Polyurea microcapsules and liquid surfactant systems containing the same

Abstract

Polyurea microcapsules are presented, which can be obtained by reacting di- and / or polyisocyanates with guanidine carbonate in the presence of a chemically modified biopolymer colloid protectant. The capsules can be loaded with, for example, a perfume and show high anticaking properties in non-structured (viscosity 10-300 cps), anionic surfactant based liquid products.

Description

Field of the invention

[0001] The present invention relates to the field of microcapsules and encompasses polyurea type microcapsules having improved anti-agglomeration properties and liquid surfactant systems comprising the same. BACKGROUND

[0002] There are many methods of producing microencapsulated perfumes, each different process changes the properties of the capsules produced. Some applications are sensitive to capsules made with many colloidal protectants. When most colloids are used, non-structured liquid laundry and body wash applications experience capsule agglomeration over time.

[0003] An example of this agglomeration is shown in Figure 1 where G-type capsules exhibit dispersion at 0.3% w / w in a commercially available non-structured liquid laundry detergent. The sample was aged in an oven at 40°C for 1 week to storage at room temperature for about 4 weeks.

[0004] Related Prior Art

[0005] WO 2018 002214 Al (FIRMENICH) discloses a method of making a core- complex shell microcapsule slurry for delivering a hydrophobic active ingredient, such as a perfume ingredient of a fragrance oil. The method includes forming an outer shell around an inner phase containing a hydrophobic active ingredient by coacervation; forming an inner shell at the interface between the inner phase and the outer shell by interfacial polymerization. The inner phase comprises a hydrophobic active ingredient. The microcapsules are typically incorporated into a consumer product, where the complex outer shell prevents release of the hydrophobic active ingredient until needed, typically during use of the consumer product.

[0006] WO 2018 019 894 Al (FIRMENICH) relates to a method of making microcapsules comprising the steps of: 1) mixing a hydrophobic active ingredient with at least one polyisocyanate having at least three isocyanate functional groups to form an oil phase, with the proviso that the oil phase is essentially free of diisocyanates; 2) dissolving an ionic or non-ionic emulsifier in water to form an aqueous phase, wherein the ionic emulsifier is selected from gum arabic, carboxymethylcellulose, soy protein, sodium caseinate, gelatin, bovine serum albumin, sugar sweet pectin, hydrolyzed soy protein, hydrolyzed silk gum, pseudocollagen, biopolymer SA-N, Pentacare-NA PF and mixtures thereof, wherein the non-ionic emulsifier is selected from polyvinyl alcohol, modified polyvinyl alcohol, modified starch, modified cellulose, polysaccharide and mixtures thereof; 3) adding the oil phase to the aqueous phase to form an oil-in-water dispersion; 4) applying conditions sufficient to induce interfacial polymerization and form microcapsules in the form of a slurry.

[0007] ​US 2013 0337023 A (IFF) claims a process for making a polyurea capsule composition comprising (a) preparing an oil phase comprising an active material and a polyisocyanate; (b) preparing a surfactant solution; (c) emulsifying the oil phase into the surfactant solution to form a fragrance emulsion; (d) adding a crosslinker to the fragrance emulsion to form a capsule slurry; (e) curing the capsule slurry.

[0008] Inventive Objectives

[0009] It has been found that capsules having a polyurea shell are rather stable even in aqueous solutions having a high concentration of preferably anionic surfactants, such as liquid detergents and softeners. However, polyurea microcapsules also show a severe tendency to form agglomerates, especially when introduced into aqueous anionic surfactant compositions, stability over time and temperature. It is therefore an object of the present invention to provide modified polyurea microcapsules having improved resistance to agglomerate formation, especially in unstructured products containing anionic surfactants, such as ordinary liquid laundry formulations. SUMMARY

[0010] A first object of the present invention relates to a polyurea microcapsule obtainable or obtained according to the following steps:

[0011] (a) providing an oil phase comprising at least one aliphatic and / or aromatic di- and / or polyisocyanate and optionally

[0012] one or more active substances for encapsulation and / or at least one oil component;

[0013] (b) providing a first water phase comprising at least one modified biopolymer colloid protective agent and optionally at least one non

[0014] interfering emulsifier;

[0015] (c) providing a second water phase comprising guanidinium carbonate and optionally at least one cationic surfactant;

[0016] (d) mixing the oil phase and the first water phase to form an emulsion;

[0017] (e) adding the second water phase to the emulsion formed in step (d) to form a dispersion of crude microcapsules (d);

[0018] (f) curing the mixture, and optionally

[0019] (g) removing the solvent to obtain the microcapsules.

[0020] A further object of the present invention covers a corresponding process for making a polyurea microcapsule comprising or consisting of the following steps:

[0021] (a) providing an oil phase comprising at least one aliphatic and / or aromatic di- and / or polyisocyanate and optionally

[0022] at least one oil component;

[0023] (b) providing a first water phase comprising at least one modified biopolymer colloid protector;

[0024] (c) providing a second water phase comprising guanidine carbonate;

[0025] (d) mixing the oil phase and the first water phase to form an emulsion;

[0026] (e) adding the second water phase to the emulsion formed in step (d) to form a dispersion of crude microcapsules;

[0027] (f) curing the mixture, and optionally

[0028] (g) removing the solvent to obtain microcapsules.

[0029] Surprisingly it was found that the addition of specific modified biopolymer colloid protectors, in particular chemically modified biopolymers such as starch, gum arabic and modified cellulose, significantly reduces the tendency of polyurea capsules to aggregate.

[0030] Di- and / or polyisocyanates

[0031] The formation of the polyurea capsule shell occurs by reaction of a compound having at least two isocyanate groups with guanidine carbonate having four amine groups. In a preferred manner, the isocyanate contains two, three or more aliphatic and / or aromatic isocyanate groups. While diisocyanate compounds can be of aliphatic origin, preferred embodiments include aromatic or alicyclic compounds or mixtures thereof, such as

[0032] • diphenylmethane diisocyanate (MDI);

[0033] • toluene diisocyanate (TDI);

[0034] • hexamethylene diisocyanate (HDI);

[0035] • isophorone diisocyanate (IPDI);

[0036] • 4,4-dicyclohexylmethane diisocyanate (H12MDI)

[0037] and mixtures thereof.

[0038] Particularly preferred is toluene diisocyanate which is for example commercially available under the trademark (COVESTRO) is obtained. With regard to the properties of the end product, it is particularly preferred to include about 50 to about 80 mol% of the 2,4-isomer of toluene diisocyanate.

[0039] Oil component

[0040] The oil phase can consist of the isocyanate component itself, but preferably it includes one or more oil components as solvents, having a ClogP (octanol:water partition coefficient) value of greater than 4, for example:

[0041] (i) straight-chain or branched-chain saturated paraffins (mineral oils) having 15 or more carbon atoms, in particular having 18 to 45 carbon atoms;

[0042] (ii) esters having 12 or more carbon atoms of straight-chain or branched-chain fatty acids having 6 to 30 carbon atoms and straight-chain or branched-chain, saturated or unsaturated mono-, di- or triols having 3 to 30 carbon atoms, which do not have free

[0043] hydroxyl groups;

[0044] (iii) esters of benzoic acid and straight-chain or branched-chain, saturated or unsaturated monoalkanols having 8 to 20 carbon atoms;

[0045] (iv) mono- or diesters of alcohols having 3 to 30 carbon atoms and naphthalene- mono- or di-carboxylic acids; in particular naphthalene mono-carboxylic acid C6-C 18 esters and naphthalene di-carboxylic acid di-C6-C 18 esters;

[0046] (v) straight-chain or branched-chain, saturated or unsaturated di-C6-C 18 -alkyl ethers;

[0047] (vi) silicone oils;

[0048] (vii) 2-alkyl-1-alkanols of the formula (III)

[0049]

[0050] wherein

[0051] Q1 is a straight-chain or branched-chain alkyl group having 6 to 24 carbon atoms and

[0052] Q2 is a straight-chain or branched-chain alkyl group having 4 to 16 carbon atoms.

[0053] The oil phase or oil component in the narrower (and preferred) sense of the invention, i.e. the substances which are limited or only present in small amounts in the invention, includes the following groups of substances:

[0054] (i) straight-chain or branched-chain saturated paraffins having 20 to 32 carbon atoms

[0055] (ii) esters of linear or branched, saturated fatty acids having 8 to 24 carbon atoms and linear or branched, saturated or unsaturated mono-, di- or triols having 3 to 24 carbon atoms, which do not have free hydroxyl groups, having at least 14 carbon atoms;

[0056] (iii) esters of benzoic acid with linear or branched, saturated monoalkanols having 10 to 18 carbon atoms;

[0057] (iv) alkylene glycol dioctanoate decanoate, in particular propylene glycol dioctanoate decanoate;

[0058] (v) linear or branched, saturated di-C6-C18-alkyl ethers, in particular (linear) di-C6-C12-alkyl ethers;

[0059] (vi) silicone oils selected from the group consisting of cyclotrisiloxane, cyclopentasiloxane, dimethylpolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane and mixtures thereof;

[0060] (vii) 2-alkyl-1-alkanols having 12 to 32 carbon atoms of the formula (III), wherein Q1 is an (preferably linear) alkyl group having 6 to 18 carbon atoms and Q2 is an (preferably linear) alkyl group having 4 to 16 carbon atoms.

[0061] The oil phase in the most narrow (and most preferred) sense of the present application comprises the following group of substances:

[0062] (i) linear or branched, saturated paraffins having 20 to 32 carbon atoms, such as isoeicosane or squalane;

[0063] (ii) esters of linear or branched, saturated fatty acids having 8 to 18 carbon atoms and linear or branched, saturated mono-, di- or triols having 3 to 18 carbon atoms, which do not have free hydroxyl groups, having at least 16 carbon atoms;

[0064] (iii) esters of benzoic acid with linear or branched, saturated monoalkanols having 12 to 15 carbon atoms, in particular benzoic acid C 12-15 alkyl esters;

[0065] (iv) alkylene glycol dioctanoate decanoate, in particular propylene glycol dioctanoate decanoate

[0066] (v) linear di-C6-C 10 alkyl ethers; in particular di-n-octyl ether (dioctyl ether)

[0067] (vi) silicone oils selected from the group consisting of undecamethyltrisiloxane, cyclomethicone, decamethylcyclopentasiloxane, dimethylpolysiloxane, diethylpolysiloxane, methylphenyl-polysiloxane and diphenylpolysiloxane;

[0068] (vii) 2-alkyl-l-alkanols of the formula (III) having 12 to 32 carbon atoms, wherein Q1 is an alkyl radical having 6 to 18 carbon atoms, preferably linear, and Q2 is an alkyl radical having 4 to 16 carbon atoms, preferably linear.

[0069] Particularly preferred components of type (i) in the oil phase are as follows: isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, oleyl oleate, oleyl erucate, oleyl oleate, oleyl erucate, 2-ethylhexyl isostearate, isotridecyl isononanoate, 2-ethylhexyl cocoate, caprylic / capric triglyceride, alkylene glycol dicaprylate / caprate, especially propylene glycol dicaprylate / caprate; and synthetic, semi-synthetic and natural mixtures of such esters, such as jojoba oil.

[0070] The fatty acid triglycerides (oil components of type (i) in the oil phase) can also be in the form of synthetic, semi-synthetic and / or natural oils or constituents, such as, for example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and mixtures thereof.

[0071] Particularly preferred oil components of type (vii) in the oil phase are as follows: 2-butyl-l-octanol, 2-hexyl-l-decanol, 2-octyl-l-dodecanol, 2-decyltetradecanol, 2-dodecyl-l-hexadecanol and 2-tetradecyl-l-octadecanol.

[0072] Particularly preferred oil components in the oil phase are mixtures comprising C12-C15-alkyl benzoate and 2-ethylhexyl isostearate, mixtures comprising C12-C15-alkyl benzoate and isotridecyl isononanoate, mixtures comprising C12-C15-alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate, mixtures comprising cyclomethicone and isotridecyl isononanoate and mixtures comprising cyclomethicone and 2-ethylhexyl isostearate.

[0073] Preferred oil bodies, which are components of O / W emulsions, are, for example, esters of straight-chain C6-C22-fatty acids and straight-chain or branched C6-C22-aliphatic alcohols, or esters of branched C6-C13-carboxylic acids and straight-chain or branched C6-C22-aliphatic alcohols, such as tetradecyl myristate, tetradecyl palmitate, tetradecyl stearate, tetradecyl isostearate, tetradecyl oleate, tetradecyl behenate, tetradecyl erucate, hexadecyl myristate, hexadecyl palmitate, hexadecyl stearate, hexadecyl isostearate, hexadecyl oleate, hexadecyl behenate, hexadecyl erucate, octadecyl myristate, octadecyl palmitate, octadecyl stearate, isostearate, hexadecyl oleate, hexadecyl behenate, hexadecyl erucate, octadecyl myristate, octadecyl palmitate, octadecyl stearate, isostearate, etc. Octadecyl stearate, octadecyl oleate, octadecyl behenate, octadecyl erucic acid, isooctadecyl myristate, isooctadecyl palmitate, isooctadecyl stearate, isooctadecyl isostearate, isooctadecyl oleate, isooctadecyl behenate, isooctadecyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucic acid, docosyl myristate, docosyl palmitate, docosyl stearate, isostearate, docosyl oleate, docosyl behenate, docosyl erucic acid, myristate mustard, palmitate mustard, stearate mustard, isostearate mustard, oleate mustard, behenate mustard and mustard mustard. Additionally, suitable options include esters of straight-chain C6-C22-fatty acids with branched-chain alcohols, particularly 2-ethylhexanol; esters of C18-C38-alkylhydroxycarboxylic acids with straight-chain or branched C6-C22-aliphatic alcohols, particularly dioctyl malate; esters of straight-chain and / or branched-chain fatty acids with polyols (such as, for example, propylene glycol, dimerdiol, or trimertriol) and / or Guerbet alcohol; and glycerols based on C6-C10-fatty acids. Esters, mixtures of liquid mono- / di- / triglycerides based on C6-C18 fatty acids, esters of C6-C22-aliphatic alcohols and / or Guerbet alcohols with aromatic carboxylic acids, particularly benzoic acid, esters of C2-C12-dicarboxylic acids with straight-chain or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, carbonates of straight-chain and branched C6-C22-aliphatic alcohols, such as, for example, dioctyl carbonate ( CC), Guerbet carbonates based on aliphatic alcohols having 6 to 18, preferably 8 to 10, carbon atoms, and esters of benzoic acid with straight-chain and / or branched C6-C22-ols (e.g., C6-C22-ols). TN), straight-chain or branched, symmetrical or asymmetrical dialkyl ethers, each alkyl group having 6 to 22 carbon atoms, such as, for example, dioctyl ether (TN). OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and / or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.

