EP2711414B1 - Stabilisation of capsule systems in detergent and cleaning compositions - Google Patents

Description

Field of the invention

The invention relates to the use of 2,3-bis (12-hydroxy¬octadecanol¬oxy) propyl-12-hydroxyoctadecanoate as a rheology stabilizer for capsules in detergents and cleaners, wherein the capsules contain active ingredients or ingredients and an average particle size distribution of 0.1 nm to 1 micron.

State of the art

The incorporation of certain active ingredients (eg bleaches, enzymes, perfumes, dyes, etc.) into liquid detergents and cleaners can cause problems. For example, incompatibilities between the individual active ingredient components of the liquid detergents and cleaners may occur. This can lead to undesirable discoloration, agglomeration, odor problems and destruction of detergent active ingredients. The consumer, however, requires liquid detergents and cleaning agents which, even after storage and transport, develop optimally at the time of use. This implies that the ingredients of the liquid detergent and cleaning agent have previously neither sedimented, decomposed or volatilized.

A concept for the incorporation of sensitive, chemically or physically incompatible as well as volatile components is the use of capsules and in particular microcapsules in which these ingredients are trapped stable storage and transport. For example, detergents and cleaners may contain the following active ingredients and ingredients which can be encapsulated: softeners, fragrances, pH adjusters, fluorescers, dyes, hydrotopes, silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, anti-crease agents, antimicrobial agents, germicides, fungicides , Antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, bleaching agents, acidifying agents and UV absorbers; just to name a few. The stabilization of the capsule in formulations often presents a challenge.

Fragrances, for example, are an essential ingredient in the formulation for detergents and cleaners. So laundry should have a pleasant and fresh fragrance both in the wet and in the dry state. Therefore, it is expedient that fragrances have a good absorption on the fiber and stick to it, then releasing the fragrances releasing again, so that the laundry over a longer period of time gives off a pleasant fragrance. The demands on fragrances are therefore quite high. The fundamental problem with the use of fragrances is that fragrances are volatile substances. This property, however, also causes its scent effect. One stands therefore with the employment of Fragrances in textile and surface treatment agents face the challenge of stabilizing these volatile fragrances long enough so that they do not all evaporate within a very short time and no longer produce a fragrance effect. The fragrances should evaporate after cleaning within a certain period of time, thereby causing a long-lasting and constant as possible fragrance effect. A problem with fragrances is the fact that the fragrance of a perfume changes over time, because the fragrances that represent the fresh and light notes of the perfume vaporize faster by their high vapor pressure than the fragrances that represent the heart and base notes. Therefore, fragrances are often encapsulated to stabilize the fragrance impression over a longer period of time. However, this leads to the problem that the capsules, which are such fragrances, but also other ingredients that are common for detergents and cleaners, usually after a long time, sediment or frame and thus destroy the stability of the formulation.

In WO 2011 031940 A1 An external structuring system (ESS) for the stabilization of aqueous detergents and cleaners is described. The ESS comprises glyceride crystals, preferably of hardened castor oils, alkanolamines and anions derived from anionic surfactants.

From the cosmetics sector are in the British patent specification GB 1 471 406 B liquid aqueous cleaning agents containing at least 2 wt.% Triethanolaminlaurylsulfat, a total of 8 to 50 wt.% Surfactant and 0.1 to 5 wt.% Suspended phase, for example, contain spherical capsules with a diameter of 0.1 to 5 mm, and a pH Value of 5.5 to 11. A homogeneous distribution of the suspended phase is achieved by using water-soluble acrylic acid polymers such as Carbopol 941.

One way to suspend particles or capsules in a liquid is to use structured liquids. A distinction is made between internal and external structuring. External structuring can be achieved, for example, by using structuring gums such as, for example, xanthan gum, guar gum, locust bean gum, gellan gum, wellan gum or carrageenan or of polyacrylate thickeners.

From an aesthetic point of view, it is desirable that the liquid detergents in which the particles are suspended are transparent or at least translucent. However, the use of structuring gums often leads to cloudy composition.

In the WO 2000/036078 A1 describes transparent / translucent liquid detergents which are capable of suspending particles having a size of 300 to 5000 microns, comprising at least 15 wt .-% of surfactant and 0.01 to 5 wt.% Of a polymeric gum.

A disadvantage of using these structurizing or thickening agents is their sensitivity to ionic compounds, in particular to the anionic surfactants which are obligatory in cleaning applications. At high concentrations of polymeric thickeners in systems with simultaneously high concentrations of anionic surfactants, drastic increases in viscosity can occur, which greatly impair the handling of the detergents and cleaners (for example, pumping, pouring or metering). In the EP 1 502 944 A1 For example, liquid laundry detergent products that are aqueous and that are in the form of suspensions of visibly dissimilar globules in an externally structured fluid matrix are described. Castor oil and its derivatives may be considered as an organic external structural agent, whereby THIXCIN® should be considered as such.

In the US 2010/150975 A1 there are disclosed structured liquid compositions comprising a liquid matrix comprising: a fiber network structurant in an amount of about 0.05 to about 1 percent by weight of the composition, wherein the fiber network structurant comprises non-polymeric crystalline hydroxyl functional materials; a bacterial cellulose network; and mixtures thereof; and water in an amount of from about 0.1% to about 75% by weight of the composition and a plurality of encapsulated actives in an amount of from about 0.5% to about 70% by weight of the composition.

In the WO 2011/120772 A1 discloses methods for introducing microcapsules having an anionic charge into a structured, aqueous, concentrated liquid detergent. an external structuring agent is THIXCIN®.

In the US 2011/0269657 A1 is about microcapsules that have been improved in their permeability properties. More concretely, the document describes various consumer products containing many microcapsules with a low permeability. THIXCIN® is used as a suspending agent.

It was an object of the present invention to develop and provide a rheology stabilizer for capsules containing active ingredients and ingredients in formulations, such as in detergents and cleaners.

This rheology stabilizer should not only ensure a good storage stability of the formulation, but also build a network in the formulation that hold the capsules with the active ingredients and ingredients in the balance so that they do not sediment or cream in the formulation. This ensures easy dosing without destabilizing the formulation and rapid re-stabilization of the capsules in the formulation once the mechanical action is removed.

Surprisingly, compositions have been found which are suitable as rheology stabilizer for such capsules in detergents and cleaners. The rheology stabilizer of the present invention is suitable for capsules having an average particle size distribution of 0.1 nm to 1 μm. A rheology stabilizer according to the invention comprises at least one rheology modifier which is 2,3-bis (12-hydroxy-octadecanol-oxy) -propyl-12-hydroxyoctadecanoate.

