EP1657299A1 - Microcapsules - Google Patents

Abstract

Aqueous preparation (I) comprises surface-active substances (a) and micro capsules (b) consisting of a covering (obtained by reaction of a protein with an anionic polymer), an oil phase and/or an active agent. An independent claim is also included for a preparation of micro capsules with an average diameter of 0.1-500 micros, comprising pH-induced coacervation of oil phases and/or active substances into a covering (made of proteins and anionic polymers), cross linking the resulting covering by contacting with an aldehyde component; and treating the reaction products (with a large extent of anionic charge in the covering order) with cationic surfactants and/or polymers with neutral or cationic character.

Description

Field of the invention

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.

State of the art

The term "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. According to a third method, particles are coated alternately with polyelectrolytes of different charge ("layer-by-layer" method). The microscopic capsules can be dried like powder. Besides 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.

Examples of 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) ,

In this connection, reference should be made in particular to the European patent application EP 0937496 A2 (Unilever), from which microcapsules are known, 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.

On the one hand, 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. Particularly popular is the use of such systems in the field of washing, rinsing, cleaning and especially finishing agents. As a rule, 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). In particular, 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.

Although the use of such color or fragrance capsules for the mentioned range is well known from the prior art, the known solutions are still unsatisfactory from a technical point of view. In particular, the resistance of the capsules in surfactant solution is unsatisfactory, in particular the lack of resistance to cationic surfactants, especially esterquats, which are typically constituents of softening agents. In addition, the inadequate properties are particularly evident when the preparations are exposed to even higher temperatures or even have to withstand a certain pressure, as is typically the case with forced application to fibers, yarns and papers.

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.

Description of the invention

• (a) oberflächenaktive Substanzen und
• (b) Mikrokapseln, bestehend aus einer Hülle, die durch Reaktion eines Proteins mit einem anionischen Polymer gebildet wird, und einer darin eingeschlossenen Ölphase und/oder einem Wirkstoff.

The invention relates to aqueous preparations containing

• (a) surfactants and
• (b) microcapsules consisting of a shell formed by reaction of a protein with an anionic polymer and an oil phase and / or agent included therein.

It has surprisingly been found that 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.

method

• (a) Ölphasen und/oder Wirkstoffe durch pH-induzierte Koazervation in eine Hülle einschließt, die von Proteinen und anionischen Polymeren gebildet wird,
• (b) die Hülle der resultierenden Mikrokapseln zunächst durch Inkontaktbringen mit einer Aldehydkomponente vernetzt und
• (c) den Reaktionsprodukten, die über eine weitgehend anionische Ladung in der Hülle verfügen, durch Behandlung mit kationischen Tensiden und/oder Polymeren eine neutralen oder kationischen Charakter verleiht.

Another object of the invention relates to a process for the preparation of microcapsules having an average diameter of 0.1 to 500, preferably 1 to 250 and in particular 10 to 100 micras, in which

• (a) enclosing oil phases and / or agents by pH-induced coacervation in an envelope formed by proteins and anionic polymers,
• (B) the shell of the resulting microcapsules initially crosslinked by contacting with an aldehyde component and
• (c) imparts a neutral or cationic character to the reaction products having a substantially anionic charge in the shell by treatment with cationic surfactants and / or polymers.

Surface-active substances

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

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-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 acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the 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.

• Alkylbenzenesulfonates

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. Especially suitable of these are dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts.

• alkyl and / or alkenyl sulfates

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. Typical examples of 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. In the case of 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®. Another possibility are 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

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.

• soaps

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. Preferably, coconut or palm kernel fatty acids are used in the form of their sodium or potassium salts.

Nonionic surfactants

Typical examples of 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.

• fatty alcohol polyglycol ethers

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.

• Alkoxylated fatty acid esters

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. Usually, 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. Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettsäuremethylestern.