[0074] Most preferred oil components are triglycerides, especially those of natural origin.

[0075] Active

[0076] In a preferred embodiment, the microcapsules of the present application are loaded with one or more active substances, such as, for example, a perfume or fragrance oil. For certain applications, other additives can also be used. With regard to perfumes and fragrance oils, the polyurea capsules allow loading in amounts of up to 80 wt.-%, based on the total weight of the capsule. The active substances are preferably incorporated into the oil phase, however, depending on their polarity, they can also be incorporated into the first water phase.

[0077] Suitable fragrances and perfume oils are mixtures of natural odorants and synthetic odorants. Natural odorants include extracts from flowers (lily, lavender, rose, jasmine, orange blossom, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peels (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, orris, calamus), woods (pine, sandalwood, guaiac wood, cedarwood, rosewood), grasses and reeds (tarragon, lemon grass, sage, thyme), pine needles and branches (spruce, fir, pine, dwarf-pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, can also be used. Typical synthetic odorant compounds are ester, ether, aldehyde, ketone, alcohol and hydrocarbon products. Examples of ester odorants are benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether; while aldehydes include, for example, the linear alkyl aldehydes having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. Examples of suitable ketones are the ionones, alpha-isomethyl ionone and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, iso-eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons include mainly the terpenes and balsams. However, mixtures of different odorant compounds are preferably used, which together produce a pleasant odor. Further suitable perfume oils are the essential oils which are less volatile and are used as aroma components. Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil and lavender oil. The following substances are preferably used individually or in mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, hexyl cinnamal, geraniol, benzyl acetone, cyclamen aldehyde, linalool, ethoxy- methoxy c cyclododecan, ambroxan, indole, hedione, sandelice, citrus oils, mandarin oil, orange oil, allyl amyl glycol, cyclovertal, bright lavender oil, sage oil, damascone, bourgone- la oil, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, 2-ethyl-hexyl ethanoate (irotyl) and 2-tert.-butylcyclohexylethyl carbonate (floramat).

[0078] Colloidal protectant

[0079] The oil phase comprises at least an isocyanate compound and optionally an oil component and / or an active, the first water phase comprises an encapsulation aid, i.e. the colloidal protective agent, which is preferably selected from the group comprising chemically modified biopolymers, preferably chemically modified starch, modified gum arabic or modified cellulose. These belong to the class of EI 450 and represent for example starches (typically from corn, quinoa, oat, waxy barley or potato), gum arabic or chemically modified cellulose, for example by octenyl succinic anhydride (OSA). Corresponding products are available on the market, for example CAPSUL TM STARCH or HI-CAP TM 100 (Ingredion Inc.). Typically, an aqueous solution comprising 1 to 5 wt.-% of the aid is used.

[0080] Emulsifiers

[0081] To facilitate emulsification, it is useful to add a non-interfering (non-agglomerating) emulsifier selected from non-ionic, anionic, amphoteric and cationic surfactants and mixtures thereof to the first water phase already comprising the encapsulation aid.

[0082] Suitable non-ionic emulsifiers include for example:

[0083] • addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide to linear C 8-22 aliphatic alcohols, to C 12-22 addition products of fatty acids to alkylphenols having 8 to 15 carbon atoms in the alkyl group;

[0084] • C 12 / 18 fatty acid mono- and diesters;

[0085] • saturated and unsaturated fatty acid glycerol mono- and diesters and sorbitan mono- and diesters containing 6 to 22 carbon atoms and ethylene oxide addition products thereof;

[0086] • addition products of 15 to 60 mol of ethylene oxide to castor oil and / or hydrogenated castor oil;

[0087] • polyol esters, especially polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimer oil isostearate. Also suitable are mixtures of a plurality of such compounds;

[0088] • addition products of 2 to 15 mol of ethylene oxide to castor oil and / or hydrogenated castor oil;

[0089] • based on linear, branched, unsaturated or saturated C 6 / 22 • partial esters of fatty acids, of ricinoleic acid and of 12-hydroxy stearic acid with glycerol, polyglycerol, pentaerythrit, di-pentaerythrit, sugar alcohols (e.g. sorbitol), alkylglucosides (e.g. methylglucoside, butylglucoside, laurylglucoside) and polyglucosides (e.g. cellulose);

[0090] • mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG alkyl phosphates and salts thereof;

[0091] • lanolin alcohols;

[0092] • polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;

[0093] • mixed esters of pentaerythrit, fatty acids, citric acid and fatty alcohols and / or C 6-22 • mixed esters of fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol;

[0094] • polyglycols and

[0095] • glycerol carbonate.

[0096] Addition products of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids and alkylphenols, fatty acid or castor oil glycerol mono- and diesters and sorbitan mono- and diesters are commercially available products. Herein is meant a homologous mixture whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate used in the addition reaction. C 12 / 18 Fatty acid mono- and diesters are known as superfatting agents for cosmetic preparations. Preferred emulsifiers are listed in detail below:

[0097] Partial glycerides. Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures which still contain small amounts of triglycerides from the production process. Addition products of 1 to 30 and preferably 5 to 10 moles of ethylene oxide with the above-mentioned partial glycerides are likewise suitable.

[0098] Sorbitol esters. Suitable sorbitol esters include sorbitol monoisostearate, sorbitol sesquiisostearate, sorbitol diisostearate, sorbitol triisostearate, sorbitol monooleate, sorbitol sesquioleate, sorbitol dioleate, sorbitol trioleate, sorbitol monoerucic acid ester, sorbitol sesquierucic acid ester, sorbitol dierucic acid ester, sorbitol trierucic acid ester, sorbitol monoricinoleate, sorbitol sesquirucic acid ester, sorbitol diricinoleate, sorbitol triricinoleate, and sorbitol monoricinoleate. Sorbitol monohydroxy stearate, sorbitan sesquihydroxy stearate, sorbitan dihydroxy stearate, sorbitan trihydroxy stearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate, and mixtures thereof. Addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide with the above-mentioned sorbitan esters are also suitable.

[0099] Polyglycerol esters. A typical example of a suitable polyglycerol ester is polyglycerol-2-dimeric hydroxystearate (…). PGPH), polyglycerol-3-diisostearate ( TGI), polyglycerol-4 isostearate ( GI 34), polyglycerol-3 oleate, polyglycerol-3 diisostearate ( PDI), polyglycerol-3-methylglucose distearate (Tego) 450), polyglycerol-3 beeswax (Cera) ), polyglycerol-4-decanoate (polyglycerol decanoate T2010 / 90), polyglycerol-3-ceryl ether ( NL), polyglycerol-3 distearate ( GS32) and polyglycerol polyricinoleate ( WOL 1403), polyglyceryl diisostearate esters, and mixtures thereof. Other suitable examples of polyol esters are monoesters, diesters, and trimers of lauric acid, coconut oil acid, tartrate, palmitic acid, stearic acid, oleic acid, behenic acid, etc., reacted with 1 to 30 moles of ethylene oxide with trimethylolpropane or pentaerythritol.

[0100] Tetraalkyl quaternary ammonium salts. Cationic surfactants comprise a hydrophobic macromolecular group which, by dissociation in aqueous solution, has the required surface activity in cations. An important group of representatives of cationic surfactants is the tetraalkyl quaternary ammonium salts of the general formula (R 1 R 2 R 3 R 4 N + )X - Here, R 1 represents a Ci-C8alk(en)yl group, R 2 , R 3 and R 4 independently of one another represent an alk(en)yl group containing 1 to 22 carbon atoms. X is a counterion, preferably selected from the group comprising halides, alkyl sulphates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted by two long acyl groups and two short alk(en)yl groups.

[0101] Ester quaternary ammonium salts. An important group of cationic surfactants which is used in particular as co-surfactants in accordance with the application are the so-called ester quaternary ammonium salts. Ester quaternary ammonium salts generally mean quaternized fatty acid triethanolamine ester salts. They are known compounds and can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91 / 01295 Al, in which triethanolamine is esterified with fatty acid moieties in the presence of hypophosphorous acid, air is passed through the reaction mixture and subsequently the whole is quaternized with dimethyl sulphate or ethylene oxide. Furthermore, the German patent DE 4308794 Cl describes a process for the preparation of solid ester quaternary ammonium salts, in which the quaternization of the triethanolamine ester is carried out in the presence of a suitable dispersant, preferably a fatty alcohol.

[0102] Typical examples of ester quats suitable for use in the present application are products in which the acyl component is derived from a monocarboxylic acid of the formula RCOOH - wherein RCO is an acyl group containing 6 to 10 carbon atoms - and the amine component is triethanolamine (TEA). Examples of said monocarboxylic acids are caproic acid, caprylic acid, capric acid and technical mixtures thereof such as, for example, so-called head fraction fatty acids. It is preferred to use ester quats in which the acyl component is derived from a monocarboxylic acid containing 8 to 10 carbon atoms. Other ester quats are those in which the acyl component is derived from a dicarboxylic acid such as malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, sorbic acid, pimelic acid, azelaic acid and / or dodecanedioic acid, but preferably adipic acid. In general, it is preferred to use ester quats in which the acyl component is derived from a mixture of a monocarboxylic acid containing 6 to 22 carbon atoms and adipic acid. The molar ratio of monocarboxylic acid and dicarboxylic acid in the final ester quat is 1 :99 to 99:1, and preferably 50:50 to 90:10 and more particularly 70:30 to 80:20. In addition to the quaternized fatty acid triethanolamine ester salts, other suitable ester quats are quaternized ester salts of mono / dicarboxylic acid mixtures with diethanolalkylamines or 1,2-dihydroxypropyl dialkylamines. The ester quats can be derived from fatty acids and from corresponding triglycerides mixed with the corresponding dicarboxylic acids. One such process, which is representative of the relevant prior art, is proposed by European patent EP 0750606 B1. For the preparation of the quaternized ester, a mixture of mono and dicarboxylic acids with triethanolamine in a molar ratio of 1.1 :1 to 3:1 - based on the available carboxylic functional groups - can be used. Considering the performance of the ester quats, a ratio of 1.2:1 to 2.2:1, and in particular a ratio of 1.5:1 to 1.9:1, has proven to be particularly advantageous. The preferred ester quats are technical mixtures of mono, di and tri esters with an average degree of esterification of 1.5 to 1.9.

[0103] It is further advantageous to use a combination of anionic and / or amphoteric surfactants with one or more non-ionic surfactants. In one preferred embodiment according to the present application, the composition further comprises an emulsifier selected from the group consisting of:

[0104] • alkyl phosphate derivatives

[0105] • glycerol oleate citrate derivatives

[0106] • glycerol stearate citrate derivatives

[0107] • stearates

[0108] • sorbitol esters

[0109] • ethoxysorbitol esters

[0110] • ethoxylated glycerol mono-, di- and triglycerides

[0111] • methylglucose esters

[0112] Emulsions and dispersions

[0113] In a first step, an emulsion is prepared by mixing the oil phase (comprising the isocyanate component and optionally the oil component and / or the active) and the first water phase (comprising the encapsulation aid and the colloidal protective agent). Preferably, emulsification is performed by subjecting the mixture to high shear, for example using an Ultra-Turrax at 3,000 to 5,000 rpm for about 20 to about 120 seconds.

[0114] Once the emulsion is prepared, it is mixed with the second water phase comprising the guanidine carbonate, which forms the polyurea by reaction of the amine groups of the guanidine carbonate with the isocyanate component. The mixture is also subjected to high shear under similar conditions as described above.

[0115] Guanidine carbonate is a white crystalline solid of the formula

[0116]

[0117] which is available, for example, from Sigma-Aldrich. The isocyanate and the guanidine carbonate are typically reacted in a molar ratio of 1 : 1 to 5: 1, preferably 1.2: 1 to 3: 1, calculated on the basis of the ratio between isocyanate and amine groups. In other words, a (small) excess of isocyanate is preferred.