Description of the invention

The present invention is the use of 2,3-bis (12-hydroxy-octadecanol-oxy) propyl-12-hydroxyoctadecanoate as a rheology stabilizer for capsules in liquid detergents and cleaners, the 0.5 to 15 wt .-% of a solvent component comprising dipropylene glycol and 1,2-propanediol, wherein the capsules have an average particle size of 0.1 nm to 1 micron. 2,3-bis (12-hydroxy-octadecanol-oxy) -propyl-12-hydroxyoctadecanoate is available under the tradename Thixcin® from Elementis Specialitis. The core of the capsules preferably comprises active ingredients and ingredients for the care, conditioning and / or aftertreatment of textiles and preferably substances selected from the group consisting of perfumes, builders, bleaches, bleach activators, enzymes, grayness inhibitors, foam inhibitors, inorganic salts, solvents, pH adjusters, fluorescers, dyes, hydrotopes, silicone oils, soil release compounds, optical brighteners, grayness inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, swelling and anti-slip agents, UV absorbers, acidifiers.

The rheology modifier used in the invention is 2,3-bis (12-hydroxyoctadecanoloxy) propyl 12-hydroxyocta-decanoate, which is Thixcin®.

In a preferred embodiment, the active substances and ingredients in the capsules to be stabilized are preferably selected from the group consisting of fragrances, builders, bleach activators, enzymes, grayness inhibitors, dyes, hydrotopes, antimicrobial agents, germicides, fungicides, antioxidants. These active substances and ingredients are particularly preferably fragrances, builders and enzymes. Very particular preference is given to containing fragrances in the capsules.

The invention relates to the use of 2,3-bis (12-hydroxyoctadecanoloxy) propyl 12-hydroxyoctadecanoate for the stabilization of perfume capsules in detergents and cleaners.

The present invention also relates to liquid detergents and cleaners, having a content of 0.5 to 15 wt .-% of a solvent component comprising dipropylene glycol and 1,2-propanediol and a content of 0.01 to 10 wt .-% of capsules with a average particle size of 0.1 nm to 1 μm containing 2,3-bis (12-hydroxy-octa-decanol-oxy) -propyl-12-hydroxy-octadecanoate in an amount of 0.15 to 25% by weight. The detergents and cleaners are particularly preferably aqueous, that is to say they have a water content of greater than 5% by weight, preferably greater than 15% by weight and more preferably greater than 25% by weight.

The active ingredients and ingredients contained in the detergents and cleaning agents according to the invention are described in detail below. However, the list of such active ingredients and ingredients is not limiting and may include other active ingredients and ingredients that are not further discussed below.

fragrances

Preferred perfumes or perfume oils which can be incorporated into the compositions are not subject to any restrictions. Thus, as perfumes, individual fragrance compounds, both synthetic or natural compounds of the ester type, ethers, aldehydes, ketones, alcohols, hydrocarbons, acids, carbonic esters, aromatic hydrocarbons, aliphatic hydrocarbons, saturated and / or unsaturated hydrocarbons and mixtures thereof can be used. As fragrant aldehydes or Duftketone thereby all usual fragrance aldehydes and fragrance ketones can be used, which are typically used to bring about a pleasant fragrance sensation. Suitable fragrance aldehydes and fragrance ketones are well known to those skilled in the art. The fragrance ketones can all comprise ketones which can impart a desired fragrance or sensation of freshness. It is also possible to use mixtures of different ketones. For example, the ketone may be selected from the group consisting from buccoxime, isojasmon, methyl beta-naphthyl ketone, musk indanone, tonalid / musk plus, alpha-damascon, beta-damascone, delta-damascone, iso-damascone, damascenone, damarose, methyl dihydrojasmonate, menthone, carvone, camphor, fenchone , Alphalons, beta-ionone, dihydro-beta-ionone, gamma-methyl so-called ionone, fleuramon, dihydrojasmon, cis-jasmone, iso-E-super, methyl-cedryl-ketone or methyl-cedrylon, acetophenone, methyl-acetophenone, Para-methoxy-acetophenone, methyl-beta-naphthyl-ketone, benzyl-acetone, benzophenone, para-hydroxy-phenyl-butanone, Celery ketone or livescone, 6-isopropyldecahydro-2-naphthone, dimethyl-octenone, Freskomenth, 4- (e.g. 1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methyl-heptenone, 2- (2- (4-methyl-3-cyclohexen-1-yl) -propyl) -cyclopentanone, 1- (p- Menthene-6 (2) -yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1, 1,2,3,3-pentamethyl-4 (5H) -indanone, 4-damascol, dulcinyl or cassion, gelson, hexalon, isocyclone E, methyl cyclocitron , Methyl-lavender-ketone, Orivon, para-tert-butyl-cyclohexanone, Verdon, Delphon, Muscone, Neobutenon, Plicaton, Velouton, 2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran , Hedione and mixtures thereof. Preferably, the ketones may be selected from alpha damascone, delta damascone, iso damascone, carvone, gamma-methyl-ionone, iso-E-super, 2,4,4,7-tetramethyl-oct-6-en-3-one, benzylacetone , Beta Damascone, Damascenone, Methyl Dihydrojasmonate, Methyl Cedrylon, Hedione and mixtures thereof.

