by weight of water) and these stored for 2 weeks at 20 or 40 ° C. The staining of the aqueous color as a measure of the release of blue dye from the capsules was visually monitored. The results are summarized in Table 1. They show that the capsules according to the invention have a significantly higher surfactant resistance than the comparison systems.
EP04026980A 2004-11-12 2004-11-12 Microcapsules Withdrawn EP1657299A1 (fr)

Priority Applications (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3041250A1 (fr) * 2015-09-18 2017-03-24 Capsum Dispersions comprenant au moins un agent colorant
CN114845803A (zh) * 2019-12-27 2022-08-02 花王株式会社 微胶囊水分散液

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565753A (en) * 1967-07-17 1971-02-23 Ncr Co Capsule-cellulose fiber units and products made therewith
GB1343526A (en) * 1970-07-27 1974-01-10 Fuji Photo Film Co Ltd Methods of producing microcapsules
GB1478788A (en) * 1974-04-09 1977-07-06 Fuji Photo Film Co Ltd Microencapsulation process
US4402856A (en) * 1980-04-26 1983-09-06 Bayer Aktiengesellschaft Microcapsules with a defined opening temperature, a process for their production and their use
US5126061A (en) * 1989-02-27 1992-06-30 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
EP0674942A1 (fr) * 1994-03-31 1995-10-04 Copigraph Procédé de production de microcapsules à fort tau d'extrait sec contenant liquide hydrophobe, microcapsules obtenues par ledit procédé et procédé d'obtention d'un papier sensible à la pression à l'aide de ces microcapsules
US6733790B1 (en) * 1999-07-02 2004-05-11 Cognis Iberia S. L. Microcapsules and processes for making the same using various polymers and chitosans

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565753A (en) * 1967-07-17 1971-02-23 Ncr Co Capsule-cellulose fiber units and products made therewith
GB1343526A (en) * 1970-07-27 1974-01-10 Fuji Photo Film Co Ltd Methods of producing microcapsules
GB1478788A (en) * 1974-04-09 1977-07-06 Fuji Photo Film Co Ltd Microencapsulation process
US4402856A (en) * 1980-04-26 1983-09-06 Bayer Aktiengesellschaft Microcapsules with a defined opening temperature, a process for their production and their use
US5126061A (en) * 1989-02-27 1992-06-30 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
EP0674942A1 (fr) * 1994-03-31 1995-10-04 Copigraph Procédé de production de microcapsules à fort tau d'extrait sec contenant liquide hydrophobe, microcapsules obtenues par ledit procédé et procédé d'obtention d'un papier sensible à la pression à l'aide de ces microcapsules
US6733790B1 (en) * 1999-07-02 2004-05-11 Cognis Iberia S. L. Microcapsules and processes for making the same using various polymers and chitosans

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3041250A1 (fr) * 2015-09-18 2017-03-24 Capsum Dispersions comprenant au moins un agent colorant
CN114845803A (zh) * 2019-12-27 2022-08-02 花王株式会社 微胶囊水分散液
EP4082653A4 (fr) * 2019-12-27 2023-11-29 Kao Corporation Solution de dispersion aqueuse de microcapsules

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