• alkyl and / or alkenyl oligoglycosides

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. The index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides and stands For a number between 1 and 10. While p in a given compound always has to be an integer, and above all can assume the values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic variable, usually a fractional one Number represents. Preference is given to using 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. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). 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

in der R¹⁴CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁵ und R¹⁶ unabhängig voneinander für Wasserstoff oder R¹⁴CO, R¹⁵ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_m4H-Gruppe, ml, m2 und m3 in Summe für 0 oder Zahlen von 1 bis 12, m4 für Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (VIII) als besonders vorteilhaft erwiesen, in der R¹⁴CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R¹⁵ für R¹⁵CO, R¹⁶ für Wasserstoff, R¹⁷ für eine Methylgruppe, ml, m2 und m3 für 0 und Y für Methylsulfat steht.Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyl distearyl ammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VIII)

in the R ¹⁴ CO for an acyl radical having 6 to 22 carbon atoms, 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 and Y is halide, alkylsulfate or alkyl phosphate. Typical examples of 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. Preferably _12/18 coconut fatty acids technical C. and in particular partly hydrogenated C _16/18 tallow or palm oil fatty acids and elaidic C _16/18 fatty acid used. To prepare the quaternized esters, the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used. In view of the performance properties of the esterquats, 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). From an application point of view, 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.

in der R¹⁸CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁹ für Wasserstoff oder R¹⁸CO, R²⁰ und R²¹ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m5 und m6 in Summe für 0 oder Zahlen von 1 bis 12 und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Als weitere Gruppe geeigneter Esterquats sind schließlich die quaternierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (X) zu nennen,

in der R²²CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²³ für Wasserstoff oder R²²CO, R²⁴, R²⁵ und R²⁶ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m7 und m8 in Summe für 0 oder Zahlen von 1 bis 12 und X wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Schließlich kommen als Esterquats noch Stoffe in Frage, bei denen die Ester- durch eine Amidbindung ersetzt ist und die vorzugsweise basierend aufDiethylentriamin der Formel (XI) folgen,

in der R²⁷CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²⁸ für Wasserstoff oder R²⁷CO, R²⁹ und R³⁰ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Marke Incroquat® (Croda) im Markt erhältlich.In addition to the quaternized fatty acid triethanolamine ester salts, 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. Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines of the formula (X) should be mentioned as a further group of suitable esterquats.

in the 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 and X again represents halide, alkyl sulfate or alkyl phosphate. Finally, 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.

Amphoteric or zwitterionic surfactants

in der R³¹ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R³² für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³³ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, De-cyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische. Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (XIII) folgen,

in der R³⁴CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R³⁵ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³⁶ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q2 für Zahlen von 1 bis 6, q3 für Zahlen von 1 bis 3 und Z wieder für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dime-thylaminopropylamid mit Natriumchloracetat. Weiterhin kommen auch Imidazoliniumbetaine in Betracht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C_12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Examples of suitable amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable 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. Also suitable are carboxyalkylation products of amidoamines which follow the formula (XIII) ,

in the 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. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred. Furthermore, 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. 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.

Dyes and perfumes

The object of the present invention has been to provide color and fragrance capsules available. In view of the problems described in the application of other encapsulation systems, however, 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 Deutsche Forschungsgemeinschaft, 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.

As perfume oils - which are usually present as an oil phase - may be mentioned mixtures of natural and synthetic fragrances. 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). Furthermore, animal raw materials come into question, such as civet and Castoreum. 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, α-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. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as flavoring components, 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. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-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, irotyl and floramate alone or in mixtures. 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.

microcapsules

As explained in the introduction, the encapsulation of active ingredients by coacervation of proteins and anionic polymers in general and gelatin and CMC in particular is known to those skilled in the art. In particular, the already cited EP 0937496 A2 contains a detailed description of the preparation process, even if it is not absolutely necessary for the purposes of the present invention, to comply with the limitations mentioned there in terms of the molecular weight of the polymer. Otherwise, the content of this document is encompassed by the disclosure of the present technical teaching.