Suitable fragrance aldehydes may be any aldehydes which, in accordance with the fragrance ketones, impart a desired fragrance or sensation of freshness. In turn, they may be individual aldehydes or aldehyde mixtures. Suitable aldehydes are, for example, Melonal, Triplal, Ligustral, Adoxal, Anisaldehyde, Cymal, Ethylvanillin, Florhydral, Floralozon, Helional, Heliotropin, Hydroxycitronellal, Koavon, Laurinaldehyde, Canthoxal, Lyral, Lilial, Adoxal, Anisaldehyde, Cumal Methyl-nonyl-acetaldehyde, Citronellal , Citronellyloxyacetaldehyde, Cyclamenaldehyde, Bourgeonal, p, t-Bucinal, Phenylacetaldehyde, Undecylenaldehyde, Vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecene-I-al, alpha-n-amylcinnamaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) -propanal, 2-methyl-3- (paramethoxyphenylpropanal), 2-methyl-4- (2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl -2,6-octadiene-1-al, 3,7-dimethyl-6-octene-1-al, [(3,7-dimethyl-6-octenyl) oxy] acetaldehyde, 4-isopropylbenzyaldehyde, 1,2,3 , 4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxyaldehyde, 2-methyl-3- (isopropylphenyl) propanal, decyl aldehyde , 2,6-dimethyl-5-heptenal; 4- (tricyclo [5.2.1.0 (2,6)] - decylidene-8) butanal; octahydro-4,7-methano-IH-indenecarboxaldehyd; 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7 carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyl octanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) - 3-cyclohexene-carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctane 1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3- (4-tert-butyl) propanal, 3- (4-ethylphenyl) -2,2-dimethylpropanal, 3- (4-methoxyphenyl) -2-methylpropanal, methylnonylacetaldehyde, 2-phenylpropan-1-al, 3-phenylprop-2-en-1-al, 3 Phenyl-2-pentylprop-2-en-1-al, 3-phenyl-2-hexylprop-2-enal, 3- (4-isopropylphenyl) -2-methylpropan-1-al, 3- (4-ethylphenyl) - 2,2-dimethylpropan-1-al, 3- (4-tert-butylphenyl) -2-methyl-propanal, 3- (3 , 4-methylenedioxyphenyl) -2-methylpropan-1-al, 3- (4-ethylphenyl) -2,2-dimethylpropanal, 3- (3-isopropylphenyl) -butan-1-al, 2,6-dimethylhept- 5-en-1-al, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5 or 6 methoxyhexahydro-4,7-methanoindan-1 or 2-carboxyaldehyde, 3,7-dimethyloctan-1-al , 1-undecanal, 10-undecene-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexene-carboxyaldehyde, 7-hydroxy-3,7-dimethyl-octanal ; trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-butenal, ortho Methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde; 5,9-dimethyl-4,8-decadienal, peony-aldehyde (6,10-dimethyl-3-oxa-5,9-undecadiene-1-al), hexahydro-4,7-methanoindan-1-carboxaldehyde, octanal, 2-methyl octanal, alpha-methyl-4- (1-methylethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxyacetaldehyde, 2-methyl-3-phenyl-2-propene-1 -al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo [2.2.1] -hept-5-ene-2-carbaldehyde, 9-decenal, 3 Methyl 5-phenyl-1-pentanal, methylnonylacetaldehyde, 1-p-menthene-q-carboxaldehyde, citral or mixtures thereof, lilial citral, 1-decanal, n-undecanal, n-dodecanal, florhydral, 2,4-dimethyl 3-cyclohexene-1-carboxaldehyde 4-methoxybenzaldehydes, 3-methoxy-4-hydroxybenzaldehydes, 3-ethoxy-4-hydroxybenzaldehydes, 3,4-methylenedioxybenzaldehyde and 3,4-dimethoxybenzaldehyde, and mixtures thereof. As exemplified above, the fragrance aldehydes and fragrance ketones may have an aliphatic, cycloaliphatic, aromatic, ethylenically unsaturated structure or a combination of these structures. There may also be further heteroatoms or polycyclic structures. The structures may have suitable substituents such as hydroxyl or amino groups. For other suitable fragrances, selected from aldehydes and ketones, is on Steffen Arctander "Published 1960 and 1969, respectively, Reprinted 2000 ISBN: Aroma Chemicals Vol. 1: 0-931710-37-5 . Aroma Chemicals Vol. 2: 0-931710-38-3 ", directed.

Suitable fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmacyclate. Fragrance compounds of the hydrocarbon type are, for example, terpenes such as limonene and pinene. Suitable fragrances of the ether type are, for example, benzyl ethyl ether and ambroxan. Suitable perfume alcohols are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5- Trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 1-octen-3-ol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6,8-dimethyl 2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, beta-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethylbenzylcarbinol, Dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvaniline, anethole, eugenol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, para-menthane-7-ol, phenylethyl alcohol, Phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadienol, trans-2-nonen-1-ol, trans-2-octenol, Undecanol, vanillin, cinnamyl alcohol, where, if more fragrance alcohols are present, these may be selected independently of each other.

Fragrances or perfume oils may also be natural fragrance mixtures as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muscat sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and orange blossom oil, neroli oil, orange peel oil and sandalwood oil. Essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, champa blossom oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, guriuri balm oil, helichrysum oil, hol oil, ginger oil, iris oil, cajeput oil, calamus oil , Chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk nut oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, origanum oil, palmarosa oil , Patchouli oil, Peruvian balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spik oil, Star aniseed oil, Turpentine oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Vermouth oil, Wintergreen oil, Ylang-ylang oil , Y-sop oil, cinnamon oil, cinnamon leaf oil, citronella oil, Z crown oil and cypress oil.

Also suitable as perfume are so-called perfume precursors (prodrugs). This class of compounds are compounds which release a desired odor and / or perfume molecule by the breaking of a chemical bond, for example by hydrolysis. Typically, to form a perfume precursor, a desired perfume raw material is chemically combined with a carrier, preferably a slightly volatile or moderately volatile carrier. The combination results in a less volatile and more hydrophobic perfume precursor with improved attachment to fabrics. The perfume is then released by breaking the bond between the perfume raw material and the carrier, for example, by a change in pH (eg, by perspiration upon wear), humidity, heat and / or sunlight during storage or drying on the skin Clothes line.

The perfume raw material for use in perfume precursors are typically saturated or unsaturated volatile compounds containing an alcohol, an aldehyde and / or a ketone group. Fragrance raw materials useful herein include any fragrant substances or mixtures of substances already described above.

Particular advantageous, useable perfume precursors obey the formula (III)

RC (OR ¹ ) (OR ² ) OR ³ (III)

in which R is hydrogen, linear C ₁ -C ₈ -alkyl, branched C ₃ -C ₂₀ -alkyl, cyclic C ₃ -C ₂₀ -alkyl, branched cyclic C ₆ -C ₂₀ -alkyl, linear C ₆ -C ₂₀ -alkenyl, branched C ₆ -C ₂₀ alkenyl, cyclic C ₆ -C ₂₀ alkenyl, branched cyclic C ₆ -C ₂₀ alkenyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, and mixtures thereof; R ¹ , R ² and R ^{3 are} independently linear, branched or substituted C ₁ -C ₂₀ alkyl; linear, branched or substituted C ₂ -C ₂₀ alkenyl; substituted or unsubstituted C ₃ -C ₂₀ cyclic alkyl; substituted or substituted C ₆ -C ₂₀ -aryl, substituted or unsubstituted C ₂ -C ₄₀ -alkyleneoxy; substituted or unsubstituted C ₃ -C ₄₀ alkyleneoxyalkyl; substituted or unsubstituted C ₆ -C ₄₀ alkylene aryl; substituted or unsubstituted C ₆ -C ₃₂ -aryloxy; substituted or unsubstituted C ₆ -C ₄₀ alkyleneoxyaryl; C ₆ -C ₄₀ -Oxyalkylenaryl and mixtures thereof. The use of such substances, especially in (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention.