[0118] The second aqueous solution can comprise at least one surfactant. Preferably, the agent is a non-ionic and / or cationic polymer, for example a suitable polymer to improve the spreading properties of the composition on the skin or hair, or to improve the water- and / or perspiration- and / or rub-off resistance of the formulation and to increase the protection factor of the composition. Examples of such polymers are: VP / Eicosene copolymer sold under the trade name Antaron V-220 by International Speciality Products, VP / Hexadecene copolymer sold under the trade name Antaron V-216 and Antaron V-516 by International Speciality Products, Tricontanyl PVP sold under the trade name Antaron WP-660 by International Speciality Products, Isohexadecane and ethylene / propylene / styrene copolymer and butylene / styrene copolymer sold under the trade name Versagel MC and MD by Penreco, hydrogenated polyisobutene and ethylene / propylene / styrene copolymer and butylene / styrene copolymer sold under the trade name Versagel ME by Penreco, acrylates / octylacrylamide copolymer sold under the trade name Dermacryl 79, Dermacryl AQF and Dermacryl LT by Akzo Nobel, polyurethane such as PPG-17 / IPDI / DMPA copolymer sold under the trade name Avalure UR 450 & 525 by Noveon, polyurethane-2 and -4 sold under the trade name Avalure UR-405, -410, -425, -430 and -445 525 by Noveon, polyurethane 5 and butyl acetate and isopropyl alcohol sold under the trade name Avalure UR-510 and -525 by Noveon, polyurethane-1 and -6 sold under the trade name Luviset PUR by BASF, hydrogenated dimer dilinoleyl / dimethyl carbonate copolymer sold under the trade name Cosmedia DC by Cognis.

[0119] Curing

[0120] Once the emulsion is mixed with the second aqueous phase, a polyaddition reaction takes place and crude microcapsules incorporating the active substance are formed. It is understood that the encapsulation aids are either incorporated into the capsule shell or onto its surface. At this point the microcapsules are not sufficiently stable in dispersion and a final curing step is required. Curing is usually performed by treating the dispersion thus obtained at an elevated temperature of from about 50 to about 90°C for about 1 to about 12 hours.

[0121] If desired, the solvent can be removed to obtain "pure" capsules, which typically exhibit an average diameter of from about 5 to about 50 microns.

[0122] Liquid surfactant systems

[0123] Another object of the present application relates to a liquid surfactant system, preferably a detergent composition, comprising the microcapsules or the dispersion comprising the microcapsules as described above. Typically, the content ranges from about 0.5 to about 5 wt.-%, preferably from about 1 to about 2 wt.-%, as pure microcapsules based on the total composition.

[0124] Suitable examples of liquid detergents include heavy duty liquid detergents, light duty liquid detergents, fabric softeners, hand dishwashing agents, all-purpose cleaners and the like. Also included are anionic lld-type surfactant systems, including body washes, particularly suitable for systems with a viscosity range of 10-300 cps c (est).

[0125] The detergent compositions according to the present application can comprise any ingredients normally present in such compositions, such as anionic, nonionic, cationic, amphoteric or zwitterionic co-surfactants, organic solvents, builders, enzymes and other adjuncts such as soil repellents, thickeners, colorants and perfumes and the like.