In practice, it has proved advantageous to prepare two separate solutions, one of which contains the protein, usually gelatin, and the other the anionic polymer. In addition to the already mentioned carboxymethylcelluloses, which have molecular weights of preferably less than 500,000 and in particular less than 250,000, salts of alginic acid are suitable. 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. However, in an alternative embodiment of the invention, anionic chitosan derivatives, e.g. Carboxylation and especially Succinylierungsprodukte in question. Alternatively, poly (meth) acrylates having average molecular weights in the range of 5,000 to 50,000 daltons come into consideration.

• (a) durch Zugabe von 0,1 bis 1 Gew.-% einer wässrigen 50 Gew.-% Glutar- oder Formaldehydlösung (Vernetzung über Amingruppen) oder
• (b) durch Zugabe von 0,1 bis 1 Gew.-% Hexamethylendiamin (Vernetzung über Carboxylgruppen) geschehen;

anschließend lässt man die Mischung über Nacht stehen. Im letzten Fall werden Mikrokapseln erhalten, die über einen kationischen Charakter verfügen und daher leicht auf üblicherweise anionisch geladene Fasern aufziehen. Im ersten Fall tragen die Mikrokapseln jedoch eine anionische Ladung, d.h. für den Einsatz beispielsweise in der Textilausrüstung müssen sie nachträglich kationisiert werden, da sie sonst von den Fasern, auf die sie aufziehen sollen, abgestoßen bzw. leicht wieder ausgewaschen werden (vgl. auch WO 01/041915 A1, MCT). Dies geschieht vorzugsweise durch Behandlung mit kationischen Tensiden, insbesondere wässrigen Lösungen von Esterquats, die eingangs schon einmal beschrieben worden sind. Die Einsatzmenge kann dabei 5 bis 10 Gew.-% bezogen auf die Mikrokapseln betragen. Über die Menge der kationischen Tenside kann hierbei die Ladung genau eingestellt werden, d.h. es ist möglich, Mikrokapseln mit schwach anionischer Natur, neutraler oder kationischer Ladung herzustellen. Alternativ kann die Kationisierung auch durch Einsatz von kationischen Polymeren erfolgen. Geeignete kationische Polymere sind beispielsweise kationische Cellulosederivate, wie z.B. eine quaternierte Hydroxyethylcellulose, die unter der Bezeichnung Polymer JR 400® von Amerchol erhältlich ist, kationische Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrrolidon/Vinylimidazol-Polymere, wie z.B. Luviquat® (BASF), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpolypeptide, wie beispielsweise Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat®L/Grünau), quaternierte Weizenpolypeptide, Polyethylenimin, kationische Siliconpolymere, wie z.B. Amodimethicone, Copolymere der Adipinsäure und Dimethylaminohydroxypropyldiethylentriamin (Cartaretine®/Sandoz), Copolymere der Acrylsäure mit Dimethyldiallylammoniumchlorid (Merquat® 550/Chemviron), Polyaminopolyamide sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quaterniertes Chitosan, gegebenenfalls mikrokristallin verteilt, Kondensationsprodukte aus Dihalogenalkylen, wie z.B. Dibrombutan mit Bisdialkylaminen, wie z.B. Bis-Dimethylamino-1,3-propan, kationischer Guar-Gum, wie z.B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 der Firma Celanese, quaternierte Ammoniumsalz-Polymere, wie z.B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 der Firma Miranol. Besonders bevorzugt ist der Einsatz von Polyquatemium-7 (Polyquat® 701/NA), modifizierter Cellulosen (z.B. Celquat®, Fa. National Starch) und amphoterer Polymere (z.B. Polyquat® Ampho, Cognis)The color or fragrances are usually introduced into the protein phase, which is heated above the melting point of the proteins, so that a homogeneous distribution is ensured; then the two solutions are mixed with vigorous stirring. Alternatively, however, it is likewise possible first to mix the solutions and then to add the fragrances or dyes. Preferably, the preparation is at this time at a temperature in the range of 40 to 60 ° C. To induce coacervation, it is necessary to lower the pH to at least 4.3, for example by adding citric acid. The formation of microcapsules is indicated by clouding of the solution. Subsequently, the temperature is lowered to 15 to 20 ° C and stirred for about 4 to 5 hours. Using, for example, oil-soluble fragrances, one can observe under the microscope the formation of an envelope around the perfume droplets which are emulsified in the outer aqueous phase. It has proved to be advantageous to crosslink the sheaths of the capsules thus obtained, in order to improve the elasticity in this way. This can