Further particularly advantageous, usable perfume precursors are acetals or ketals, preferably obeying the formula (IV)

RC (R ¹ ) (OR ³ ) -OR 2 (IV)

wherein R is linear C ₁ -C ₂₀ alkyl, branched C ₃ -C ₂₀ -alkyl, cyclic C ₆ -C ₂₀ -alkyl, branched cyclic C ₆ -C ₂₀ -alkyl, linear C ₂ -C ₂₀ -alkenyl, branched C ₃ -C ₂₀ alkenyl, C 6 -C 20 cyclic alkenyl, branched cyclic C ₆ -C ₂₀ -aryl is C ₆ -C ₂₀ alkenyl, and mixtures thereof, substituted or unsubstituted; R ^{1 is} hydrogen or R; R ² and R ^{3 are} each independently selected from the group consisting of linear C ₁ -C ₂₀ alkyl, branched C ₃ -C ₂₀ alkyl, cyclic C ₃ -C ₂₀ alkyl, branched cyclic C ₆ -C ₂₀ Alkyl, linear C ₆ -C ₂₀ alkenyl, branched C ₆ -C ₂₀ alkenyl, cyclic C ₆ -C ₂₀ alkenyl, branched cyclic C ₆ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, substituted C ₇ -C ₂₀ aryl and mixtures thereof. The use of such substances, especially in (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention.

Further particularly advantageous, usable fragrance precursor obey the formula (V)

R ⁴ OC (OR ¹ ) (OR ³ ) -OR ² (V)

wherein R ¹ , R ² , R ³ and R ^{4 are} independently linear, branched or substituted C ₁ -C ₂₀ alkyl; linear, branched or substituted C ₂ -C ₂₀ alkenyl; substituted or unsubstituted C ₅ -C ₂₀ cyclic alkyl; substituted or unsubstituted C ₆ -C ₂₀ -aryl, substituted or unsubstituted C ₂ -C ₄₀ -alkyleneoxy; substituted or unsubstituted C ₃ -C ₄₀ alkyleneoxyalkyl; substituted or unsubstituted C ₆ -C ₄₀ alkylene aryl; substituted or unsubstituted C ₆ -C ₃₂ -aryloxy; substituted or unsubstituted C ₆ -C ₄₀ alkyleneoxyaryl; C ₆ -C ₄₀ oxyalkylene aryl; and mixtures thereof. The use of such substances, especially in (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention.

It is particularly preferred if the fragrances used comprise silicic acid ester mixtures. Silica esters are represented, for example, by the formula (V)

R - (- O-Si (OR) ₂ -) _n -OR (V)

wherein R independently of one another is selected from the group which contains H, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C ₁ -C ₆ -hydrocarbon radicals and the perfume alcohol radicals and / or biocide alcohol radicals, and m values from the range 1 to 20 and n assumes values from the range 2 to 100. The silicic acid esters of the formulas preferably contain at least one perfume alcohol residue and / or biocide alcohol residue.

The silicic ester mixtures can be encapsulated, but also used without encapsulation. The presence of silicic ester mixtures often leads to the fact that the scent impression achievable, both in terms of appeal and intensity, even further can be improved. The fragrance impression is not only qualitative, ie the pleasing, better, but also longer.

The silicic acid ester mixtures may also be contained in the microcapsules. If the silicic acid ester mixtures in the microcapsules preferably make up at least 2% by weight of the total encapsulated amount of fragrance,% by weight, based on the amount of the encapsulated fragrances, a preferred embodiment of the invention provides a further improvement in the desired fragrance effect causes the drying.

Particularly suitable perfume precursors are reaction products of compounds comprising at least one primary and / or secondary amine group, for example, an amino-functional polymer, especially an amino-functional silicone, and a perfume ingredient selected from ketone, aldehyde, and mixtures thereof. The use of such substances, in particular in (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the

The total amount of fragrances in the washing and cleaning agent according to the invention is preferably between 0.01 and 5 wt.%, Particularly preferably between 0.1 and 3 wt.% And most preferably between 0.5 and 2 wt.% Based on the total amount of the composition.

Preference is given to using mixtures of different fragrances (from the various above-mentioned classes of fragrance) which together produce an appealing fragrance. In this case, the total amount of the at least one perfume is the amount of all the perfumes in the mixture together relative to the total amount of the agent.

These fragrances and perfume oils are preferably encapsulated, so that the stabilizing system according to the invention for capsules is used thereon.

Liquid detergents

The liquid detergents may contain further commercial constituents, such as, for example, surfactants, builders, bleaches, bleach activators, thickeners, enzymes, electrolytes, pH adjusters, dyes and fragrances, foam inhibitors, antiredeposition agents, optical brighteners, grayness inhibitors, anti-crease agents, antimicrobial agents, preservatives, Antioxidants, antistatic agents, UV adsorbers, heavy metal complexing agents and the like. These auxiliaries are described in more detail below:

A. Surfactants

As surfactants for the preparation of the detergents or cleaners, anionic, cationic, amphoteric and / or nonionic surfactants and branched alkyl sulfates can be used in addition to the nonionic surfactants.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO, 4 EO or 7 EO, C9-11 alcohol with 7 EO, C13-5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12 Alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-4 alcohol with 3 EO and C12-8 alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

Another class of nonionic surfactants which can be used to advantage for the production of detergents or cleaners are the alkylpolyglycosides (APG). Usable Alkypolyglycoside satisfy the general formula RO (G) Z, in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable for the preparation of the detergents or cleaners. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

R-CO-N (R1) - [Z] in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula R-CO-N (R 1 -O-R 2) - [Z] in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched one or a cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1-4 -alkyl or phenyl radicals and [Z ] represents a linear polyhydroxyalkyl radical whose alkyl chain has at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of nonionic surfactants is the liquid detergents and cleaners preferably 5 to 30 wt.%, Preferably 7 to 20 wt.% And in particular 9 to 15 wt.%, Each based on the total agent.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type are preferably C9-3-alkylbenzenesulfonates, Olefinsulfonate, i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C12-8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation, into consideration. Also suitable are alkanesulfonates which are obtained from C 12-8 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Also suitable are sulfonation of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%. In particular, preferred are alpha-sulfofatty acid alkyl esters which have an alkyl chain with not more than 4 C atoms in the ester group, for example methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of the alpha - sulfo fatty acids (MES), but also their saponified disalts are used.

Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C12-C18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, C12-C16 alkyl sulfates and C12-C15 alkyl sulfates and C14-C15 alkyl sulfates are preferred. 2,3-Alkyl sulfates, which can be obtained, for example, as commercial products of the Shell Oil Company under the name DAN (R), are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C7-21 alcohols ethoxylated with from 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols having on average 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of preferred liquid detergents and cleaners to anionic surfactants is 1 to 30 wt.%, Preferably 4 to 25 wt.% And in particular 5 to 22 wt.%, Each based on the total agent. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight and more preferably at least 3% by weight and especially preferably at least 4% by weight.

Other surfactants which may be used to prepare the detergents or cleaners according to the invention are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Gemini surfactants for the preparation of detergents or cleaners are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or Dimeralkoholbis and trimeric tris-sulfates and ether sulfates according to the German patent application DE-A-195 03 061 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the liquid washing and cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid detergent and cleaning agent.

B. builders

Suitable builders or builders which may be present in the liquid detergents and cleaners are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, organic cobuilders, phosphates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} ^* H2O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both beta - and delta - sodium disilicates Na ₂ Si ₂ O ₅ ^* yH ₂ O preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

A useful fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite MAP ™ (commercial product the company Crosfield) particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ) marketed by the company SASOL under the trade name VEGOBOND AX (R) and by the formula

n Na ₂ O ^* (1-n) K ₂ O ^* Al ₂ O _3. (2-2.5) ^* SiO _2. (3.5-5.5) ^* H ₂ O,

can be described
equivalent. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the case where the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups, C ₁₂ -C ₁₄ fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Suitable builders are organic cobuilders, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and also phosphonates.

Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol. For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Your molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-Alkylallylsulfonsaeure and sugar derivatives ,

Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to co-builder properties, also have a bleach-stabilizing action.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C6 of the saccharide ring may be particularly advantageous.

A preferred dextrin is in the British patent application GB 9,419,091 B1 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP 032202 A . EP 0427349 A . EP 0472042 A and EP 0542496 A as well as the international patent applications WO 1992/018542 A . WO 1993/008251 A . WO 1994/028030 A . WO 1995/007303 A . WO 1995/012619 A and WO 1995/020608 A known. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat US 4,524,009 . US 4,639,325 In the European patent application EP 0150930 A and Japanese Patent Application JP 1993/339896 A to be discribed.

Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in the international patent application WO 1995/020029 A described.

Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular when the detergents and cleaners also contain bleach, it is preferable to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned for the preparation of the compositions.

In addition, all compounds that are capable of forming complexes with alkaline earth ions can be used as co-builders.

Further useful organic builders are also the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents and / or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

C. Bleaching agents and bleach catalysts

Among the compounds serving as bleaching agents in water H2O2, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peroxyacids or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergents and cleaners. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2 , 5-dihydrofuran. In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be incorporated into the fabric treatment agents. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

D. thickener

A liquid detergent and cleanser may contain a thickener. The thickener may include, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, carrageenan, carboxymethyl cellulose, bentonites, wellan gum, locust bean gum, agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein include. But also modified natural substances such as modified starches and celluloses, exemplified here carboxymethyl cellulose and other cellulose ethers, called hydroxyethyl and propyl cellulose and gum ethers, can be used as a thickener.

Examples of polyacrylic and polymethacrylic thickeners include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from BF Goodrich under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight 1,250,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C1- 4-alkanols formed esters (INCI AcrylatesCopolymer), which includes about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2 ) or of butyl acrylate and methyl methacrylate ( CAS 25852-37-3 ) and which are available, for example, from Rohm and Haas under the trade names Aculyn® and Acusol® and from Degussa (Goldschmidt) under the trade name Tego® Polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 ( CAS 25852-37-3 ); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C10-30 alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C1-4-alkanols formed, esters (INCI Acrylates / C10-30Alkyl Acrylate Crosspolymer) and which are available, for example, from the company. BF Goodrich under the trade name Carbopol®, eg the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C10-30Alkyl Acrylate Crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).

Another preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by xanthomonascampestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain of beta-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum. In particular, a fatty alcohol is also suitable as thickener. Fatty alcohols may be branched or unbranched, of native or of petrochemical origin. Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preference is given to using mixtures of different C chain lengths, such as tallow fatty alcohol or coconut oil fatty alcohol. Examples are Lorol® Spezial (C12-14-ROH) or Lorol® Technical (C12-18-ROH) (both ex Cognis). Preferred liquid detergents and cleaners contain 0.01 to 3% by weight, and preferably 0.1 to 1% by weight, of thickening agent, based on the total agent. The amount of thickener used depends on the type of thickener and the desired degree of thickening.

E. Enzymes

The detergents and cleaning agents may contain enzymes in encapsulated form and / or directly in the washing and cleaning agent. Suitable enzymes are, in particular, those from the classes of the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, beta-glucanases, oxidases, peroxidases, perhydrolases and / or laccases and mixtures the enzymes mentioned in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases contribute to color retention and to increasing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicolainsolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing Mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and p-glucosidases, which are also cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers to protect against premature degradation. The proportion of enzymes, of the enzyme liquid formulation (s) or of the enzyme granules directly in detergents and cleaners can be, for example, about 0.01 to 5% by weight, preferably 0.12 to about 2.5% by weight.

It may, for example, in special detergents and cleaners for consumers with allergies, but also be preferred that the washing and cleaning agent contains no enzymes.

F. Electrolytes

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the detergents and cleaners is preferred. The proportion of electrolytes in the washing and cleaning agent is usually 0.1 to 5 wt .-%.

G. Solvent

Non-aqueous solvents which can be used in the liquid detergents and cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents may be used in the liquid detergents and cleaners in amounts of between 0.5 and 15% by weight, but preferably below 12% by weight and in particular below 9% by weight.

H. Viscosity

The viscosity of the washing and cleaning agents in liquid form can be measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas for liquid detergents , Preferred liquid detergents and cleaners have viscosities of 700 to 4000 mPas, with values between 1000 and 3000 mPas being particularly preferred. The viscosity of fabric softeners is preferably 20 to 4000 mPas, with values between 40 and 2000 mPas being particularly preferred. The viscosity of fabric softeners is particularly preferably from 40 to 1000 mPas.