[0126] Anionic and zwitterionic co-surfactants

[0127] Typical examples of anionic and zwitterionic surfactants include: almondamidopropylamine oxide, almondamidopropyl betaine, aminopropyl lauryl glutamide, ammonium C12-15 pareth sulfate, ammonium C12-16 pareth sulfate, ammonium capryl ether sulfate, ammonium glyceryl cocoate sulfate, ammonium coco-sulfate, ammonium cocoyl isethionate, ammonium cocoyl methylamide, ammonium C12-15 pareth sulfate, ammonium C9-10 perfluoroalkylsulfonate, ammonium dinonyl sulfosuccinate, ammonium dodecylbenzenesulfonate, ammonium isostearate, ammonium laureth-6 carboxylate, ammonium laureth-8 carboxylate, ammonium laureth sulfate, ammonium laureth-5 sulfate, ammonium laureth-7 sulfate, ammonium laureth-9 sulfate, ammonium laureth-12 sulfate, ammonium lauroyl methylamide, ammonium lauryl sulfate, ammonium lauryl sulfosuccinate, ammonium myreth sulfate, ammonium myristyl sulfate, ammonium nonoxynol-4 sulfate, ammonium nonoxynol-30 sulfate, ammonium oleate, ammonium palm kernel oil sulfate, ammonium stearate, ammonium tallate, AMPD salt of isostearyl hydrolyzed collagen, AMPD salt of rosin (acyl) hydrolyzed collagen, AMP salt of isostearyl hydrolyzed collagen, AMP salt of isostearyl hydrolyzed keratin, AMP salt of isostearyl hydrolyzed soy protein, AMP salt of isostearyl hydrolyzed wheat protein, apricot kernelamidopropyl betaine, arachidic acid, arginine hexyldecyl phosphate ester, avocadoamidopropyl betaine, avocado glyceryl oleate, babassu seed oil acid, babassu oilamidopropylamine oxide, babassu oilamidopropyl betaine, beeswax acid, behenamidopropyl betaine, behenamine oxide, beheneth-25, beheneth-30, behenic acid, behenyl betaine, bis-Cetearyl alcohol polyether-23, Cetearyl alcohol polyether-24, Cetearyl alcohol polyether-25, Cetearyl alcohol polyether-27, Cetearyl alcohol polyether-28, Cetearyl alcohol polyether-29, Cetearyl alcohol polyether-30, Cetearyl alcohol polyether-33, Cetearyl alcohol polyether-34, Cetearyl alcohol polyether-40, Cetearyl alcohol polyether-50, Cetearyl alcohol polyether-55, Cetearyl alcohol polyether-60, Cetearyl alcohol polyether-80, Cetearyl alcohol polyether-100, Cetearyl alcohol polyether-25 carboxylic acid, Cetearyl alcohol polyether-2 phosphate, Cetearyl alcohol polyether-4 phosphorus Cetearyl ester, cetearyl alcohol polyether-5 phosphate, dicetearyl alcohol polyether-10 phosphate, cetearyl alcohol polyether-20, cetearyl alcohol polyether-23, cetearyl alcohol polyether-24, cetearyl alcohol polyether-25, cetearyl alcohol polyether-30, cetearyl alcohol polyether-40, cetearyl alcohol polyether-45, cetearyl alcohol polyether-150, cetearyl alcohol polyether-8 phosphate, cetearyl alcohol polyether-10 phosphate, cetearyl alcohol polyether-20 phosphate, cetearyl oil alcohol polyether-22, cetearyl oil alcohol polyether-24, cetearyl oil alcohol polyether-25, cetearyl oil alcohol polyether-30, cetyl betaine, Chrysanthemum SINENSE flower extract, C12-14 hydroxyalkyl hydroxyethyl β-alanine, C12-14 hydroxyalkyl hydroxyethyl sarcosine, cocamidoethyl betaine, cocamidopropylamine oxide, cocamidopropyl betaine amide MEA chloride, cocamidopropyl betaine, cocamidopropyl hydroxysulfonate betaine, cocamidoamine oxide, cocoaminobutyric acid, cocoaminopropionic acid, cocoal alcohol polyether-7 carboxylic acid, cocoal alcohol polyether Ether-4 glucoside, cocoamphopropionic acid, cocobetaine amide amphoteric propionate, cocobetaine, cocodimethylammonium hydroxypropyl hydrolyzed rice protein, cocodimethylammonium hydroxypropyl hydrolyzed soybean protein, cocodimethylammonium hydroxypropyl hydrolyzed wheat protein, cocoglucoside, cocoglucoside hydroxypropyltrimethylammonium chloride, cocodihydroxysulfonate betaine, cocodimorpholine oxide, coconut oil acid, coconut oil glycerol polyether-8 Esters, cocamidopropyl betaine, cocoyl-sulfobetaine, (coconut oil / sunflower oil) amamidopropyl betaine, cocoylcholine methyl sulfate, cocoyl glutamate, cocoyl hydrolyzed collagen, cocoyl hydrolyzed keratin, cocoyl hydrolyzed oat protein, cocoyl hydrolyzed rice protein, cocoyl hydrolyzed silk, cocoyl hydrolyzed soybean protein, cocoyl hydrolyzed wheat protein, cocoyl sarcosine, corn oleic acid, cotton Cottonseed oil acid, cottonseed oil glycerol polyether-8 esters, C10-16 alkanol polyether-1, C10-16 alkanol polyether-2, C11-13 alkanol polyether-6, C11-13 alkanol polyether-9, C11-13 alkanol polyether-10, C11-15 alkanol polyether-30, C11-15 alkanol polyether-40, C12-13 alkanol polyether-1, C12-13 alkanol polyether-23C12-14 pareth-5, C12-14 pareth-9, C13-15 pareth-21, C14-15 pareth-8, C20-22 pareth-30, C20-40 pareth-40, C20-40 pareth-95, C22-24 pareth-33, C30-50 pareth-40, C9-11 pareth-6 carboxylic acid, C9-11 pareth-8 carboxylic acid, C11-15 pareth-7 carboxylic acid, C12-13 pareth-5 carboxylic acid, C12-13 pareth-7 carboxylic acid, C12-13 pareth-8 carboxylic acid, C12-13 pareth-12 carboxylic acid, C12-15 pareth-7 carboxylic acid, C12-15 pareth-8 carboxylic acid, C12-15 pareth-12 carboxylic acid, C14-15 pareth-8 carboxylic acid, C6-10 pareth-4 phosphate, C12-13 pareth-2 phosphate, C12-13 pareth-10 phosphate, C12-15 pareth-6 phosphate, C12-15 pareth-8 phosphate, C12-15 pareth-10 phosphate, C12-16 pareth-6 phosphate, C4-18 perfluoroalkylethylmerapropyltrimethylammonium chloride, Theobroma grandiflorum fatty amide propyl betaine, C12-13 alcohol sulfate DEA salt, C12-15 alcohol sulfate DEA salt, Cetyl stearyl ether-2 phosphate DEA salt, Cetyl alcohol sulfate DEA salt, Cocamphodipropionate DEA salt, C12-13 pareth-3 sulfate DEA salt, Cyclocarboxypropyl oleate DEA salt, Dodecylbenzenesulfonic acid DEA salt, Isostearyl acid DEA salt, Lauryl ether sulfate DEA salt, Lauryl alcohol sulfate DEA salt, Linoleic acid DEA salt, Myristate methyl sulfonic acid DEA salt, Myristyl ether sulfate DEA salt, Myristic acid DEA salt, Myristyl alcohol sulfate DEA salt, Oleyl ether-5 phosphate DEA salt, Oleyl ether-20 phosphate DEA salt, DEA PG-oleate, Deceth-7 carboxylic acid, Deceth-7 glucoside, Deceth-9 phosphate, Decyl amine oxide, Decyl betaine, Undecyl glucoside, Decyl myristyl ether-30, Decyl myristyl amine oxide, Laurylamid-MEA sulfosuccinate diammonium, Lauryl sulfosuccinate diammonium, Oleamidopropyl PEG-2 sulfosuccinate diammonium, Dibutoxymethane, Di C12-15 pareth-2 phosphate, Di C12-15 pareth-4 phosphate, Di C12-15 pareth-6 phosphate, Di C12-15 pareth-8 phosphate, Di C12-15 pareth-10 phosphate, Dilauryl alcohol butane tetra carboxylate, Lauryl ether sulfate diethylamine salt, Disodium sulfosuccinate diethylhexyl ester, Di(hydroxyethyl) C8-10 alcoxypropyl amine oxide, Di(hydroxyethyl) C9-11 alcoxypropyl amine oxide,Di(hy droxyethyl) C12-15 Pareth Oxide, Di(hy droxyethyl) Cocamine Oxide, Di(hy droxyethyl) Laurylamine Oxide, Di(hy droxyethyl) Stearamine Oxide, Di(hy droxyethyl) Tallowamine Oxide, Dimethicone PEG-7 Phosphate, Dimethicone PEG-10 Phosphate, Dimethicone PEG / PPG-7 / 4 Phosphate, Dimethicone PEG / PPG-12 / 4 Phosphate, Dimethicone / Polyglycerin-3 Crosspolymer, Dimethiconol PG Betaine, Dimyristyl Phosphate, Dioleylamidoethyl Hydroxyethylmonium Methosulfate, DIPA Salt of Hydrogenated Cocoate, DIPA Salt of Lanolate, DIPA Salt of Myristate, Dipotassium Octanoyl Glutamate, Dipotassium Lauryl Sulfosuccinate, Dipotassium Undecylenoyl Glutamate, Dipotassium Babassuamido MEA-Sulfosuccinate, Dipotassium Decoate Diacetate, Dipotassium Decoate Dipropionate, Dipotassium Octoate Diacetate, Dipotassium Octoate Dipropionate, Dipotassium Octanoyl Glutamate, Dipotassium Cetearyl Sulfosuccinate, Dipotassium Cetyl Phenyl Ether Disulfonate, Dipotassium Cetyl Sulfosuccinate, Dipotassium Cocamido MEA-Sulfosuccinate, Dipotassium Cocamido MIPA PEG-4 Sulfosuccinate, Dipotassium Cocamido MIPA-Sulfosuccinate, Dipotassium Cocamido PEG-3 Sulfosuccinate, Dipotassium Coceth-3 Sulfosuccinate, Dipotassium Cocoyl Carboxyethylhydroxpropyl Sulfate, Dipotassium Cocoyl Diacetate, Dipotassium Cocoyl Dipropionate, Dipotassium Cocoyl-Glucoside Sulfosuccinate, Dipotassium Cocoyl-Sulfosuccinate, Dipotassium Cocoyl Glyceroxypropylsulfonate, Dipotassium Cocoyl Glutamate, Dipotassium C12-14 Pareth-1 Sulfosuccinate, Dipotassium C12-14 Pareth-2 Sulfosuccinate, Dipotassium C12-15 Pareth Sulfosuccinate, Dipotassium C12-14 Sec-Pareth-3 Sulfosuccinate, Dipotassium C12-14 Sec-Pareth-5 Sulfosuccinate, Dipotassium C12-14 Sec-Pareth-7 Sulfosuccinate, Dipotassium C12-14 Sec-Pareth-9 Sulfosuccinate, Dipotassium C12-14 Sec-Pareth-12 Sulfosuccinate, Dipotassium Deceth-5 Sulfosuccinate, Dipotassium Deceth-6 Sulfosuccinate, Dipotassium Decyl Phenyl Ether Disulfonate, Dipotassium Dihydroxyethyl Sulfosuccinyl Undecylenate, Dipotassium Diisococoylethylenediamine PEG-15 Disulfate, Dipotassium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Dipotassium Hydrogenated Tallowoyl Glutamate, Dipotassium Hydroxylauryl Sulfate, Dipotassium Isodecyl Sulfosuccinate, Dipotassium Isostearamido MEA-Sulfosuccinate, Dipotassium Isostearamido MIPA-MEA-Sulfosuccinate, Dipotassium Isostearylamido Diacetate, Dipotassium Isostearylamido Dipropionate, Dipotassium Isostearylsulfosuccinate, Dipotassium Laneth-5 Sulfosuccinate,Disodium lauramide MEA-sulfosuccinate, disodium lauramide MIPA ethylene glycol sulfosuccinate, disodium lauramide PEG-2 sulfosuccinate, disodium lauramide PEG-5 sulfosuccinate, disodium lauryl ether-5 carboxyamphodiacetate, disodium lauryl ether-7 citrate, disodium lauryl ether sulfosuccinate, disodium lauryl ether-6 sulfosuccinate, disodium lauryl ether-9 sulfosuccinate, disodium lauryl ether-12 sulfosuccinate, disodium lauryliminobis(hydroxypropyl)sulfonate, disodium lauryliminodiacetate, disodium lauryliminodiapropionate, disodium lauryliminodiapropionate tocopherol phosphate salt, disodium lauroylamphodiacetate, disodium lauroylamphodiapropionate. Disodium N-lauroyl aspartate, disodium lauroyl glutamate, disodium lauryl phenyl ether disulfonic acid, diammonium lauryl sulfosuccinate, disodium myristamide MEA-sulfosuccinate, disodium nonylphenol polyether-10 sulfosuccinate, disodium oleamide MEA sulfosuccinate, disodium oleamide MIPA sulfosuccinate, disodium oleamide PEG-2 sulfosuccinate, disodium oleoyl amphoteric dipropionate, disodium oleyl alcohol polyether-3 sulfosuccinate, disodium oleyl alcohol phosphate, disodium oleyl alcohol sulfosuccinate, disodium palmitamide PEG-2 sulfosuccinate, disodium palmitamide-based PEG-2 sulfosuccinate, disodium PEG-4 cocoamide MIPA-sulfosuccinate, disodium PEG-12 polydimethylsiloxane sulfonate Disodium sulfosuccinate, disodium PEG-8 palmitoleic acid glyceride sulfosuccinate, disodium PPG-2-isodecyl alcohol polyether-7 carboxyamphodiacetate, disodium ricinoleic acid amide MEA sulfosuccinate, disodium sitosterol polyether-14 sulfosuccinate, disodium soybean oil amphoteric diacetate, disodium stearamide MEA sulfosuccinate, disodium stearyl iminodipropionate, disodium stearyl amphoteric diacetate, disodium stearyl glutamate, disodium sulfosuccinate monoacyl stearamide, disodium stearyl alcohol sulfosuccinate, disodium 2-sulfolarate, disodium 2-sulfopalatate, disodium tallow oleamide MEA sulfosuccinate, disodium tallow amide MEA sulfosuccinate, disodium tallow amphoteric diacetate, disodium tallow iminodipropionate Sodium, disodium sulfosuccinate monoacyl tallowamine, disodium tridecyl sulfosuccinate, disodium undecenoamide MEA sulfosuccinate, disodium undecenoamide PEG-2 sulfosuccinate, disodium undecenoyl glutamate, disodium monowheat germ oleoyl MEA sulfosuccinate, disodium monowheat germ oleoyl PEG-2 sulfosuccinate, disodium wheat germ oleoyl amphoteric diacetate, cocamidoacetic acid di-TEA salt, oleamide PEG-2 sulfosuccinate di-TEA salt, palmitoyl aspartate di-TEA salt, sodium didecyl sulfosuccinate, dodecylbenzene sulfonic acid, erucamide propyl hydroxysulfobetaine, ethylhexyl alcohol polyether-3 carboxylic acid, ethyl PEG-15 cocoamine sulfate salt, octyl glyceryl ether, hexyl decanoic acidHydrogenated cocoate, Hydrogenated lanolin alcohol polyglycol ether-25, Hydrogenated menhaden oil fatty acids, Hydrogenated palmitoleate, Hydrogenated palm kernel amido oxide, Hydrogenated tallowate, Hydrogenated tallow amido oxide, Hydrogenated tallow betaine, Hydrogenated tallow glycol ether-25, Hydrogenated tallowoyl glutamate, Hydrogenated yeast extract, Hydroxycetyltrimonium chloride, Hydroxylethyl acetoxy methyl ammonium PG- dimethicone, Hydroxyethyl butylamine lauryl ether sulfate, Hydroxyethyl carboxymethyl cocaminopropyl amine, Hydroxyethyl hydroxylpropyl C12-15 alkyl oxypropyl amine oxide, Hydroxyethyl / hydroxypropyl betaine, Hydroxystearic acid, Hydroxysuccinimide C10-40 isoparaffate ethylhexyl ester, Hydroxysuccinimide C21-22 isoparaffate ethylhexyl ester, Hydroxysultaine, IPDI / PEG-15 soyamide oxide, IPDI / PEG-15 soyamide ethanol sulfate methyl ester copolymer, IPDI / PEG-15 soy glycinamide copolymer, lsoceteth-30, Isodecyl ether-4 phosphate, Isodiglyceryl-3 polydimethylsiloxy, Isodiglyceryl-3 polydimethylsiloxy, Laneth-40, Laneth-50, Laneth-60, Laneth-75, Lanolin acid, Laurylamidopropyl amine oxide, Laurylamidopropyl betaine, Laurylamidopropyl hydroxysultaine, Lauryl amine oxide, Lauryl amino propionic acid, Lauryl dimethyl hydroxypropyl decyl glycoside chloride, Lauryl dimethyl lauryl glycoside hydroxypropyl chloride, Lauryl glycol ether-16, Lauryl glycol ether-20, Lauryl glycol ether-21, Lauryl glycol ether-23, Lauryl glycol ether-25, Lauryl glycol ether-30, Lauryl glycol ether-38, Lauryl glycol ether-40, Lauryl glycol ether-3 carboxylic acid, Lauryl glycol ether-4 carboxylic acid, Lauryl glycol ether-5 carboxylic acid, Lauryl glycol ether-6 carboxylic acid, Lauryl glycol ether-8 carboxylic acid, Lauryl glycol ether-10 carboxylic acid, Lauryl glycol ether-11 carboxylic acid, Lauryl glycol ether-12 carboxylic acid, Lauryl glycol ether-13 carboxylic acid, Lauryl glycol ether-14 carboxylic acid, Lauryl glycol ether-17 carboxylic acid, Lauryl glycol ether-6 citrate, Lauryl glycol ether-7 citrate, Lauryl glycol ether-1 phosphate, Lauryl glycol ether-2 phosphate, Lauryl glycol ether-3 phosphate, Lauryl glycol ether-4 phosphate, Lauryl glycol ether-7 phosphate, Lauryl glycol ether-8 phosphate, Lauryl glycol ether-7 tartrate, Lauryl acid, Lauryl imino bispropyl glycol, Lauryl imino dipropionic acid,Lauryl amidopropyl betaine, Lauryl beta-alanine, Lauryl collagen amino acids, Lauryl ethyltrimonium methosulfate, Lauryl hydrolyzed collagen, Lauryl hydrolyzed elastin, Lauryl methyl glucamide, Lauryl sarcosine, Lauryl silk amino acids, Lauryl sultaine, Lauryl dimethicone / polyglyceryl-3 crosspolymer, Lauryl dimethyl hydroxypropyl coco gluco- sidine ammonium chloride, Lauryl glucoside, Lauryl glucoside hydroxypropyltrimonium chloride, Laurylglycol hydroxypropyl ether, Lauryl hydroxysultaine, Lauryl malamide, Lauryl methyl glucamide, (Lauryl / myristyl) glycol hydroxypropyl ether, (Lauryl / myristyl) wheat straw / straw extract, Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, Lauryl pyrrolidone, Lauryl dimethyl sulfaine betaine, Linoleic acid, Linolenic acid, Linoleic acid, Lysine cocoyl, Macadamia seed oil glycereth-8 esters, Magnesium coceth sulfate, Magnesium cocoyl sulfate, Magnesium isododecylbenzenesulfonate, Magnesium lauryl ether-11 carboxylate, Magnesium lauryl ether sulfate, Magnesium lauryl ether-5 sulfate, Magnesium lauryl ether-8 sulfate, Magnesium lauryl ether-16 sulfate, Magnesium lauryl ether-3 sulfosuccinate, Magnesium lauryl hydroxypropyl sulfonate, Magnesium lauryl sulfate, Magnesium methyl cocoyl taurate, Magnesium myristyl ether sulfate, Magnesium oleyl ether sulfate, Magnesium / TEA cocoyl sulfate, Mannitan Glacier Mud, MEA cocoyl, MEA lauryl ether-6 carboxylate, MEA lauryl ether sulfate, MEA PPG-6-lauryl ether-7 carboxylate, MEA PPG-8-stearyl ether-7 carboxylate, MEA undecylenate, Merocin 108, Merocin 174, Merocin 178, Merocin 254, Merocin 255, Merocin 258, Merocin 314, Methoxy PEG-450 amido pentanedioic succinamide, Methoxy PEG-450 amido hydroxysuccinimidyl succinate, Methoxy PEG-450 maleimide, Methyl morpholine oxide, Milk amido propyl amine oxide, Milk amido propyl betaine, Mink amido propyl amine oxide, Mink amido propyl betaine, MIPA C12-15 pareth sulfate, MIPA dodecylbenzenesulfonate, MIPA lauryl ether sulfate, MIPA lauryl sulfate, Mixed isopropanolamine lanolin acid salt, Mixed isopropanolamine lauryl sulfate, Mixed isopropanolamine myristate, Morpholine oleate, Morpholine stearate, Myristyl ether-3 carboxylate, Myristyl ether-5 carboxylate, Myristyl benzyl dimethyl ammonium chloride, Myristamido propyl amine oxide, Myristamido propyl betaine, Myristamido propyl dimethyl amine phosphate, Myristamido propyl hydroxysultaine, Myristamido propyl PG-dimethyl ammonium chloride phosphate, Myristamine oxide, Myristyl aminopropionic acid, Myristic acid, Myristyl ethyltrimonium methosulfate,Myristoyl Glutamate, Myristoyl Hydrolyzed Collagen, Myristoyl Methionine, Myristyl Betaine, Myristyl / Cetyl Amine Oxide, Myristyl Dimethyl Hydroypropyl Cocoyl Glucoside Chloride, Myristyl Glucoside, Myristyl Phosphorostearate, Nonyl Phenol Ethoxylate-20, Nonyl Phenol Ethoxylate-23, Nonyl Phenol Ethoxylate-25, Nonyl Phenol Ethoxylate-30, Nonyl Phenol Ethoxylate-35, Nonyl Phenol Ethoxylate-40, Nonyl Phenol Ethoxylate-44, Nonyl Phenol Ethoxylate-50, Nonyl Phenol Ethoxylate-100, Nonyl Phenol Ethoxylate-120, Nonyl Phenol Ethoxylate-5 Carboxylic Acid, Nonyl Phenol Ethoxylate-8 Carboxylic Acid, Nonyl Phenol Ethoxylate-10 Carboxylic Acid, Nonyl Phenol Ethoxylate-3 Phosphate, Nonyl Phenol Ethoxylate-4 Phosphate, Nonyl Phenol Ethoxylate-6 Phosphate, Nonyl Phenol Ethoxylate-9 Phosphate, Nonyl Phenol Ethoxylate-10 Phosphate, Dinonyl Phenol Ethoxylate-30, Dinonyl Phenol Ethoxylate-49, Dinonyl Phenol Ethoxylate-100, Dinonyl Phenol Ethoxylate-150, Dinonyl Phenol Ethoxylate-7 Phosphate, Dinonyl Phenol Ethoxylate-8 Phosphate, Dinonyl Phenol Ethoxylate-9 Phosphate, Dinonyl Phenol Ethoxylate-10 Phosphate, Dinonyl Phenol Ethoxylate-11 Phosphate, Dinonyl Phenol Ethoxylate-15 Phosphate, Dinonyl Phenol Ethoxylate-24 Phosphate, Oat Amino Acid Phytosterol, Octoxynol-16, Octoxynol-25, Octoxynol-30, Octoxynol-33, Octoxynol-40, Octoxynol-70, Octoxynol-20 Carboxylic Acid, Octyldodecanol Ethoxylate-20, Octyldodecanol Ethoxylate-25, Octyldodecanol Ethoxylate-30, Oleamide MEA, Oleamidopropyl Betaine, Oleamidopropyl (Hydroxy Sulfone) Propyl Dimethyl Ammonium, Oleyl Amine Oxide, Oleic Acid, Oleoyl Hydrolyzed Collagen, Oleoyl Methionine, Oleyl Ethoxylate-20, Oleyl Ethoxylate-23, Oleyl Ethoxylate-24, Oleyl Ethoxylate-25, Oleyl Ethoxylate-30, Oleyl Ethoxylate-35, Oleyl Ethoxylate-40, Oleyl Ethoxylate-44, Oleyl Ethoxylate-50, Oleyl Ethoxylate-3 Carboxylic Acid, Oleyl Ethoxylate-6 Carboxylic Acid, Oleyl Ethoxylate-10 Carboxylic Acid, Oleyl Betaine, Olivoyl MEA, Olivoylaminopropyl Betaine, Olivoyl Acid, Olivoyl Hydrolyzed Wheat Protein, Ophiopogon Extract Stearate, Ozone-1 Oleyl Ethoxylate, Ozone-PEG-10 Oleate, Ozone-PEG-14 Oleate, Ozone- Polysorbate 80, Palmitoleic Acid, Palmitoleamidopropyl Betaine, Palmitoleyl Ethoxylate-2 Phosphate, Palmitamidopropyl Amine Oxide, Palmitamidopropyl Betaine, Palmitamine Oxide, Palmitic Acid, Palmitoyl Collagen Amino Acids, Palmitoyl Glycine, Palmitoyl Hydrolyzed Collagen, Palmitoyl Hydrolyzed Milk Protein, Palmitoyl Hydrolyzed Wheat Protein, Palmitoyl Keratin Amino Acids, Palmitoyl Oligopeptide, Palmitoyl Silk Amino Acids, Palm Kernel Acid, Palm Kernelamidopropyl Betaine, Peach Kernel Glycereth-8 Esters, Peanut Acid, PEG-10 Castor Oil, PEG-40 Castor Oil, PEG-44 Castor Oil, PEG-50 Castor Oil, PEG-54 Castor Oil, PEG-55 Castor Oil,PEG-60 castor oil, PEG-80 castor oil, PEG-100 castor oil, PEG-200 castor oil, PEG-11 cocamide, PEG-6 cocamidopropyl phosphate, PEG-4 cocamine, PEG-8 cocamine, PEG-12 cocamine, PEG-150 dibehenate, PEG-90 diisostearate, PEG-75 dilaurate, PEG-150 dilaurate, PEG-75 dioleate, PEG-150 dioleate, PEG-75 distearate, PEG-120 distearate, PEG-150 distearate, PEG-175 distearate, PEG-190 distearate, PEG-250 distearate, PEG-30 glyceryl cocoate, PEG-40 glyceryl cocoate, PEG-78 glyceryl cocoate, PEG-80 glyceryl cocoate, PEG-30 glyceryl isostearate, PEG-40 glyceryl isostearate, PEG-50 glyceryl isostearate, PEG-60 glyceryl isostearate, PEG-90 glyceryl isostearate, PEG-23 glyceryl laurate, PEG-30 glyceryl laurate, PEG-25 glyceryl oleate, PEG-30 glyceryl oleate, PEG-30 glyceryl soyaoleate, PEG-25 glyceryl stearate, PEG-30 glyceryl stearate, PEG-40 glyceryl stearate, PEG-120 glyceryl stearate, PEG-200 glyceryl stearate, PEG-28 glyceryl tallowate, PEG-80 glyceryl tallowate, PEG-82 glyceryl tallowate, PEG-130 glyceryl tallowate, PEG-200 glyceryl tallowate, PEG-45 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-54 hydrogenated castor oil, PEG-55 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG-100 hydrogenated castor oil, PEG-200 hydrogenated castor oil, PEG-30 hydrogenated lanolin, PEG-70 hydrogenated lanolin, PEG-50 hydrogenated palmitamide, PEG-2 isostearate, PEG-3 isostearate, PEG-4 isostearate, PEG-6 isostearate, PEG-8 isostearate, PEG-10 isostearate, PEG-12 isostearate, PEG-20 isostearate, PEG-30 isostearate, PEG-40 isostearate, PEG-26 jojoba acid, PEG-40 jojoba acid, PEG-15 jojoba alcohol, PEG-26 jojoba alcohol, PEG-40 jojoba alcohol, PEG-35 lanolin, PEG-40 lanolin, PEG-50 lanolin, PEG-55 lanolin, PEG-60 lanolin, PEG-70 lanolin, PEG-75 lanolin, PEG-85 lanolin, PEG-100 lanolin, PEG-150 lanolin, PEG-75 lanolin oil, PEG-2 lauramide,PEG-3 lauryl amine oxide, PEG-20 laurate, PEG-32 laurate, PEG-75 laurate, PEG-150 laurate, PEG-70 mango seed oil glycerides, PEG-20 mannitoi laurate, PEG-8 methyl ether dimethicone, PEG-120 methyl glucose dioleate, PEG-80 methyl glucose laurate, PEG-120 methyl glucose trioleate, PEG-4 montanate, PEG-30 oleyl amine, PEG-20 oleate, PEG-23 oleate, PEG-32 oleate, PEG-36 oleate, PEG-75 oleate, PEG-150 oleate, PEG-20 palmitate, PEG-150 polyglyceryl-2 triisostearate, PEG / PPG-28 / 21 acitate dimethicone, PEG / PPG-24 / 18 butyl ether dimethicone, PEG / PPG-3 / 17 copolymer, PEG / PPG-5 / 35 copolymer, PEG / PPG-8 / 55 copolymer, PEG / PPG-10 / 30 copolymer, PEG / PPG-10 / 65 copolymer, PEG / PPG-12 / 35 copolymer, PEG / PPG-16 / 17 copolymer, PEG / PPG-20 / 9 copolymer, PEG / PPG-20 / 20 copolymer, PEG / PPG-20 / 60 copolymer, PEG / PPG-20 / 65 copolymer, PEG / PPG-22 / 25 copolymer, PEG / PPG-28 / 30 copolymer, PEG / PPG-30-35 copolymer, PEG / PPG-30 / 55 copolymer, PEG / PPG-35 / 40 copolymer, PEG / PPG-50 / 40 copolymer, PEG / PPG-150 / 35 copolymer, PEG / PPG-160 / 30 copolymer, PEG / PPG-190 / 60 copolymer, PEG / PPG-200 / 40 copolymer, PEG / PPG-300 / 55 copolymer, PEG / PPG-20 / 22 methyl ether dimethicone, PEG-26-PPG-30 phosphate, PEG / PPG-4 / 2 propyl heptyl ether, PEG / PPG-6 / 2 propyl heptyl ether, PEG-7 / PPG-2 propyl heptyl ether, PEG / PPG-8 / 2 propyl heptyl ether, PEG / PPG-10 / 2 propyl heptyl ether, PEG / PPG-14 / 2 propyl heptyl ether, PEG / PPG-40 / 2 propyl heptyl ether, PEG / PPG-10 / 2 ricinoleate, PEG / PPG-32 / 3 ricinoleate, PEG-55 propylene glycol oleate, PEG-25 propylene glycol stearate, PEG-75 propylene glycol stearate, PEG-120 propylene glycol stearate, PEG-5 rapeseed sterol, PEG-10 rapeseed sterol, PEG-40 castor oil amide, PEG-75 shea butter glycerides, PEG-75 shorea butter glycerides,PEG-20 Sorbitan Cocoate, PEG-20 Sorbitan Isostearate, PEG-40 Sorbitan Lanolate, PEG-75 Sorbitan Lanolate, PEG-10 Sorbitan Laurate, PEG-40 Sorbitan Laurate, PEG-44 Sorbitan Laurate, PEG-75 Sorbitan Laurate, PEG-80 Sorbitan Laurate, PEG-20 Sorbitan Oleate, PEG-80 Sorbitan Palmitate, PEG-40 Sorbitan Stearate, PEG-60 Sorbitan Stearate, PEG-160 Sorbitan Triisostearate, PEG-40 Soy Sterol, PEG-2 Stearamidohydroxypropylamine, PEG-9 Stearamidohydroxypropylamine, PEG-20 Stearate, PEG-23 Stearate, PEG-25 Stearate, PEG-30 Stearate, PEG-32 Stearate, PEG-35 Stearate, PEG-36 Stearate, PEG-40 Stearate, PEG-45 Stearate, PEG-50 Stearate, PEG-55 Stearate, PEG-75 Stearate, PEG-90 Stearate, PEG-100 Stearate, PEG-120 Stearate, PEG-150 Stearate, PEG-45 Stearate Phosphate, PEG-20 Tallowate, PEG-50 Tallowamide, PEG-2 Tallowamide DEA, PEG-20 Tallowate, PEG-66 Trihydroxystearin, PEG-200 Trihydroxystearin, PEG-60 Tsubaki Acid Ester Glyceryl, Nonanoic Acid, Pentadocylphenol Polyether-200, Phenol Polyether-6 Phosphate, Poloxamer 105, Poloxamer 108, Poloxamer 182, Poloxamer 183, Poloxamer 184, Poloxamer 188, Poloxamer 217, Poloxamer 234, Poloxamer 235, Poloxamer 237, Poloxamer 238, Poloxamer 288, Poloxamer 334, Poloxamer 335, Poloxamer 338, Poloxamine 908, Poloxamine 1508, Polydimethylsiloxy PEG / PPG-24 / 19 Butyl Ether Silsesquioxane, Polydimethylsiloxy PPG-13 Butyl Ether Silsesquioxane, Polyglyceryl-6 Decanoate, Polyglyceryl-10 Dilauroate, Polyglyceryl-20 Heptaoleate, Polyglyceryl-20 Hexaoleate, Polyglyceryl-2 Lauryl Ether, Polyglyceryl-10 Lauryl Ether, Polyglyceryl-20 Octaisononanoate, Polyglyceryl-6 Pentaoleate, Polyglyceryl-10 Pentaoleate, Polyglyceryl-6 Tetraoleate, Polyglyceryl-10 Tetralauroate, Polyglyceryl-6 Trioleate, Polyglyceryl-10 Trioleate, Polyquaternium-77, Polyquaternium-78, Polyquaternium-79, Polyquaternium-80, Polyquaternium-81, Polyquaternium-82,Pomera derris (Pomaderis kumera-hou) flower / leaf extract, Poria cocos extract, Abietic hydrolyzed collagen potassium, Babassu oil acid potassium, Behenyl potassium, C9-15 Alkyl Potassium Phosphate, C11-15 Alkyl Potassium Phosphate, C12-13 Alkyl Potassium Phosphate, C12-14 Alkyl Potassium Phosphate, Decanoic acid potassium, Dipotassium Octanoyl Glutamate, Potassium Octanoyl Hydrolyzed Rice Protein, Potassium Ricinoleate, Potassium Cocoate, Potassium Coco-Glutamate, Potassium Coco-Glycinate, Potassium Coco-Hydrolyzed Caseinate, Potassium Coco-Hydrolyzed Collagen, Potassium Coco-Hydrolyzed Zein, Potassium Coco-Hydrolyzed Keratin, Potassium Coco-Hydrolyzed Avena Protein, Potassium Coco-Hydrolyzed Potato Protein, Potassium Coco-Hydrolyzed Rice Bran Protein, Potassium Coco-Hydrolyzed Rice Protein, Potassium Coco-Hydrolyzed Silk, Potassium Coco-Hydrolyzed Soy Protein, Potassium Coco-Hydrolyzed Wheat Protein, Potassium Coco-Hydrolyzed Yeast Protein, Potassium Coco-PCA, Potassium Coco-Sarcosinate, Potassium Coco-Taurate, Potassium Cornate, Potassium Cyclohexylpropyl Oleate, Potassium Di-Hydroxyethyl Cocoamine Oxide Phosphate, Potassium Dimethicone PEG-7 Phosphate, Potassium Dodecylbenzenesulfonate, Potassium Hempseed Acid, Potassium Hydrogenated Cocoate, Potassium Hydrogenated Palmate, Potassium Hydrogenated Tallowate, Potassium Hydroxystearate, Potassium Hydroxystearate, Potassium Lanolate, Potassium Laurate, Potassium Laureth-3 Carboxylate, Potassium Laureth-4 Carboxylate, Potassium Laureth-5 Carboxylate, Potassium Laureth-6 Carboxylate, Potassium Laureth-10 Carboxylate, Potassium Laureth Phosphate, Potassium Laurdimonium Collagen Amino Acids, Potassium Laurdimonium Glutamate, Potassium Laurdimonium Hydrolyzed Collagen, Potassium Laurdimonium Hydrolyzed Pea Protein, Potassium Laurdimonium Hydrolyzed Soy Protein, Potassium Laurdimonium PCA, Potassium Laurdimonium Pea Amino Acids, Potassium Laurdimonium Sarcosinate, Potassium Laurdimonium Silk Amino Acids, Potassium Laurdimonium Wheat Amino Acids, Potassium Laureth Phosphate, Potassium Laureth Sulfate, Potassium Linoleate, Potassium Metaphosphate, Potassium Methyl Coco-Taurate, Potassium Myristate, Potassium Myristoyl Glutamate, Potassium Myristoyl Hydrolyzed Collagen, Potassium Octoxynol-12 Phosphate, Potassium Oleate, Potassium Oleoyl Hydrolyzed Collagen, Potassium Oleylate, Potassium Oleyl Hydrolyzed Avena Protein, Potassium Oleyl Hydrolyzed Wheat Protein, Potassium Oleyl / Laurdimonium Wheat Amino Acids, Potassium Oleyl PCA, Potassium Palmate, Potassium Palmitate, Potassium Palmitoyl Hydrolyzed Zein, Potassium Palmitoyl Hydrolyzed Avena Protein, Potassium Palmitoyl Hydrolyzed Rice Protein, Potassium Palmitoyl Hydrolyzed Sweet Almond Protein, Potassium Palmitoyl Hydrolyzed Wheat Protein, Potassium Palm Kernelate, Potassium Peanutate, Potassium Rapate, Potassium Ricinoleate, Potassium Safflowerate, Potassium Soyate, Potassium Stearate, Potassium Stearoyl Hydrolyzed Collagen, Potassium Tallate, Potassium Tallowate, Potassium Taurate, Potassium Taurate Laurate, Potassium Trideceth-3 Carboxylate, Potassium Trideceth-4 Carboxylate, Potassium Trideceth-7 Carboxylate, Potassium Trideceth-15 Carboxylate, Potassium Trideceth-19 Carboxylate, Potassium Trideceth-6 Phosphate, Potassium Trideceth-7 Phosphate, Potassium Camellia Oilate, Potassium Undecylenate, Potassium Undecylenoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Rice Protein,PPG-30-buteth-30, PPG-36-buteth-36, PPG-38-buteth-37, PPG-30-oceth-4 phosphate, PPG-10 cetyl ether phosphate, PPG-2 C9-11 pareth-8, PPG-1-deceth-5, PPG-3-deceth-2 carboxylic acid, PPG-30-ethylhexeth-4 phosphate, PPG-20-glycereth-30, PPG-2 hydroxyethyl coco / isostearamide, PPG-2-isodeceth-8, PPG-2-isodeceth-10, PPG-2-isodeceth-18, PPG-2-deceth-25, PPG-4-deceth-10, propyltrimethylammonium hydrolyzed collagen, Quaternium-24, Quaternium-52, Quaternium-87, rapeseed acid, rice bran acid, rice oil glycereth-8 esters, ricinoleamidopropyl betaine, ricinoleic acid, ricinoleth-40, safflower acid, Sapindus Oahuensis fruit extract, Saponaria officinalis root powder, saponins, potassium saponate, sodium / potassium saponate, saponated, potassium saponated, sesame oil glycereth-8 esters, sesame oil amido propylamine oxide, sesame amido propyl betaine, shea amido propyl betaine, shea glycereth-8 esters, sodium arachidate, Sodium Arganampohoacetate, Sodium Buxus Starfruit Brown Oil, Sodium Avocado Oil, Sodium Babassu