• (A) by adding 0.1 to 1 wt .-% of an aqueous 50 wt .-% glutaric or formaldehyde solution (crosslinking over amine groups) or
• (b) by addition of 0.1 to 1 wt .-% hexamethylenediamine happen (crosslinking via carboxyl groups);

then leave the mixture overnight. In the latter case, microcapsules are obtained which have a cationic character and therefore readily attract on usually anionically charged fibers. In the first case, the microcapsules carry an anionic charge, ie for use for example in the textile equipment they need to be cationized, otherwise they will be repelled by the fibers to which they are to raise or slightly washed out again (see. Also WO 01/041915 A1, MCT). This is preferably done by treatment with cationic surfactants, in particular aqueous solutions of esterquats, which have already been described at the outset. The amount used may be 5 to 10 wt .-% based on the microcapsules. The amount of cationic surfactants can be used to precisely adjust the charge, ie it is possible to produce microcapsules of weak anionic nature, neutral or cationic charge. Alternatively, the cationization can also be carried out by using cationic polymers. Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethylcellulose which is obtainable under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) , Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of Acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides and their crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, if appropriate distributed in microcrystalline form, Condensation products of dihaloalkylene, such as dibromobutane with bis-dialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar gum, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt Polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol. Particularly preferred is the use of Polyquaternium-7 (Polyquat® 701 / NA), modified celluloses (eg Celquat®, National Starch) and amphoteric polymers (eg Polyquat® Ampho, Cognis).

In particular, however, 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:

Unlike most hydrocolloids, which are negatively charged at biological pH levels, 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. For the production of 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. Preference is given to using those types having an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 daltons and / or a Brookfield viscosity (1% strength by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and having an ash content of less than 0.3% by weight. For reasons of better solubility in water, the chitosans are generally used in the form of their salts, preferably as glycolates.

At the conclusion of 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. By varying the stirring speed, the diameter of the capsules can be significantly influenced, with high stirring speeds favoring small diameters.

Industrial Applicability

• von Fasern oder Textilien, speziell mit Hilfe des Verfahrens der Zwangsapplikation,
• von Hygienepapieren, speziell von Toilettenpapieren
• von Gebrauchspapieren.

The preparations according to the invention are preferably detergents, dishwashing detergents, cleaning agents or softeners. However, further objects of the present invention also relate to the use of these preparations for the equipment

• of fibers or textiles, especially by means of the forced application procedure,
• of sanitary papers, especially of toilet paper
• of utility papers.

Examples Production Example 1

Two aqueous solutions containing one containing 2.4% by weight of gelatin (Gelatine 115 B 25/30 PS, Rousselot), the other containing 0.6% by weight of carboxymethylcellulose (DS-07, Aldrich, MW = 90,000) and 0.3 wt .-% of the dye Larania® CI 15510 (Ciba) were prepared at 45 ° C and adjusted by addition of 1 N NaOH to pH = 6.5. The carboxymethylcellulose solution was stirred into the gelatin solution while mixing vigorously, and then the pH was lowered to 4.25 by addition of 1N HCl. The formation of capsules by coacervation was indicated by clouding of the solution. For curing, 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 μm.

Production Example 2

Two aqueous solutions containing one containing 2.4% by weight of gelatin (Geltec® SG-730 N, Extraco), the other containing 0.8% by weight of carboxymethylcellulose (AV 27088D, Aldrich, MW = about 38,000) and 18 wt .-% jasmine oil concentrate were prepared at 45 ° C and adjusted by the addition of 1 N NaOH to pH = 6.5. The carboxymethylcellulose solution was stirred into the gelatin solution while mixing vigorously, and then the pH was lowered to 4.25 by addition of 1N HCl. The formation of capsules by coacervation was indicated by clouding of the solution. For curing, 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 μm.