I. pH adjusting agent

In order to bring the pH of the liquid detergents and cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 7% by weight of the total formulation. The pH of liquid detergents and cleaners is preferably between 4 and 10, and preferably between 5.5 and 8.5. The pH of liquid fabric softeners is preferably between 1 and 6 and preferably between 1.5 and 3.5.

J. Dyes

In order to improve the aesthetic impression of the textile treatment agents, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents and cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

K. Anti-redeposition agent

Suitable soil-release polymers, which are also referred to as "antiredeposition agents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ethers and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.

L. Optical brightener

Optical brighteners (so-called "whiteners") can be added to the detergents and cleaning agents in order to eliminate graying and yellowing of the treated textile fabrics. These fabrics impinge on the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible long wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and the yellow color of the broomed or yellowed wash as pure white results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulphonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, Benzisoxazole and benzimidazole systems and substituted by heterocycles pyrene derivatives. The optical brighteners are usually used in amounts of between 0% and 0.3% by weight, based on the finished detergent and cleaner.

M. Graying inhibitors

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. For this purpose, water-soluble colloids are mostly of organic nature, for example glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the detergents and cleaners.

N. Anti-crease agent

Since textile fabrics, in particular of rayon, viscose staple, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and squeezing transversely to the fiber direction, the detergents and cleaners may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, - alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

O. Antimicrobial agents

To combat microorganisms, the detergents and cleaning agents may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate Washing and cleaning agents can be completely dispensed with these compounds.

P. Preservative

The detergents and cleaners according to the invention may contain preservatives, it being preferred to use only those which have no or only a low skin-sensitizing potential. Examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof. A suitable preservative is the solvent-free, aqueous combination of diazolidinyl urea, sodium benzoate and potassium sorbate (available as Euxyl® K 500ex Schülke and Mayr), which can be used in a pH range up to 7. In particular, preservatives based on organic acids and / or their salts are suitable for preserving the skin-friendly detergents and cleaners according to the invention.

Q. Antioxidants

To prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by oxygen and other oxidative processes, the detergents and cleaners may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.

R. Antistatic agents

An increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the detergents and cleaners. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. Antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textile fabrics or as an additive to detergents and cleaners, wherein a softening effect is additionally achieved.

S. foam inhibitors

To improve the rewettability of the treated fabrics and to facilitate the ironing of the treated fabrics, for example, silicone derivatives may be used in the fabric treatment agents. These additionally improve the rinsing out of the detergents and cleaning agents by their foam-inhibiting properties Properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total detergent and cleaning agent can be used.

T. UV absorber

Finally, the detergents and cleaners may also contain UV absorbers which wick onto the treated fabrics and improve the lightfastness of the fibers. Compounds exhibiting these desired properties include, for example, the non-radiative deactivation compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

U. heavy metal complexing agent

In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates. A preferred class of complexing agents are the phosphonates, which are contained in preferred textile treatment agents in amounts of from 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and in particular from 0.03 to 1.5% by weight. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2, 4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.

Preparation of the preparations

The liquid detergents are prepared by customary and known methods and processes in which, for example, the constituents are simply mixed in stirred kettles, whereby water, nonaqueous solvents and surfactants are expediently introduced and the further constituents are added in portions. Thus, liquid detergents and cleaners can be prepared by the acidic components such as the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, etc. and the nonionic surfactants are presented. The solvent component is preferably also added at this time, but the addition may also be made at a later time. To these components is added the polyacrylate. Subsequently, a base such as NaOH, KOH, Triethanolamine or monoethanolamine followed by the fatty acid, if any. Subsequently, the remaining ingredients and the remaining solvents of the aqueous liquid detergent and cleaner are added to the mixture and the pH is adjusted to about 8.5. Finally, the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid washing and cleaning agent by mixing.

The compositions according to the invention are preferably detergents which are suitable both for manual or machine washing, in particular for textiles. It can also be detergents or cleaning agents for industrial or household use. Cleaning agents can also be used, for example, for cleaning hard surfaces. These may be, for example, dishwashing detergents used for manual or automatic dishwashing. It can also be common industrial or household cleaners, which are used to clean hard surfaces such as furniture surfaces, tiles, tiles, wall and floor coverings. In addition to tableware, all other hard surfaces, in particular of glass, ceramic, plastic or metal, in household and in trade are also considered hard surfaces.

The detergents and cleaners are liquid formulations, which may be solutions, emulsions, dispersions suspensions, microemulsions, gels or pastes.

As a surface treatment agent, the composition may accordingly contain conventional ingredients of detergents in conventional amounts. For example, surface treatment agents may contain as cleaning agents, alkyl ether sulfates, alkyl and / or aryl sulfonates, alkyl sulfates, amphoteric surfactants, anionic surfactants, nonionic surfactants, cationic surfactants, solvents, thickeners, dicarboxylic acid (salts) and other auxiliaries and additives.

Some of these additional ingredients are already explained in detail in the front and are also valid for use in detergents (see eg nonionic surfactants). As auxiliaries and additives - especially in hand dishwashing detergents and cleaners for hard surfaces, in particular UV stabilizers, perfume, pearlescing agents (INCI Opacifying Agents, for example glycol distearate, eg Cutina® AGS the company Henkel KGaA, or mixtures containing this, eg Euperlane® from Henkel KGaA), SRP (soil repellent polymers), PEG terephthalates, dyes, bleaches (eg hydrogen peroxide), corrosion inhibitors, preservatives (eg the technical 2-bromo-2-nitropropane, also referred to as bronopol). 1,3-diol ( CAS 52-51-7 ), which is commercially available, for example, as Myacide® BT or BootsBronopol BT from Boots) and skin feel-improving or nourishing additives (eg dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, Sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate-fatty acid condensates, liposomes, polypropylene glycol, Nutrilan ™ Chitosan ™, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe Vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, in amounts of usually not more than 5% by weight, small quantities of enzymes can be used to increase the performance, preference is given to proteases (eg BLAP (Henkel), Savinase (NOVO), Durazym (NOVO), Maxapemm, etc.), Amylases (eg Fermamyl (NOVO), etc.), Lipases (eg Lipolase (NOVO), etc.), Peroxidases, Gluconases, Cellulases, Mannasen, etc., in amounts of preferably 0.001 to 1.5 wt.% And particularly preferably less than 0.5 wt.%.

capsules

The stabilizing system of the present invention is applied to capsules containing active ingredients and ingredients. The capsules in the present invention may be particles, microcapsules or speckles, but also granules, compounds and fragrance beads, with microcapsules or speckles being preferred.