Oil Amphoacetate, Sodium Babassu Oil, Sodium Babassu Oil Sulfate, Sodium Behenate, Sodium Bis-Glycinate Ricinoleate Sulfosuccinate, Sodium Bis-Hydroxyethylglycinate Cocoglycocide Crosspolymer, Sodium Bis-Hydroxyethylglycinate Laurylglycocide Crosspolymer, Sodium Bis-Hydroxypropylamido PG-Dimethylamidonium Chloride Phosphate, Sodium Butylphenol Ethoxylate-12 Sulfate, Sodium Butylglucoside Hydroxypropyl Phosphate, Sodium C13-17 Alkyl Sulfonate, Sodium C14-18 Alkyl Sulfonate, Sodium C12-15 Alkoxypropyl Imidodi propionate, Sodium C10-16 Alkyl Sulfate, Sodium C11-15 Alkyl Sulfate, Sodium C12-13 Alkyl Sulfate, Sodium C12-15 Alkyl Sulfate, Sodium C12-18 Alkyl Sulfate, Sodium C16-20 Alkyl Sulfate, Sodium C9-22 Secondary Alkyl Sulfonate, Sodium C14-17 Secondary Alkyl Sulfonate, Sodium Caprate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropyl Sulfonate, Sodium Capryloamphopropionate, Sodium Caprylmethyltaurate, Sodium Caprylate, Sodium Capryl Ether-2 Carboxylic Acid, Sodium Capryl Ether-9 Carboxylic Acid, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropyl Sulfonate, Sodium Capryloamphopropionate, Disodium Capryloyl Glutamate, Sodium Capryloyl Hydrolyzed Wheat Protein, Sodium Capryl PG-Sulfonate, Sodium Capryl Sulfonate, Sodium Castor Oil Acid, Sodium Ceteareth-13 Carboxylic Acid, Sodium Cetearyl Sulfate, Sodium Cetyl Ether-13 Carboxylic Acid, Sodium Cetyl Sulfate, Sodium Cocoamidopropyl PG-Dimethylamidonium Phosphate, Sodium Cocoamino Propionate, Sodium Cocoeth Sulfate,Sodium Coco-yl / Palmoyl / Sunfloweroyl Glutamate, Sodium Cocoyl Proline, Sodium Cocoyl Sarcosinate, Sodium Cocoyl Taurate, Sodium Cocoyl Wheat Amino Acids, Sodium C12-14 Olefin Sulfonate, Sodium C14-16 Olefin Sulfonate, Sodium C14-18 Olefin Sulfonate, Sodium C16-18 Olefin Sulfonate, Sodium Cornoyl Propionate, Sodium Cottonseedoyl Acylate, Sodium C9-11 Pareth-6 Carboxylate, Sodium C11-15 Pareth-7 Carboxylate, Sodium C12-13 Pareth-5 Carboxylate, Sodium C12-13 Pareth-8 Carboxylate, Sodium C12-13 Pareth-12 Carboxylate, Sodium C12-15 Pareth-6 Carboxylate, Sodium C12-15 Pareth-7 Carboxylate, Sodium C12-15 Pareth-8 Carboxylate, Sodium C14-15 Pareth-8 Carboxylate, Sodium C12-14 Sec-Pareth-8 Carboxylate, Sodium C14-15 Pareth-PG Sulfonate, Sodium C12-13 Pareth-2 Phosphate, Sodium C13-15 Pareth-8 Phosphate, Sodium C9-15 Pareth-3 Sulfate, Sodium C10-15 Pareth Sulfate, Sodium C10-16 Pareth-2 Sulfate, Sodium C12-13 Pareth Sulfate, Sodium C12-15 Pareth Sulfate, Sodium C12-15 Pareth-3 Sulfate, Sodium C13-15 Pareth-3 Sulfate, Sodium C12-14 Sec-Pareth-3 Sulfate, Sodium C12-15 Pareth-3 Sulfonate, Sodium C12-15 Pareth-7 Sulfonate, Sodium C12-15 Pareth-15 Sulfonate, Sodium Deceth-2 Carboxylate, Sodium Deceth Sulfate, Sodium Decyl Benzene Sulfonate,Decyl Glucoside Hydroxypropylphosphoglycol Sodium, Decyl Glucoside Hydroxypropylsulfo- glycocol Sodium, Disodium Coco-GLYCOLS PCTA, Disodium Coco-GLYCOLS PCTA, Disodium Dilaureth-7 Citrate, Disodium Dilaureth-10 Phosphate, Disodium Dilauroylmethyl- propyl PG-Dimethylcocoammonium Phosphate, Disodium Dilaurylphosphate, Disodium Dimerdilaurate, Disodium Dioleylphosphate, Disodium Lauryl Sulfosuccinate, Disodium 2- Sulfolaurate, Disodium Glycerol Monoleate Phosphate, Disodium Glyceryl Soyate PG- Dimethylcocoammonium Phosphate, Disodium Glyceryl Soyate Amphoteric Acetate, Disodium Glyceryl Soyate, Disodium Hempseedamphoacetate, Sodium Hexanol-4 Carboxylate, Sodium Hydrogenated Cocoate, Sodium Hydrogenated Coco-Gluceth-50, Sodium Hydrogenated Palmitate, Sodium Hydrogenated Tallowate, Sodium Hydrogenated Tallowamido Gama- Carboxylic Acid, Sodium Hydroxylauryldimethylammonium Ethyl Phosphate, Sodium Hydroxypropyl Palmitamide Sulfonate, Sodium Hydroxypropyl Phosphoglycol Crosspolymer Decyl Glucoside, Sodium Hydroxypropyl Phosphoglycol Crosspolymer Lauryl Glucoside, Sodium Hydroxypropyl Sulfonate Coco-Glucoside Crosspolymer, Sodium Hydroxypropyl Sulfonate Decyl Glucoside Crosspolymer, Sodium Hydroxypropyl Sulfonate Lauryl Glucoside Crosspolymer, Sodium Hydroxystearate, Sodium Isostearate, Sodium Isosteareth-6 Carboxylate, Sodium Isosteareth-11 Carboxylate, Sodium Isostearamphoacetate, Sodium Isostearamphopropionate, Sodium N-Isostearamidomethyl Taurate, Sodium Laneth Sulfate, Sodium Lanolate, Sodium Lardate, Sodium Laurylamidodiacetate, Sodium Laurylaminopropionate, Sodium Laurylate, Sodium Laureth-3 Carboxylate, Sodium Laureth-4 Carboxylate, Sodium Laureth-5 Carboxylate, Sodium Laureth-6 Carboxylate, Sodium Laureth-8 Carboxylate, Sodium Laureth-11 Carboxylate, Sodium Laureth-12 Carboxylate, Sodium Laureth-13 Carboxylate, Sodium Laureth-14 Carboxylate, Sodium Laureth-16 Carboxylate, Sodium Laureth-17 Carboxylate, Sodium Laureth Sulfate, Sodium Laureth-5 Sulfate, Sodium Laureth-7 Sulfate, Sodium Laureth-8 Sulfate, Sodium Laureth-12 Sulfate, Sodium Laureth-40 Sulfate, Sodium Laureth-7 Tartrate, Disodium Lauryliminodipropionate, Disodium Lauryliminodipropionate, Sodium Lauryl Amphoacetate, Sodium Lauryl PG-Acetate Phosphate, Sodium Lauryl Amphopropionate, Sodium Lauryl Aspartate, Sodium Lauryl Collatamidopropionate, Sodium Lauryl Glutamate Propionate, Sodium Lauryl Hydrolyzed Collagen, Sodium Lauryl Hydrolyzed Silk, Sodium Lauryl Hydroxypropylsulfonate, Sodium Lauryl Isethionate, Sodium Lauryl Methyl Aminopropionate, Sodium Lauryl Methyl Gluceth-50, Sodium Lauryl Milletamidopropionate, Sodium Lauryl / Myristoyl Aspartate, Sodium Lauryl / Oat Amino Acid, Sodium Lauryl Sarcosinate, Sodium Lauryl Silk Amino Acid, Sodium Lauryl Taurate, Sodium Lauryl Wheat Amino Acid, Sodium Lauryl Bis-Ethylaminoethyl Amidoethylamine, Sodium Lauryl Glucose Carboxylate, Sodium Lauryl Glucoside Hydroxypropyl Phosphate, Sodium Lauryl Glucoside Hydroxypropyl Sulfonate, Sodium Lauryl Glycereth Carboxylate, Sodium Lauryl Glycerylphospholipid Sodium Lauryl Hydroxyethylamidoethyl Sulfate,Sodium Lauryl Sulfate, Sodium Lauryl Sulfoacetate, Sodium Linoleate, Sodium Macadamia Seedate, Sodium Mangoate, Sodium Mango Seedate, Sodium Laureth-2 Sulfosuccinate, Sodium Methoxy PPG-2 Acetate, Sodium Methyl Cocoyl Taurate, Sodium Methyl Lauroyl Taurate, Sodium Methyl Myristoyl Taurate, Sodium Methyl Oleoyl Taurate, Sodium Methyl Palmitoyl Taurate, Sodium Methyl Stearoyl Taurate, Sodium 2-Methyl-2-Sulfolaurate, Sodium 2-Methyl-2-Sulfopalmirate, Sodium Isopalmoyl Methyl Taurate, Sodium Cocoyl Methyl Taurate, Sodium Myreth Sulfate, Sodium Myristate, Sodium Myristoyl Amphoacetate, Sodium Myristoyl Glutamate, Sodium Myristoyl Hydrolyzed Collagen, Sodium Myristoyl Isethionate, Sodium Myristoyl Sarcosinate, Sodium Myristyl Sulfate, Sodium Nonyl Phenene Ethoxylate Phosphate, Sodium Nonyl Phenene Ethoxylate Phosphate, Sodium Nonyl Phenene Ethoxylate Sulfate, Sodium Nonyl Phenene Ethoxylate Sulfate, Sodium Nonyl Phenene Ethoxylate Sulfate, Sodium Nonyl Phenene Ethoxylate Sulfate, Sodium Nonyl Phenene Ethoxylate Sulfate, Sodium Octoxynol-2 Ethylsulfate, Sodium Octoxynol-2 Sulfate, Sodium Octoxynol-6 Sulfate, Sodium Octoxynol-9 Sulfate, Sodium Oleate, Sodium Oleamphoacetate, Sodium Oleamphopropyl Sulfonate, Sodium Oleamphopropionate, Sodium Oleamidopropyl Collagen, Sodium Oleamidopropyl Hydroxyethyl Sulfonate, Sodium Oleamidopropyl Ethoxysulfate, Sodium Oleamidopropyl Hydroxyethyl Sulfonate, Sodium Olivamphoacetate, Sodium Olivate, Sodium Olivoyl Glutamate, Sodium Palmamphoacetate, Sodium Palmate, Sodium Palmeth-45 Itaureate, Sodium Palmitate, Sodium Palmitoyl Hydrolyzed Collagen, Sodium Palmitoyl Hydrolyzed Wheat Protein, Sodium Palmitoyl Sarcosinate, Sodium Palmityl Oleate, Sodium Palmoyl Hydroxyethyl Sulfonate, Sodium Palmoyl Glutamate, Sodium Passiflora Incarnata Seedate, Sodium Peanutamphoacetate, Sodium Peanutate, Sodium PEG-6 Cocamide Carboxylate, Sodium PEG-8 Cocamide Carboxylate, Sodium PEG-4 Cocamide Sulfate, Sodium PEG-3 Lauramide Carboxylate, Sodium PEG-4 Lauramide Carboxylate, Sodium PEG-8 Palm Glycerate Carboxylate, Sodium Pentaerythrityl Hydroxypropyl Imidazdiacetate Copolymer, Sodium Propoxy PPG-2 Acetate, Sodium Rapeseedate, Sodium Rice Branamphoacetate, Sodium Ricinoleate, Sodium Ricinoleamphoacetate, Sodium Rose Hipsamphoacetate, Sodium Rosinate, Sodium Safflowerate, Sodium Saffloweroyl Hydrolyzed Soy Protein, Sodium Sesaminate, Sodium Sesamoleamphoacetate, Sodium Sheabutteramphoacetate, Sodium Soyate, Sodium Soyamidopropyl Collagen, Sodium Stearate, Sodium Stearamphoacetate, Sodium Stearamphopropyl Sulfonate, Sodium Stearamphopropionate, Sodium Stearoyl Caseinate, Sodium Stearoyl Glutamate, Sodium Stearoyl Hyaluronate, Sodium Stearoyl Hydrolyzed Collagen, Sodium Stearoyl Hydrolyzed Corn Protein, Sodium Stearoyl Hydrolyzed Silk,Sodium stearoyl hydrolyzed soybean protein, sodium stearoyl hydrolyzed wheat protein, sodium stearoyl whey protein, sodium stearoyl methyl hydroxyethanesulfonate, sodium stearoyl oat protein, sodium stearoyl pea protein, sodium stearoyl soybean protein, sodium stearoyl dimethyl glycinate, sodium stearyl alcohol sulfate, sodium sunflower seed oleoyl amphotericin, sodium subtilis lipopeptide, sodium sweet almond oleoyl amphotericin, sodium sweet almond oil, sodium talloyl amphotericin propionate, sodium talloyl oleate, sodium tallow oleoyl amphotericin, sodium tallow acid, sodium tallow alcohol sulfate, Callophyllum In-OPHYLLUM Sodium Seed Oil, Sodium Taurate, Sodium Cocoyl Methyl Taurate, Sodium Lauroyl Taurate, Sodium Lauroyl Collagen Amino Acid / TEA Salt, Sodium Lauroyl Hydrolyzed Collagen / TEA Salt, Sodium Lauroyl Hydrolyzed Keratin / TEA Salt, Sodium Lauroyl Keratin Amino Acid / TEA Salt, Sodium Undecenoyl Collagen Amino Acid / TEA Salt, Sodium Undecenoyl Hydrolyzed Collagen / TEA Salt, Sodium Undecenoyl Hydrolyzed Corn Gluten / TEA Salt, Sodium Undecenoyl Hydrolyzed Soybean Gluten / TEA Salt, Sodium Undecenoyl Hydrolyzed Wheat Gluten / TEA Salt, Theobroma GRANDIFLORUM) Sodium seed oil, sodium tridecyl alcohol polyether-3 carboxylate, sodium tridecyl alcohol polyether-4 carboxylate, sodium tridecyl alcohol polyether-6 carboxylate, sodium tridecyl alcohol polyether-7 carboxylate, sodium tridecyl alcohol polyether-8 carboxylate, sodium tridecyl alcohol polyether-12 carboxylate, sodium tridecyl alcohol polyether-15 carboxylate, sodium tridecyl alcohol polyether-19 carboxylate, sodium tridecyl alcohol polyether sulfate, sodium tridecylbenzene sulfonate, sodium tridecyl alcohol sulfate, sodium trimethylolpropane hydroxypropyl iminodiacetic acid (TAPHA) resin, sodium undecyl alcohol polyether-5 carboxylate, sodium undecenoate, sodium undecenoyl amphoteric acid, sodium undecenoyl amphoteric propionate, disodium undecenoyl glutamate, sodium wheat germ oil amphoteric acid, sorbitol polyether-160 tristearate, soybean oleic acid, soybean oleamide propylamine oxide, soybean oleamide propyl betaine, soybean glyceryl polyether-8 ester, isostearamide propylamine oxide Stearoamide propyl betaine, stearamide oxide, stearyl alcohol polyether-15, stearyl alcohol polyether-16, stearyl alcohol polyether-20, stearyl alcohol polyether-21, stearyl alcohol polyether-25, stearyl alcohol polyether-27, stearyl alcohol polyether-30, stearyl alcohol polyether-40, stearyl alcohol polyether-50, stearyl alcohol polyether-80, stearyl alcohol polyether-100, stearyl alcohol polyether-2 phosphate, stearyl alcohol polyether-3 phosphate, stearic acid, stearoxypropyltrimethyl Stearoyl glutamic acid, stearoyl sarcosine, stearyl betaine, stearyl dimethyl butyl glucoside hydroxypropyl ammonium chloride, stearyl dimethyl decyl glucoside hydroxypropyl ammonium chloride, stearyl dimethyl lauryl glucoside hydroxypropyl ammonium chloride, sulfated castor oil, sulfated coconut oil, sulfated glyceryl oleate, sulfated olive oil, sulfated peanut oil, sunflower oil oleamide MEA, sunflower seed oleic acid, sunflower seed oleamide propyl hydroxyethyl dimethyl ammonium chloride,Sunflower seed oil glycereth-8 esters, tall oil acid, tallow acid, tallowamidopropylamine oxide, tallowamidopropyl betaine, tallowamidopropyl hydroxysultaine, tallowyl amine oxide, tallowyl betaine, tallowyl dihydroxyethyl betaine, tallowoyl ethyl glycol, retinyl hydrolyzed collagen TEA salt, C12-14 olefin phosphate TEA salt, C10-15 alkyl sulfate TEA salt, C11-15 olefin sulfate TEA salt, C12-13 alkyl sulfate TEA salt, TEA-C12-14 alkyl sulfate TEA salt, TEA-C12-15 alkyl sulfate TEA salt, TEA C14-17 secondary alkyl sulfonate TEA salt, TEA canola oil acid, TEA cocoamide diacetate, TEA cocoate, TEA coco sulfate, TEA cocoyl alanine, TEA cocoyl glutamate, TEA cocoyl glutamide, TEA cocoyl glycinate, TEA cocoyl hydrolyzed collagen, TEA cocoyl hydrolyzed soy protein, TEA cocoyl sarcosinate, TEA dimethicone PEG-7 phosphate, TEA dodecylbenzenesulfonate, TEA hydrogenated cocoate, TEA hydrogenated tallow glutamate, TEA isostearate, TEA- isostearyl hydrolyzed collagen TEA salt, TEA lauraminopropionate, TEA laurate, TEA laurate / myristate, TEA lauryl ether sulfate, TEA lauroyl collagen amino acids, TEA lauroyl glutamate, TEA lauroyl hydrolyzed collagen, TEA lauroyl keratin amino acids, TEA lauroyl methylaminopropionate, TEA lauroyl / myristoyl aspartate, TEA lauroyl sarcosinate, TEA lauryl phosphate, TEA lauryl sulfate, TEA myristaminopropionate, TEA myristate, TEA myristoyl hydrolyzed collagen, TEA oleate, TEA oleyl hydrolyzed collagen, TEA oleyl sarcosinate, TEA oleyl sulfate, TEA palmitate, TEA palmityl sarcosinate, TEA PEG-3 cocoamide sulfate, TEA pinoic acid, TEA stearate, TEA tallate, TEA tridecylbenzenesulfonate, TEA undecylenate, TEA undecylenoyl hydrolyzed collagen, tetramethyldecynediol, tetrasodium dicarboxyethylhydroxyethylsulfonamide, TIPA lauryl ether sulfate, TIPA myristate, TIPA stearate, tocopheryl phosphate, trehalose undecanoate, TM-C12-15 pareth-2 phosphate, TM-C12-15 pareth-6 phosphate, TM-C12-15 pareth-8 phosphate, TM-C12-15 pareth-10 phosphate, trideceth-20, trideceth-50, trideceth-3 carboxylic acid, trideceth-4 carboxylic acid, trideceth-7 carboxylic acid, trideceth-8 carboxylic acid,Tridecyl alcohol polyether-15 carboxylic acid, tridecyl alcohol polyether-19 carboxylic acid, tridecyl alcohol polyether-10 phosphate, tridecylbenzene sulfonic acid, tris(lauroyl polyether-9) citrate, trimethylolpropane hydroxypropyl dihydroxyethylamine resin, tris(lauroyl amphoteric PG-acetic acid sodium chloride) phosphate, undecanoic acid, undecanoyl alcohol polyether-5 carboxylic acid, undecenoyl ammonium amine oxide, undecenoyl ammonium betaine, undecenoic acid, undecenoyl collagen amino acid, undecenoyl glycine, undecenoyl hydrolyzed collagen, undecenoyl wheat amino acids, undecyl glucoside, wheat germ fatty acid, wheat germ oleamide propylamine oxide, wheat germ oleamide propyl betaine, Yucca schidigera leaf / root / stem extract, Yucca schidigera stem extract, zinc cocoyl alcohol polyether sulfate and zinc cocoyl alcohol sulfate.