Production Example 3

Two aqueous solutions, one containing 2.8% by weight of gelatin (Geltec® SG-730 N, Extraco), the other containing 1.2% by weight of carboxymethylcellulose (AV 27088D, Aldrich, MW = about 38,000) and 0.3% by weight of indanthrene blue was prepared at 45 ° C. and adjusted to pH = 6.5 by addition of 1N NaOH. The carboxymethylcellulose solution was stirred into the gelatin solution while mixing vigorously, and then the pH was lowered to 4.25 by addition of 1N HCl. The formation of capsules by coacervation was indicated by clouding of the solution. For curing, 0.5 wt .-% hexamethylenediamine was added to the preparations. After a reaction time of 4 h at 25 ° C, the capsules were filtered off using a Buchner funnel. The average particle diameter was 45.5 μm.

Production Example 4

Two aqueous solutions containing one containing 2.4% by weight of gelatin (Geltec® SG-730 N, Extraco), the other containing 1.4% by weight of carboxymethylcellulose (AV 27088D, Aldrich, MW = about 38,000) and 0.5 wt .-% indanthrene blue were prepared at 45 ° C and adjusted by addition of 1 N NaOH to pH = 6.5. The carboxymethylcellulose solution was stirred into the gelatin solution while mixing vigorously, and then the pH was lowered to 4.25 by addition of 1N HCl. The formation of capsules by coacervation was indicated by clouding of the solution. For curing, 0.5 wt .-% hexamethylenediamine was added to the preparations. The capsules, whose average particle diameter was 46 μm, were not filtered, instead 0.6 wt.% Of xanthan gum was added to the preparation to prevent sedimentation.

Comparative Example C1

Dissolved 0.5 g indanthrene blue RS (CI 69800) in 100 ml of a 2 wt .-% solution of sodium alginate and added dropwise via a nozzle in a 1.5 w / v% aqueous calcium chloride solution. Subsequently, the resulting preparation was gelled for 5 minutes and the capsules thus obtained were washed and filtered off. Finally, the capsules were placed in a 2 w / v% aqueous chitosan solution and crosslinked.

formulation example

55 g of 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.

surfactant resistance

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. <b><u> Table 1 </ u></b> Microcapsule stability storage example 1 Comparative Example C1 - after 1 w, 20 ° C no discoloration light blue color - after 1 w, 40 ° C no discoloration clear blue coloration - after 2 w, 20 ° C no discoloration clear blue coloration - after 2 w, 40 ° C light blue color clear blue coloration

Claims (11)

Aqueous preparations containing (a) surfactants and (b) microcapsules consisting of a shell obtained by reaction of a protein with an anionic polymer and an oil phase and / or agent included therein. Preparations according to Claim 1, characterized in that they contain as surface-active substances (component a) anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Preparations according to claim 2, characterized in that they contain as component (a) cationic surfactants of the esterquat type. Preparations according to at least one of claims 1 to 3, characterized in that they have a content of surface-active substances in the range of 1 to 50 wt .-%. Preparations according to at least one of claims 1 to 4, characterized in that they contain as component (b) microcapsules containing as active ingredients a content of dyes and / or fragrances. Preparations according to at least one of claims 1 to 5, characterized in that they contain as component (b) microcapsules obtainable by coacervation of gelatin and anionic polymers. Preparations according to at least one of claims 1 to 6, characterized in that they are detergents, dishwashing detergents, cleaning agents or softening agents. Process for the preparation of microcapsules with an average diameter of 0.1 to 500 micras, in which (a) enclosing oil phases and / or agents by pH-induced coacervation in an envelope formed by proteins and anionic polymers, (B) the shell of the resulting microcapsules initially crosslinked by contacting with an aldehyde component and (c) the reaction products, which have a largely anionic charge in the shell have a neutral or cationic character by treatment with cationic surfactants and / or polymers. Use of preparations according to claim 1 for finishing fibers or textiles. Use of preparations according to claim 1 for the equipment of hygiene papers. Use of preparations according to claim 1 for the equipment of utility papers.

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