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 of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. 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. Preferred are mononuclear microcapsules with a continuous shell. 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, e.g. 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 shell materials include chemically modified celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, as well as starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

Preferably, the capsules are microcapsules which comprise a water-insoluble wall material, preferably polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and compounds containing NH groups.

The procedure in microcapsule preparation as such is well known to those skilled in the art. Suitable methods for microcapsule preparation are familiar to the expert and are for. In US 3,870,52 , in US 3,516,941 , in US 3,415,758 or in EP 0026914 A1 described. The latter describes, for example, the production of microcapsules by acid-induced condensation of melamine-formaldehyde precondensates and / or their C ₁ -C ₄ -alkyl ethers in water, in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid.

Preferably, for example, melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules can be used, for. Available from 3M Corporation or BASF.

Suitable microcapsules are z. B. also in WO 2001/049817 A2 described.

The microcapsules are accessible by methods known in the art, with coacervation and interfacial polymerization being the most important. As microcapsules, all surfactant-stable microcapsules available on the market can be used, for example the commercial products (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), Coletica thalaspheres (marine collagen), Lipotec millicapsules (alginic acid, agar-agar) , Also unispheres (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanospheres (phospholipids).

Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckles".

A preferred matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution which also contains the active ingredient or the active ingredients to be entrapped is dripped and then cured in a precipitation bath containing Ca.sup.2 + ions or Al.sub.3.sup. + Ions. It may be advantageous that the alginate-based speckles are then washed with water and then washed in an aqueous solution with a complexing agent to free Ca 2+ ions or free Al 3+ ions, which undesirable interactions with ingredients of the liquid detergent and cleaning agent, eg fatty acid soaps, can be washed out. Subsequently, the alginate-based speckles are washed again with water to remove excess complexing agent. Alternatively, other, matrix-forming materials can be used instead of alginate. Examples of matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hyaluronic acid, Carboxymethylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. The matrix formation in these materials takes place for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the art as well as the production of particles with these matrix-forming materials.

The particles can be stably dispersed in the aqueous liquid detergent and cleaner. Stable means that the compositions are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably at least 6 weeks, without the medium creaming or sedimenting

The capsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their largest spatial extent, depending on the components contained in their interior and the application between 0.1 nm (not visually recognizable as a capsule) and 1 micron. The shell of the microcapsules surrounding the core or (filled) cavity has an average thickness in the range of between about 75 and 300 nm, preferably between about 80 nm and about 250 nm, in particular between about 90 nm and about 200 nm. Microcapsules, the fulfill the aforementioned parameters are particularly well stabilized in detergents and cleaners and thus show good results in the context of the invention.

Inside the capsules, sensitive, chemically or physically incompatible as well as volatile components (= active ingredients) of the liquid detergent and cleaning agent can be enclosed stable in storage and transport. The capsules may include, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti redeposition agents, pH adjusters, electrolytes, foam inhibitors and UV absorbers are located. In addition, the capsules of the aqueous liquid detergents and cleaners may contain cationic surfactants, vitamins, proteins, preservatives, detergency boosters or pearlescers. The fillings of the capsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The release of the active ingredients from the capsules is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action. In the invention, the liquid detergents and cleaners contain identical or different capsules in amounts of from 0.01 to 10% by weight, in particular from 0.03 to 5% by weight and very preferably from 0.05 to 2.5% by weight.

The liquid detergents and cleaners according to the invention with capsules are cloudy and have no sediment.

The present invention also encompasses a process for the preparation of liquid detergents and cleaners containing from 0.5 to 15% by weight of a solvent component comprising dipropylene glycol and 1,2-propanediol and containing from 0.01 to 10% by weight. Capsules having an average particle size of 0.1 nm to 1 μm The rheology stabilizer 2,3-bis (12-hydroxyoctadecanoloxy) propyl 12-hydroxyoctadecanoate is provided in a first step (a) and then in a solvent comprising dipropylene glycol and 1,2-propanediol stirred to obtain a mixture. Suitable solvents are aqueous solutions, such as surfactant solutions and / or alcoholic. Preference is given to solvents which are typical for detergents and cleaners and have already been described above. The mixture is heated to at least 85 ° C, preferably from 85 ° C to 90 ° C and from 85 ° C to 88 ° C, respectively. The rheology modifier is then preferably melted in the solvent at these temperatures. The mixture is then cooled to 40 ° C with stirring and then added to a detergent formulation.

Of course, the process steps can also be modified, for example by first stirring only part of the rheology modifier in the solvent, heating it and thus predissolving it.

Examples

The invention is further illustrated by the following examples. All information is given in weight percent, in each case based on the total mean.

example 1

1. a) Stabilisierungssystem H1:
   Thixcin ® wird in eine Menge von 0,2-0,4% in einem Gemisch aus Natriumbenzolsulfonat und Wasser zu gegeben und auf mind. 85°C erwärmt. Anschließend wird das Gemisch gerührt bis die Temperatur ca. 40°C erreicht hat. Zuletzt wird der Rest der Formulierung zu gegeben (Rezeptur in Tabelle 1).
2. b) Stabilisierungssysteme H2 bis H5 (Vergleichssysteme): HASE-Polyacrylate bzw. ASE-Polyacrylate (Novethix™ L10 Polymer, Polygel W301, Polygel W400, Carbopol® Aqua 30 Polymer) wird in eine Menge von 0.2 - 1.5% in Kombination mit Lithium-Magnesium-Natriumsilikat (Laponite ® OG), in eine Menge von 0.1 - 0.3% in die Rezeptur (Tabelle 1) eingerührt.
3. c) Vergleichssysteme V1:
   Es wird die Basisrezeptur (Tabelle 1) ohne weitere Zusätze verwendet.
4. d) Vergleichssysteme V2 bis V5:
   HASE-Polyacrylate bzw. ASE-Polyacrylate (Novethix™ L10 Polymer, Polygel W301, Polygel W400, Carbopol® Aqua 30 Polymer) wird in eine Menge von 0.2 - 1.5% ohne Lithium-Magnesium-Natriumsilikat (Laponite® OG) in die Rezeptur (Tabelle 1) eingerührt.