[0128] Nonionic co-surfactants

[0129] Alkyl alcohols. The added nonionic surfactant is preferably alkoxylated and / or propoxylated, particularly preferably a primary alcohol containing 8-18 carbon atoms per mole of alcohol and an average of 1-12 moles of ethylene oxide (EO) and / or 1-10 moles of propylene oxide (PO). Particularly preferred are C8-C alcohols with a degree of ethoxylation of 2-10, preferably 3-8, and / or a degree of propoxylation of 1-6, preferably 1.5-5. 16 - Alcohol alkoxylates, preferably ethoxylates and / or propoxylates C 10 -C 15 - Alcohol alkoxylates, especially C 12 -C 14 Alcohol alkoxylates. The degrees of ethoxylation and propoxylation constitute a statistical average, which may be an integer or a fraction for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homologue distribution (narrow range ethoxylate / propoxylate, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols having more than 12EO can also be used. Examples include (butter) fatty alcohols having 14EO, 16EO, 20EO, 25EO, 30EO, or 40EO.

[0130] Alkyl glycosides In addition, as an extra nonionic surfactant, RO(G) can be added. xalkyl glycosides, such as, for example, as compounds, in particular together with nonionic surfactants, in which R is a linear or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G represents a monosaccharide unit having 5 or 6 carbon atoms, preferably glucose. The degree of glycosylation x, which defines the distribution of monoglycosides and oligoglycosides, is a number between 1 and 10, preferably between 1.1 and 1.4.

[0131] Fatty acid ester alkoxylates. Another class of preferred nonionic surfactants, which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, in particular with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably fatty acid methyl esters having 1 to 4 carbon atoms in the alkyl chain, more particularly, for example, those described in Japanese Patent Application JP-A-58 / 217 598 or preferably prepared by the process described in International Patent Application WO-A-90 / 13533. Particularly preferred are C 12 -C 18 Fatty acid methyl esters

[0132] Amine oxides. Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and also fatty acid alkanolamides of the type are suitable. The amount of these nonionic surfactants is preferably not greater than the amount of ethoxylated fatty alcohols, in particular not more than half the amount thereof.

[0133] Gemini surfactants. Further surfactants are so-called gemini surfactants. In general, this class of compounds is understood to mean compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a "spacer". This spacer is usually a carbon chain, the length of which should be sufficient to enable the hydrophilic groups to act independently of one another. This class of surfactants is usually characterized by very low critical concentrations and a very great reduction in the surface tension of water. Special cases of gemini surfactants are, however, not only di- but also tri- surfactants. Suitable gemini surfactants are, for example, the sulfated hydroxy mixed ethers from German Patent Application DE 4321022 A1 or the di- and tri- polyol-sulfates and -ether sulfates according to International Patent Application 96 / 23768 A1. The capped di- and tri- mixed ethers according to German Patent Application DE 19513391 A1 are characterized by their di- and multifunctionality. It is also possible to use gemini polyhydroxy fatty acid amides or polyhydroxy fatty acid amides such as those described in International Patent Applications WO 95 / 19953 A1, WO 95 / 19954 A1 and WO 95 / 19955 A1.

[0134] Cationic co-surfactants

[0135] Tetraalkyl quaternary ammonium salts. Cationic active surfactants in aqueous solution contain a hydrophobic polymer group required for the surface activity of the dissociated cation. Important representatives of cationic surfactants are tetraalkyl quaternary ammonium salts of the general formula (R 1 R 2 R 3 R 4 N + )X - wherein R 1 represents a Ci-C8alk(en)yl group, R 2 , R 3 and R 4 independently of one another represent an alk(en)yl group containing 1 to 22 carbon atoms. X is a counterion, preferably selected from the group consisting of halides, alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen atom is substituted by two long acyl groups and two short alk(en)yl groups.

[0136] Ester quaternary ammonium salts. Cationic surfactants which are particularly used as auxiliary surfactants in accordance with the application are represented by the ester quaternary ammonium salts. Ester quaternary ammonium salts are generally understood to be quaternized fatty acid triethanolamine ester salts. These are known compounds which can be obtained by the methods known per se in organic chemistry. Reference is made to the international patent application WO 91 / 01295 A1, in which triethanolamine is esterified with fatty acid moieties in the presence of hypophosphorous acid, air is passed into the reaction mixture and subsequently dimethyl sulfate or ethylene oxide is used for the overall quaternization. Furthermore, the German patent DE 4308794 C1 describes a process for the preparation of solid ester quaternary ammonium salts, in which the quaternization of the triethanolamine ester is carried out in the presence of a suitable dispersant, preferably a fatty alcohol.

[0137] A typical example of an esterquat which is suitably used according to the present application is a product whose acyl component is derived from a monocarboxylic acid corresponding to the formula RCOOH, wherein RCO is an acyl group containing 6 to 10 carbon atoms, and the amino component is triethanolamine (TEA). Examples of such monocarboxylic acids are caproic acid, caprylic acid, capric acid and technical mixtures thereof, such as for example the so-called head fraction fatty acids. Preferably used esterquats whose acyl component is derived from a monocarboxylic acid containing 8 to 10 carbon atoms. Other esterquats are those whose acyl component is derived from a dibasic carboxylic acid such as malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid, but preferably adipic acid. In general, esterquats whose acyl component is derived from a mixture of a monocarboxylic acid containing 6 to 22 carbon atoms and adipic acid are preferred. The molar ratio of monocarboxylic acid and dibasic carboxylic acid in the final esterquat is 1 :99 to 99:1 and preferably 50:50 to 90:10 and in particular 70:30 to 80:20. In addition to the quaternized fatty acid triethanolamine ester salts, other suitable esterquats are mono / dibasic carboxylic acid mixtures with diethanolalkylamines or 1,2-dihydroxypropyl dialkylamines. The esterquats can be obtained from a mixture of fatty acids and the corresponding triglycerides with the corresponding dibasic carboxylic acid. One such process, which can be considered as representative of the relevant prior art, is described in European patent EP 0750606 B1. In order to produce the quaternized ester, the mixture of mono and dibasic carboxylic acid and triethanolamine can have a molar ratio of 1.1 :1 to 3:1 based on the available carboxylic functions. In view of the performance of the esterquats, it has proven particularly advantageous to have a ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to 1.9:1. The preferred esterquats are technical mixtures of mono, di and tri esters having an average degree of esterification of 1.5 to 1.9.

[0138] Amphoteric co-surfactants

[0139] Zwitterions. Zwitterionic or amphoteric surfactants possess multiple functional groups which can ionize in aqueous solution and thereby - depending on the medium conditions - impart anionic or cationic properties to the compound (see DIN 53900, July 1972). Near the isoelectric point (about pH 4), amphoteric surfactants form internal salts and thereby become weakly soluble or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and zwitterions, the latter of which exhibit in solution a zwitterionic character. Ampholytes are zwitterionic electrolytes, i.e. compounds which simultaneously possess an acidic and a basic hydrophilic group and thus behave as an acid or as a base depending on the conditions. In particular, zwitterions are known surfactants which are produced mainly by carboxyalkylation, preferably carboxymethylation, of amine compounds. The starting material is preferably condensed with a halogenated carboxylic acid or a salt thereof, in particular sodium chloroacetate, one mole of salt being formed per mole of zwitterion. Addition of unsaturated carboxylic acids, for example acrylic acid, is also possible. Examples of suitable zwitterions are carboxyalkylation products of secondary, in particular tertiary, amines which correspond to the general formula R1 R 2 R 3 N-(CH2) q COOX, wherein R 1 is an alkyl group having 6 to 22 carbon atoms, R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms, q is a number from 1 to 6, and X is an alkali and / or alkaline earth metal or ammonium. Typical examples are hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, C 12 / 14 - cocodimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl ethylmethylamine, oleyldimethylamine, C 16 / 18 - tallowdimethylamine and their technical mixtures, and in particular carboxymethylated products of dodecylmethylamine, dodecyldimethylamine, dodecyl ethylmethylamine and their technical mixtures.

[0140] Alkylamido betaines. Other suitable betaines are carboxyalkylated products of amidoamines, which correspond to the general formula R 1 CO(R 3 )(R 4 )-NH-(CH2) p -N-(CH2) q COOX, wherein R 1 CO is an aliphatic acyl group having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms, p is a number from 1 to 6, q is a number from 1 to 3, and X is an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, such as hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, cis(9)-eicosenoic acid, behenic acid, erucic acid and their technical mixtures, with N,N-dimethylaminoethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminoethylamine and N,N-diethylaminopropylamine, which are condensed with sodium chloroacetate. Commercially available products include K and PK (Cognis Deutschland GmbH & Co., KG) and Betaine (Goldschmidt).

[0141] Imidazolines. Other suitable starting materials for betaines for the purposes of the present application are imidazolines. These substances are also known and can be obtained, for example, by cyclization condensation of 1 or 2 moles of C6-Cι2alkylamines with 1 mole of C6-Cι2alkylcarboxylic acids. 22 Cyclization condensation of fatty acids with polyfunctional amines such as aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylated products are mixtures of different open-chain betaines. A typical example is the condensation product of the above-mentioned fatty acids with AEEA, preferably imidazoline based on lauric acid, which is subsequently betainized with sodium chloroacetate. Commercially available products include G (Cognis Deutschland GmbH & Co., KG).

[0142] The (co)surfactants are preferably used in the compositions of the present application in amounts of from 0.1 to 90 wt.%, especially from 10 to 80 wt.%, and particularly preferably from 20 to 70 wt.%.

[0143] Organic solvents

[0144] Liquid light duty or heavy duty detergents can contain organic solvents, preferably those which are miscible with water. For this purpose polyglycols, ethers, alcohols, ketones, amides and / or esters are preferably used as organic solvents in amounts of from 0 to 90 wt.%, preferably from 0.1 to 70 wt.%, especially from 0.1 to 60 wt.%. Low molecular weight polar substances such as methanol, ethanol, propylene carbonate, acetone, acetonal, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof are preferred.

[0145] Enzymes

[0146] Cellulases. Optionally, cellulases can be incorporated into the present detergent compositions, when such enzymes are employed, they are preferably incorporated into the compositions in a quantity sufficient to provide up to about 5 mg, more preferably from about 0.01 mg to about 3 mg, of active enzyme per gram of composition. Unless otherwise stated, compositions of the present application preferably comprise from about 0.001% to about 5%, preferably 0.01%-1%, by weight, of a commercial enzyme preparation.

[0147] Cellulases suitable for use herein include bacterial or fungal cellulases. Preferably they have a pH optimum in the range 5-9.5. Suitable cellulases are fungal cellulases produced by Humicola insolens and a strain of Humicola grisea, DSM 1800, or cellulase 212 produced by a fungus belonging to the genus Acholeplasma, and cellulase extracted from the hepatopancreas of Dolabella auricula Solander. Suitable cellulases are also disclosed in GB 2,075,028A. Furthermore, cellulases especially suitable for use in the present application are disclosed in WO 1992 013057 Al. Most preferably, the cellulase for use in the present detergent compositions is commercially available under the trade names CERASE® and CELLUZYME® from NOVO Industries A / S.

[0148] Other enzymes. Other enzymes can be included in the detergent compositions herein for a variety of end uses, including, for example, removal of protein based, carbohydrate based or triglyceride based stains, as well as to avoid migration of shed dye and for fabric restoration. Other enzymes which can be incorporated include proteases, amylases, lipases, and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any appropriate

[0149] Generally, enough of each enzyme is included that the composition provides up to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of active enzyme per gram of composition. The compositions herein will typically contain from about 0.001% to about 5%, preferably 0.01%-1%, by weight of a commercial enzyme preparation, unless stated otherwise. The protease will typically be present in such commercial preparations at a level of 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

[0150] An example of a suitable protease is the subtilisins which is derived from Bacillus subtilis and Bacillus licheniforms. Another suitable protease is obtained from a strain of Bacillus, developed and sold by Novo Industries A / S as ESPERASE®. Proteolytic enzymes which are commercially available include those from Novo Industries A / S under the trade The preparation of such enzymes and similar enzymes is described in Novo's UK Patent GB 1,243,784. Commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the tradename Savinase® by Novo Industries A / S, and those sold under the tradename Alcalase® by Novo Industries A / S. and and those sold under the tradename Maxatase®, Maxacal®, and Properase® by International Bio-Synthetics, Inc. Other proteases include Protease A, Protease B, and Protease C sold by Genencor International, Inc. under US 5,204,015 and US 5,244,791.

[0151] Amylases include, for example, alpha-amylases such as SP 501AA® sold by Genencor International, Inc. International Bio-Synthetics, Inc., and Novo Industries.

[0152] Suitable lipases for use in detergents include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19,154. Such a lipase is available as Lipase P "Amano" from Amano Pharmaceutical Co., Ltd., Nagoya, Japan. Other commercially available lipases include Lipase PES by Amano, Lipase ex Chromobacter viscosum, for example, Chromobacter viscosum var. lipo-lyticum NRRL B 3673, available from Toyo Jozo Co.; and other Chromobacter viscosum lipases sold under the tradename Lipex® by U.S. Biochemical Corp. and Disoynth Co., and Lipase ex Pseudomonas gladioli, available from Amano Pharmaceutical Co., Ltd. Lipase ex Humicola lanuginosa (available from Novo Industries A / S) is sold under the tradename Lipolase® by Novo Industries A / S. Lipase ex Pseudomonas fluorescens is sold under the tradename Lipase PL® by Gist-Brocades.

[0153] ​Peroxidases are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e., to avoid the migration of dyes or pigments removed from substrates during the wash process onto other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Peroxidase-containing detergent compositions are disclosed, for example, in WO 1989 / 099813 Al.

[0154] Enzyme Stabilizers. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and / or magnesium ions in the finished compositions which provide these ions to the enzymes. (Calcium ions are generally more effective than magnesium ions, and calcium ions are preferred herein if only one such cation is used.) Additional stabilization can be achieved by including various other art-disclosed stabilizers, especially borate species, see US 4,537,706, herein incorporated by reference in its entirety. Typical detergents, especially liquid detergents, contain from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12 millimoles of calcium ion per liter of finished composition. In solid detergent compositions, the formulation can contain sufficient water-soluble calcium ion source to provide the desired amount of this material in the laundry water solution. Alternatively, the natural water hardness is sufficient.

[0155] It is recognized that the above levels of calcium and / or magnesium ions are sufficient to ensure enzyme stability. Additional calcium and / or magnesium ions can be added to the composition to provide additional means for grease removal. Thus, typical formulations of the compositions of the present application can contain from about 0.05% to about 2% by weight of a water-soluble calcium or magnesium ion source, or both. Of course, the amount can vary depending on the amount and type of enzyme used in the composition.

[0156] The compositions of the present application can also optionally, but preferably, contain various other stabilizers, especially borate-type stabilizers. Typically, such stabilizers are used in the compositions at levels of from about 0.25% to about 10%, preferably from about 0.5% to about 5%, and more preferably from about 0.75% to about 3% by weight (based on boric acid). Although other compounds, such as boric oxide, borax, and other alkali metal borates (e.g., sodium orthoborate, sodium metaborate, and sodium pyroborate and sodium pentaborate) are suitable, boric acid is preferred. Substituted boric acids (e.g., phenylboronic acid, butaneboronic acid, and p-bromophenylboronic acid) can also be used in place of boric acid.

[0157] Builders

[0158] Polycarboxylic acids. Useful organic co-builders are, for example, polycarboxylic acids, which can be used in the form of their sodium salts, wherein polycarboxylic acids mean carboxylic acids which carry more than one acid function. Included 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) and derivatives and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

[0159] Organic acids. It is also possible to use the acids as such. In addition to their builder action, acids often also have the effect of acidifying the ingredient, and thus can establish a relatively low and mild pH value in the detergent or cleaning composition. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof can be mentioned in particular. Other suitable acidifiers are known pH regulators such as sodium bicarbonate and sodium bisulfate.

[0160] Polymers. Particularly suitable polymeric co-builders are polyacrylates, which preferably have a molecular weight of from 2000 to 20000 g / mol. On account of their excellent solubility, short-chain polyacrylates having a molar mass of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, are preferred in this group. Suitable polymers can also include substances which consist partly or completely of vinyl alcohol units or derivatives thereof.

[0161] Other suitable copolycarboxylates are in particular copolymers 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 from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid, have proved to be particularly suitable. Their relative molecular mass, based on the free acid, is generally from 2000 to 70000 g / mol, preferably from 20000 to 50000 g / mol and especially from 30000 to 40000 g / mol. The (co)polycarboxylates can be added in aqueous solution or preferably in powder form. In order to improve the water solubility, the polymers can also contain allyl sulfonic acid monomers, such as, for example, allyloxybenzenesulfonic acid and methylallyl sulfonic acid in EP 0727448 B1.

[0162] Particularly preferred are biodegradable polymers which contain more than two different monomer units, examples being those which contain, as monomers, acrylic acid and maleic acid salts, and vinyl alcohol or vinyl alcohol derivatives in DE 4300772 A1, or those which contain, as monomers, acrylic acid and 2-alkylallyl sulfonic acid salts, and sugar derivatives. Other preferred copolymers are those described in German patent applications DE 4303320 A1 and DE 4417734 A1 and preferably comprise, as monomers, acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

[0163] Likewise, other preferred co-builders are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acid or its salts and derivatives as disclosed in German patent application DE 195 40 086 A1 which, in addition to co-builder performance, also have a bleaching stabilizing effect.

[0164] Other suitable co-builders are polyoxaalkylenes which are obtained by reacting a diacid with a polyhydroxycarboxylic acid having 5 to 7 carbon atoms and at least 3 hydroxyl groups, as described in European patent application EP 0 280 223 A1. Preferred polyoxaalkylenes are obtained from diacids such as glyoxalic acid, glutaric acid, terephthalic acid and mixtures thereof with polyhydroxycarboxylic acids such as gluconic acid and / or glucoheptonic acid.

[0165] Carbohydrates. Other suitable organic co-builders are dextrins, e.g. oligomers or polymers of carbohydrates, which are obtained by partial hydrolysis of starch. The hydrolysis can be carried out by conventional methods, e.g. acid catalysis or enzyme catalysis. Preferred are hydrolysis products having an average molar mass of from 400 to 500 000 g / mol. Preferred are polysaccharides having a dextrose equivalent (DE) of from 0.5 to 40, more particularly from 2 to 30, wherein DE is an accepted measure of the reducing power of the polysaccharide compared to dextrose having a DE of 100. