WO2000032735A1 - Active chlorine-containing preparations with stabilized fragrances - Google Patents

Abstract

The invention relates to active chlorine-containing preparations with a content of fragrances. The inventive preparations are characterized in that the fragrances are present in the preparation in microencapsulated form.

Description

Preparations containing active chlorine with stabilized fragrances

rests of the invention

The invention is in the field of bleaching and disinfecting agents and relates to active chlorine-containing preparations which contain fragrances in a microencapsulation.

State of the art

In the Middle American countries, but also in the United States, the cold washing of textiles still dominates. This results in conventional bleaching agents such as e.g. Perborates or percarbonates are rarely used because they do not show any particular activity at temperatures around 20 ° C. Liquid bleaching agents are usually added to the washing liquor, which are generally surfactant preparations with a content of up to 10% by weight of hypochlorite; comparable agents are also used to clean and disinfect hard surfaces. The hypochlorite bleaches have an unpleasant pungent chlorine smell even when diluted heavily, which is why fragrances are added to them. An overview of hypochlorite lyes can be found, for example, by J.Josa and M.Osset in Jorn.Com.Esp.Deterg. 27, 213 (1997).

In this context, reference is also made to the European patent application EP 0397246 A1, from which perfume capsules with an average size of less than 350 μm, preferably not more than 150 μm, with a water-insoluble, fragile casing and cleaning or Detergents with these perfume capsules are known.

Although a sufficiently large number of perfume oils are known from the prior art which are hypochlorite-stable even over a long period of time and are not oxidized, substances with a citrus aroma are not included. However, since this smell is associated with freshness and cleanliness by the consumer, there is a desire in the market to offer hypochlorite bleaches with a citrus scent, which despite the known chemical instability of the fragrances are sufficiently stable in storage, ie give the desired fresh fragrance when used. The object of the invention was therefore to provide the simplest possible technical solution to the problem described.

Description of the invention

The invention relates to preparations containing active chlorine and containing fragrances, which are distinguished by the fact that the fragrances are in microencapsulated form.

Surprisingly, it was found that bleaching agents and disinfectants containing active chlorine can be stably formulated when fragrances are used in microencapsulated form. The microcapsules are chemically and physically, in particular spatially, stable in the liquid compositions according to the invention, i.e. on average neither decomposition nor settling of the microcapsules occurs. In this way, bleaching agents and disinfectants can be produced with a practically free selection of fragrances, and now, in particular, storage-stable preparations with citrus aroma are also accessible.

Alkali metal pochlorites and alkali metal hydroxides

The bleaching agents according to the invention usually contain alkali hypochlorites, preferably lithium, potassium and in particular sodium hypochlorite, as the active chlorine source. The hypochlorites can be used in amounts of 0.5 to 10, preferably 3.0 to 7.0 and in particular 4 to 6% by weight, based on the composition. The bleaching agents are usually adjusted to alkaline (pH 12.5 to 14) and for this purpose contain alkali metal hydroxides, such as sodium and / or potassium hydroxide, in amounts, based on the agent, of 0.5 to 2 and preferably 0.7 to 1, 2 wt .-%.

Microcapsules

The term “microcapsule” is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell made of polymer (s). Usually, these are finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited on the material to be encapsulated after emulsification and coacervation or interfacial polymerization. Leave the microscopic capsules, also called nanocapsules drying like powder. In addition to mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known which contain two or more nuclei distributed in the continuous shell material. Single or multi-core microcapsules can also be enclosed by an additional second, third, etc. shell. Mononuclear microcapsules with a continuous shell are preferred. The shell can consist of natural, semi-synthetic or synthetic materials. Of course, wrapping 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, sucrose and waxes. Semisynthetic wrapping materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyicellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

The microcapsules can have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their greatest spatial extent can be between 10 nm (visually not recognizable as a capsule) and 10 mm, depending on the fragrance contained in them and the application. Visible microcapsules with a diameter in the range from 0.1 mm to 7 mm, in particular from 0.4 mm to 5 mm, are preferred. Microcapsules that can no longer be seen with the naked eye preferably have a diameter in the range from 20 to 500 nm, preferably 50 to 200 nm. The microcapsules can be obtained by methods known in the art, with coacervation and interfacial polymerization being of the greatest importance. All surfactant-stable microcapsules available on the market can be used as microcapsules, for example the commercial products (the shell material is given in brackets) Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapsules (alginic acid, agar agar) , Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar) and Kuhs Probiol Nanospheres (phospholipids).

The active ingredients are usually released from the microcapsules during use of the preparations containing them by destroying the shell as a result of mechanical, thermal, chemical or enzymatic action. In the bleaching agents which are usually used undiluted, the release is preferably carried out by mechanical action, in particular by mechanical forces to which the microcapsules are exposed during metering, pumping over or spinning in the washing machine or when cleaning and disinfecting hard surfaces become. In a preferred embodiment of the invention, the compositions contain identical or different microcapsules in amounts of 0.1 to 10% by weight, in particular 0.2 to 8% by weight, extremely preferably 0.5 to 6% by weight.

Fragrances

The fragrances which are used in microencapsulated form for the purposes of the invention are preferably those which are otherwise not stable in preparations containing active chlorine.

Typical examples of suitable fragrances are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, nero-, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peels (bergamot, Lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage , Thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials such as civet and castorum are also suitable.

Typical synthetic fragrances are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Ester-type fragrances are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propalate and benzylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-iso-methylionone and methylcedryl ketone, to the alcohols anethole,

Citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.

Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as fragrances, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavender oil. Bergamot oil, dihydromyrcenol, lilial, lyral, phenylethyl alcohol, α-

Hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, ß-dambonone, cyclone hexasone, geranium oil, geranium oil, geranium oil licylat, Vertofix Coeur, Vercitron, Iso-E-Super, Fixolide NP, Evernyl, Iraidein ga ma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate, used alone or in mixtures.

In addition to the substances mentioned above, naturally active chlorine-resistant fragrances can also be used in microencapsulated form, for example: Citronellol (3,7-dimethyl-6-octen-1-ol), Dimethyloctanol (3,7-Dimethyloctanol-1) , Hydroxycitroneltol (3,7-dimethyloctane-1, 7-diol), mugol (3,7-dimethyl-4,6-octatrien-3-ol), myrcenol (2-methyl-6-methylene-7-octen-2 -ol), tetrahydromyrcenol (THM, 2,6-dimethyloctan-2-ol), terpinolene (p-mentho-1, 4 (8) - diene), ethyl 2-methylbutyrate, phenylpropyl alcohol, galaxolide (1,3,4 , 6,7,8-hexahydro-4,6,6,7,8,8, - hexamethylcyclopental-2-benzopyran, tonalide (7-acetyl-1, 1, 3,4,4,6-hexamethyltetrahydronaphthalene), rose oxide , Linaloloxid, 2,6-Dimethyl-3-octanol, Tetrahydroethyl-linalool, Tetrahydroethyllinalylacetat, o-sec-Butylcyclohexylacetat and Isolonediphorenepoxid as well as Isobomeal, Dihydroteφenöl, Isobornylacetat, Dihydroterpenylacetat). Other suitable fragrances are the substances mentioned in columns 3 and 4 of European patent application EP 0622451 A1 (Procter & Gamble). As a rule, the microcapsules contain the fragrances in amounts of 1 to 95, preferably 50 to 80 and in particular 60 to 70% by weight, based on the weight of the capsule. In addition, fragrances, in particular active chlorine-resistant fragrances, can also be used in non-microencapsulated form, for example tetrahydromyrcenol.

Sequestrant

If the preparations are used to treat textiles, it is advisable to add electrolytes that serve as sequestering agents for heavy metal ions and thus counteract yellowing of the laundry. For this purpose, for example, silicates, phosphonic acids or phosphonates, polyacrylic acid compounds, alkali carbonates such as sodium carbonate, lignin sulfonates and mixtures of the electrolytes mentioned are suitable. The total amount of the sequestering agents used is usually 0.1 to 2, preferably 0.3 to 1.5 and in particular 0.5 to 1.0% by weight, based on the agent.

For the purposes of the invention, silicates are understood to mean salts and esters of orthosilicic acid Si (OH) and their self-condensation products. Accordingly, the following crystalline substances can be used as silicates:

(a) Neosilicates (island silicates) such as phenakite, olivine and zircon;

(b) Sorosilicates (group silicates), such as, for example, thortveitite and hemimoφhite; (c) cyclosilicates (ring silicates) such as, for example, benitoid, axinite, beryl, milarite, osumilite or eu-dialyth;

(d) inosilicates (chain and band silicates) such as, for example, metasilicates (e.g. diopside) or amphiboles (e.g. tremolite);

(e) phyllosilicates (leaf and layer silicates) such as talc, kaolinite or mica (e.g. Mus-covit);

(f) Tectosilicates (framework silicates) such as feldspars and zeolites as well as clathrasils or dodecasils (e.g. melanophlogite), thaumasite and neptunite.

In contrast to the ordered crystalline silicates, silicate glasses such as e.g. Soda or potash water glass used. These can be of natural origin (e.g. montmorillonite) or synthetic. In a further embodiment of the invention, aluminosilicates can also be used. Typical examples of alkali or alkaline earth silicates are sodium and / or potassium silicates with a modulus in the range from 1.0 to 3.0 and preferably 1.5 to 2.0.

Phosphonic acids are organic derivatives of the acid HP (0) (OH) 2; Phosphates are the salts and esters of these phosphonic acids. The preferred organic phosphonic acids or phosphonates are known chemical compounds which can be prepared, for example, by the Michaelis-Arbuzov reaction. For example, they follow formula (I)

(I)

I OR ²

in which R ^{1 represents} an optionally substituted alkyl and / or alkenyl radical having 1 to 22, preferably 2 to 18 and in particular 6 to 12 carbon atoms and R ^{2 represents} hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammonium and / or alkanolammonium or an optionally substituted alkyl and / or alkenyl radical having 1 to 22, preferably 2 to 18 and in particular 6 to 12 carbon atoms. Typical examples are optionally hydroxy-, nitrilo- and / or amino-substituted phosphonic acids such as ethylphosphonic acid, nitrilotris (methylenephosphonic acid), 1-amino or 1-hydroxyalkane-1, 1-diphosphonic acids. In a preferred embodiment of the invention, amine oxide phosphonic acids are used which follow the formula (II) 0 CH ₃ H

II

HO-P- (CH ₂ ) m (CH) _n -N-> 0 (II)

OR ³ H

in which R ^{3 represents} hydrogen, a (CH2) m (CHCH3) _n NH2θ group or an alkali metal, m represents numbers from 1 to 4 and n represents 0 or 1. Amine oxide phosphonic acids are builders or sequestering agents which are sold, for example, by Bozetto / IT under the Sequion® brand. For their preparation, one starts from aminophosphonic acids, which are converted to the amine oxide. For the purposes of the invention, both mono- and diamine oxides can be used in the form of the phosphonic acids or their salts, which follow the formula (II). Amine oxidephosphonic acids are preferably used in which R ^{3 is} hydrogen, m is 3 and n is 0 (amine oxide based on aminotri-methylenephosphonic acid).

Polyacrylic acid compounds are homopolymers of acrylic acid and methacrylic acid or their esters. In addition to the acids, esters of the acids can also be polymerized with alcohols having 1 to 4 carbon atoms. Polyacrylic acid compounds with a particularly advantageous stabilizing action are present as alkali salts and have an average molecular weight in the range from 1,000 to 10,000 and in particular 4,000 to 6,000 daltons.

Thickener

The use of electrolytes is a very simple and inexpensive way of adjusting the viscosity. In a preferred embodiment of the invention, however, use is made of organic thickeners which are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar , Alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, clays, such as Laponite® from Southern Clay Products or Zeothix® from Huber, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides, which can be traded to the agents in quantities s can add from 0.1 to 2% by weight. Surfactants

To support the cleaning performance, the preparations can furthermore contain chlorine-stable surfactants, such as, for example, alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid N-alkyl-glucamides. However, alkyl ether sulfates, ether carboxylates, amine oxides, alk (en) yl oligoglycosides or fatty acid salts are preferably used. The sum of all surfactants - based on the preparations - generally makes up 1 to 15 and preferably 5 to 10% by weight.

Alkyl ether sulfates are anionic surfactants which can be obtained by sulfating alkyl polyglycol ethers and subsequent neutralization. The alkyl ether sulfates which are suitable for the purposes of the invention follow the formula (III)

(III)

(III)

in which R ^{4 represents} an alkyl radical having 12 to 18, in particular 12 to 14, carbon atoms, n represents numbers 2 to 5, in particular 2 to 3 and X represents sodium or potassium. Typical examples are the sodium salts of sulfates of Ci2 / i4 coconut alcohol + 2, + 2,3- and + 3-EO adduct. The alkyl ether sulfates can have a conventional or narrow homolog distribution. The alkyl ether sulfates are preferably used in amounts of 1 to 8, preferably 1, 5 to 6 and in particular 2 to 4% by weight, based on the composition.

In the context of the present invention, ether carboxylates or ether carboxylic acids preferably satisfy the formula (IV),

RIOCH ₂ CH2] u [0 (CH ₂ ) χCH (R ^, ) (CH2) yCH (R ^,, ) (CH2) _z ] v [OCH2CH2lwOCH2COOM (IV)

in which R is a hydrocarbon radical having 6 to 28 carbon atoms, u, v are identical or different numbers from 0 to 30, where u = 0, when v = 0, w is a number from 1 to 30, the sum u + v + w ≤ 30, x, y, z are independently the numbers 0 or 1,

R ', R "are independently hydrogen, methyl or ethyl, the sum x + y + z> 0 when R' = R" = H,

M is an alkali or alkaline earth metal (= ether carboxylate) or hydrogen (= ether carbon acid).

Ether carboxylates of the formula (IV) can be obtained by alkoxylating alcohols ROH with ethylene oxide as the only alkoxide or with several alkoxides and subsequent oxidation. The sum u + v + w represents the total degree of alkoxylation of the ether carboxylate. While the numbers u, v and w and the total degree of alkoxylation at the molecular level can only be integers including zero, at the macroscopic level they are mean values in the form of fractional numbers.

In formula (IV) is

R straight-chain or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, preferably a straight-chain or branched, acyclic Cβ-22-alkyl or alkenyl radical or a d-22-alkylphenyl radical, in particular a Cβ-iβ-alkyl- or alkenyl radical or a C ₄ -i6-alkylphenyl radical, particularly preferably a Cιo-16 alkyl radical, u, v, w in total u + v + w, preferably a number from 2 to 20, in particular 3 to 17 and particularly preferably 5 to 15, x, y, z in the sum x + y + z preferably not greater than 2, in particular not greater than 1 and particularly preferably equal to 0,

R ', R "preferably hydrogen (= R'), methyl (= R") or methyl (= R '), hydrogen (= R ⁿ ) and

M in particular lithium, sodium, potassium, calcium or magnesium, of which potassium and particularly sodium are preferred.