Preparation of the sample formulations with perfume capsules

1. a) Stabilization system H1:
   Thixcin® is added in an amount of 0.2-0.4% in a mixture of sodium benzenesulfonate and water and heated to at least 85 ° C. Subsequently, the mixture is stirred until the temperature has reached about 40 ° C. Finally, the rest of the formulation is added (recipe in Table 1).
2. b) Stabilization Systems H2 to H5 (Comparative Systems): HASE polyacrylates or ASE polyacrylates (Novethix ™ L10 polymer, W301 poly- mer, W400 polymer gel, Carbopol® Aqua 30 polymer) are mixed in an amount of 0.2 - 1.5% in combination with lithium Magnesium sodium silicate (Laponite® OG), stirred in an amount of 0.1-0.3% in the recipe (Table 1).
3. c) comparison systems V1:
   The basic formulation (Table 1) is used without further additives.
4. d) comparison systems V2 to V5:
   HASE polyacrylates or ASE polyacrylates (Novethix ™ L10 polymer, W301 polyols, W400 polyols, Carbopol® Aqua 30 polymer) are added to the formulation in an amount of 0.2-1.5% without lithium magnesium sodium silicate (Laponite® OG). Table 1).

Example 2 storage test

The detergent samples were stored in 30 ml glass bottles at 23 ° C, 5 ° C and 40 ° C. After 1, 2, 3 and 4 weeks, the samples were visually assessed for separation of the (perfume) capsules. When separations were observed, the formulation was rated unstable. If no separations were observed, the sample was rated stable.

The results are shown in Table 2. Where (+) = stable and (-) = unstable.

Example 3 Rheometer

The rheological properties of the samples were carried out with the aid of a rheometer.

Measurement conditions: 23 ° C, cone / plate C60 / 2 ° Ti, CR log 0.01 1 / s-40.00 1 / s, CR log 40.00 1 / s-0.011 / s.

The results are the illustration 1 refer to:
The lower curve shows the comparative experiment (designated as V 1.1) and the upper curve shows the formulation according to the invention (designated as V 3.2).

The rheology measurement shows the increase of the required force at the beginning and the decrease of the force to the middle of the measurement, followed by a rise to the end. This shows that the sample has a high viscosity during the rest phase, which falls rapidly due to the action of force (shearing action) and recovers in the subsequent rest phase. <b> Table 1 </ b> Basic recipe for detergents basic formulation Sodium benzenesulfonate (about 50%) 10.00% Fatty alcohol ethoxylate C12-18 9EO 3.00% Sodium lauryl ether sulfate (about 28%) 40.00% Sodium lauryl sulfate (approx. 35%) 10.00% 1,2-propylene glycol 3.00% Phosphonates (about 30%) 2.00% 96% ethanol 1.50% di-sodium citrate 2.00% Perfume 0.80% SymCap® perfume capsules 0.50% water Add to 100 Storage test of the detergent samples (amounts used in%) example V1 H1 V2 H2 V3 H3 V4 H4 V5 H5 Novethix L10 polymer (Lubrizole) 2 2 Polygel W 301 (3V) 2 2 Polygel W 400 (3V) 2 2 Carbopol Aqua 30 (Lubrizole) 2 2 Laponite OG (Rockwood) 0.15 0.15 0.15 0.15 Thixcin R (Elementis) 0.2 0.2 Result (-) (+) (-) (+) (-) (+) (-) (+) (-) (+) Perfume formulation of the perfume of the basic formula component proportion of ALDEHYDE C11 UNDECYLENIC 2.0% ALDEHYDE C12 MNA 6.0% ALLYLCYCLOHEXYLPROPIONAT 2.0% ALLYLHEPTYLAT 6.0% ANETHOL NAT. EX STERNANIS 0.5% ANISALDEHYDE PURE 6.5% BORNEOL CRIST. 2.0% DAMASCONE DELTA 4.5% EUCALYPTOL NAT. 6.0% FENCHELOEL AROMA TYPE SUESS NAT. 4.5% isobornyl 24.0% CAMPER DL 8.0% MANZANATE 4.0% NEROLIN YARA YARA KRIST. 4.0% component proportion of NEROLIONE 2.0% ORANGE OIL BRAS. 6.0% PATCHOULIOEL DELETE 2.0% STYROLYLACETAT 6.0% VERTOCITRAL 4.0%

Claims (6)

1. Use of 2,3-bis(12-hydroxyoctadecanoloxy)propyl-12-hydroxyoctadecanoate as a rheology stabilizer for capsules in liquid detergents containing 0.5 to 15% by weight of a solvent component comprising dipropylene glycol and 1,2-propanediol, the capsules having an average particle size of 0.1 nm to 1 µm
2. Use according to claim 1, characterized in that the core of the capsules contains ingredients for the care, conditioning and/or after-treatment of textiles, preferably selected from the group of fragrances, builders, bleaching agents, bleach activators, enzymes, greying inhibitors, foam inhibitors, inorganic salts, solvents, pH control agents, fluorescent agents, dyes, hydrotropes, silicone oils, soil release compounds, optical brighteners, greying inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, swelling and sliding fasteners, UV absorbers, acidifying agents.
3. Use according to claim 2, characterized in that the capsules are perfume capsules.
4. Use according to claim 3, characterized in that the capsules contain fragrances selected from the group consisting of aldehyde fragrances, ketone fragrances, pro-drug or mixtures thereof.
5. A process for preparing liquid detergents and cleaners containing from 0.5 to 15% by weight of a solvent component comprising dipropylene glycol and 1,2-propanediol and containing from 0.01 to 10% by weight of capsules having an average particle size of from 0.1 nm to 1 µm comprising the following steps:

   (a) providing the rheology stabilizer 2,3-bis(12-hydroxyoctadecanoloxy)propyl-12-hydroxy-octadecanoate;

   (b) stirring the rheology stabilizer into a solvent comprising dipropylene glycol and 1,2-propanediol to obtain a mixture;

   (c) heating the mixture from step (b) to at least 85°C;

   (d) cooling the mixture from step (c) to 40°C while stirring;

   (e) adding the cooled mixture from step (d) to the detergent formulation.
6. A liquid detergent composition containing from 0.5 to 15% by weight of a solvent component comprising dipropylene glycol and 1,2-propanediol and from 0.01 to 10% by weight of capsules having an average particle size of from 0.1 nm to 1 µm containing 2,3-bis(12-hydroxyoctadecanoloxy)propyl-12-hydroxyoctadecanoate in an amount of from 0.15 to 25% by weight.

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