Preferred ether carboxylates are mixed adducts of propylene oxide (v> 0; x = y = z = 0; R '= H, R "= Me or R' = Me, R" = H) and ethylene oxide (u = 0 or u> 0) of the formula (IV-a),

R [OCH2CH2] u [OCH (R ^, ) CH (R ") z] v [OCH2CH2] wOCH ₂ COOM (IV-a)

especially those with u = 0, R '= Me and R "= H according to formula (IV-b):

R [OCH (CH3) CH2] v [OCH ₂ CH2] wOCH ₂ COOM (IV-b)

Since the recipes according to the invention are strongly alkaline, the ether carboxylic acids (M = H) can also be used instead of the ether carboxylates, which are neutralized in situ when introduced into the mixture. Suitable ether carboxylates or ether carboxylic acids are accordingly, for example, the following representatives designated by their INCI name (INCI: nomenclature for raw materials according to the International Cosmetic Ingredient Dictionary 7th Edition published by The Cosmetic, Toiletry and Fragrance Association Inc. (CTFA) Wa- shington, DC, USA): Butoxynol-5 Carboxylic Acid, Butoxynol-19 Carboxylic Acid, Capryleth-4 Carboxylic Acid, Capryleth-6 Carboxylic Acid, Capryleth-9 Carboxylic Acid, Ceteareth-25 Carboxylic Acid, Coceth-7 Carboxylic Acid, C9 -11 Pareth-6 Carboxylic Acid, C11-15 Pareth-7 Carboxylic Acid, C12-13 Pareth-5 Carboxylic Acid, C12-13 Pareth-8 Carboxylic Acid, C12-13 Pareth-12 Carboxylic Acid, C12-15 Pareth-7 Carboxylic Acid, C12-15 Pareth-8 Carboxylic Acid, C14-15 Pareth-8 Carboxylic Acid, Deceth-7 Carboxylic Acid, Laureth-3 Carboxylic Acid, Laureth-4 Carboxylic Acid, Laureth-5 Carboxylic Acid, Laureth-6 Carboxylic Acid , Laureth-8 Carboxylic Acid, Laureth-10 Carboxylic Acid, Laureth-11 Carboxylic Acid, Laureth-12 Carboxylic Acid, Laureth-13 Carboxylic Acid, Laureth-14 Carboxylic Acid, Laureth-17 Carboxylic Acid, Magnesium Laureth-11 Carboxylate, So - dium-PPG-6-Laureth-6-Carboxylate, Sodium-PPG-8-Steareth-7 Carboxylate, Myreth-3 Carboxylic Acid, Myreth-5 Carboxylic Acid, Nonoxynol-5 Carboxylic A cid, Nonoxynol-8 Carboxylic Acid, Nonoxynol-10 Carboxylic Acid, Octeth-3 Carboxylic Acid, Octoxynol-20 Carboxylic Acid, Oleth-3 Carboxylic Acid, Oleth-6 Carboxylic Acid, Oleth-10 Caώoxylic Acid, PPG-3-Deceth- 2 Carboxylic Acid, Sodium Capryleth-2 Carboxylate, Sodium Capryleth-9 Carboxylate, Sodium Ceteth-13 Carboxylate, Sodium C9-11 Pareth-6 Carboxylate, Sodium C11-15 Pareth-7 Carboxylate, Sodium C12-13 Pareth-5 Carboxylate, Sodium C12-13 Pareth-8 Carboxylate, Sodium C12-13 Pareth-12 Carboxylate, Sodium C12-15 Pareth-6 Carboxylate, Sodium C12-15 Pareth-7 Carboxylate, Sodium C12-15 Pareth-8 Carboxylate, Sodium C14-15 Pareth- 8 carboxylates, sodium deceth-2 carboxylates, sodium hexeth-4 carboxylates, sodium isosteareth-6 carboxylates, sodium isosteareth-11 carboxylates, sodium laureth-3 carboxylates, sodium laureth-4 carboxylates, sodium laureth-5 carboxylates, sodium laureth-6 carboxylates , Sodium Laureth-8 Carboxylate, Sodium Laureth-11 Carboxylate, Sodium Laureth-12 Carboxylate, Sodium Laureth- 13 carboxylates, sodium laureth-14 carboxylates, sodium laureth-17 carboxylates, sodium trideceth-3 carboxylates, sodium trideceth-6 carboxylates, sodium trideceth-7 carboxylates, sodium trideceth-8 carboxylates, sodium tride-ceth-12 carboxylates, sodium undeceth- 5 carboxylates, trideceth-3 carboxylic acid, trideceth-4 carboxylic acid, trideceth-7 carboxylic acid, trideceth-15 carboxylic acid, trideceth-19 carboxylic acid, undeceth-5 carboxylic acid.

Particularly preferred ether carboxylates are the ethoxylates (u = v = 0) of the formula (IV-c)

R [OCH2CH ₂ ] wOCH2COOM (IV-c)

in which R, w and M have the same meaning as in formula (IV) and preferably R is a Cιo-16-alkyl radical, w is from 3 to 17 and M is sodium. These are in particular the sodium lauryl ether carboxylates with a degree of ethoxylation w of 5 to 15, for example sodium laureth-6 carboxylates (w = 6) or sodium laureth-11 carboxylates (w = 11). The ether carboxylates can have a conventional or narrow homolog distribution.

Amine oxides are also known substances, which are occasionally attributed to the cationic, but usually the nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and oxidized in the presence of hydrogen peroxide. The amine oxides which are suitable as surfactant ingredients for the purposes of the invention follow the formula (V)

R ^β IR ⁵ -N-> 0 (V)

I.

R ⁷

in which R ^{5 represents} a linear or branched alkyl radical having 12 to 18 carbon atoms, and R ⁶ and R ⁷ independently of one another represent R ⁵ or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms. Amine oxides of the formula (V) are preferably used in which R ⁵ and R ^{6 are} C12 / 14 or C128-coconut alkyl radicals and R ^{7 is} a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (V) in which R ^{5 is} a C12 / 14 or C12 / 18 cocoalkyl radical and R ⁶ and R ^{7 have} the meaning of a methyl or hydroxyethyl radical. The amine oxides are preferably used in amounts of 1.5 to 6, preferably 2 to 4,% by weight, based on the composition.

Alkyl and alkenyioligoglycosides are known nonionic surfactants which follow the formula (VI),

R ⁸ 0- [G] _p (VI)

in which R ^{8 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. The alkyl and / or alkenyl oligo-glycosides, which are furthermore suitable as surfactant ingredients, can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and can in particular assume the values p = 1 to 6 here, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyioligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyioligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁸ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronalcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length Cβ-C-io (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Ciβ-coconut fatty alcohol by distillation and are contaminated with a proportion of less than 6% by weight of Ci2-alcohol can as well as alkyl oligoglucosides based on technical Cg / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁸ can 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, petroseiinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures . Alkyl oligoglucosides based on hydrogenated Ci2 / 14 coconut alcohol with a DP of 1 to 3 are preferred. The glycosides are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.

The agents according to the invention may contain fatty acid salts of the formula (VII) as further surfactants,

R ⁹ CO-OX (VII)

in which R ⁹ CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal. Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical mixtures as well as their mixtures they occur during the pressure splitting of technical fats and oils. Salts of technical coconut or tallow fatty acids are preferably used. Since the recipes according to the invention are strongly alkaline, the fatty acids which are neutralized in situ when they are introduced into the mixture can also be used instead of the salts. Those agents according to the invention preferably contain as an optional component Fatty acid salts, which require a particularly low foam level. The soaps are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.

Industrial applicability

The agents according to the invention are generally aqueous with a non-aqueous content of preferably 5 to 35% by weight and in particular 8 to 15% by weight and are particularly suitable for the treatment of textile fabrics, such as yarns, webs of fabric and in particular Textiles. They are usually used at low temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C). The agents are not only characterized by excellent stain removal, but also reliably prevent deposits of lime and metal on the fibers and thus also prevent incrustation and yellowing. Although the actual use of the agents is aimed at removing stains during washing, they are in principle also suitable for other purposes in which hypochlorite solutions are used, for example for cleaning and disinfecting hard surfaces.

In addition, the agents can contain optical brighteners, dyes and pigments in a total amount of 0.01 to 0.5% by weight, based on the agents. The optical brighteners can be, for example, the potassium salt of 4,4'-bis (1,2,3-triazolyl) - (2 -) - stilbin-2,2-suifonic acid, which is sold under the Phorwite® BHC brand 766 is distributed. Possible color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz). The agents according to the invention are produced by stirring. If necessary, the product obtained can be decanted or filtered to remove foreign bodies and / or agglomerates. The agents also have a viscosity - measured at 20 ° C. in a Brookfield viscometer (spindle 1, 10 rpm) - above 100, preferably above 200 mPas.

Examples

Various hypochlorite solutions were mixed with fragrance capsules and with the pure fragrance, filled into dark bottles and stored at 25 ° C. In each case 100 ml of the agents were assessed visually immediately after production and after storage for 1 or 4 weeks, then filled into beakers and treated with a magnetic stirrer for 1 min with poor stirring performance. The subjective impression of smell was then determined. The results are summarized in Table 1. Examples 1 to 3 are according to the invention, examples V1 and V2 serve for comparison.

Table 1 Odor impression

1) Module 2.0; 2) Sequion® (Fa.Bozetto); 3) Carbopol 497 (Goodrich) 4), Norasol® LMW 45 N (sodium salt, MW = 4,500, NorsoHaas); 5) loading: 90% by weight citrus aroma (Vercitron), wrapping material: sodium alginate 6); Loading: 90% by weight rose aroma (Terciopelo), wrapping material: sodium alginate The preparations according to the invention with the microencapsulated fragrance are homogeneous even after 4 weeks of storage, ie the capsules have not settled. While the comparison formulations, despite a 30% higher vercitron content, no longer have a citrus aroma after 1 week due to chemical decomposition and rather have a pungent chlorine smell, when the preparations according to the invention are subjected to mechanical stress, a sufficient amount of citrus aroma is released even after storage. As a result, microencapsulation proves to be suitable for preventing the chemical decomposition of the sensitive fragrances.

Claims

claims 1. Active chlorine-containing preparations containing fragrances, characterized in that the fragrances are in microencapsulated form. 2. Preparations according to claim 1, characterized in that - based on the agent - contain 0.5 to 10 wt .-% alkali hypochlorites. 3. Preparations according to claims 1 and / or 2, characterized in that they contain - based on the agent - 0.5 to 2 wt .-% alkali hydroxides. 4. Preparations according to at least one of claims 1 to 3, characterized in that they contain - based on the agent - 0.1 to 10 wt .-% microcapsules with a fragrance content. 5. Preparations according to at least one of claims 1 to 4, characterized in that they contain microcapsules, the coating substance is selected from the group formed by gum arabic, agar, agarose, maltodextrins, alginic acid, alginates, fats, fatty acids, cetyl alcohol , Collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides, celluloses, cellulose esters, cellulose ethers, starch ethers, starch esters, polyacrylates, polyamides, polyvinyl alcohols and polyvinyl pyrrolidone. 6. Preparations according to at least one of claims 1 to 5, characterized in that they contain microcapsules, the diameter of which is 0.01 to 10,000 microns along its greatest spatial extent. 7. Preparations according to at least one of claims 1 to 6, characterized in that they contain microcapsules which - based on the weight of the capsules - contain 1 to 95% by weight of fragrances. 8. Preparations according to at least one of claims 1 to 7, characterized in that they further contain sequestering agents. 9. Preparations according to at least one of claims 1 to 8, characterized in that they further contain thickeners. 0. Preparations according to at least one of claims 1 to 9, characterized in that they have a Brookfield viscosity above 100 mPas.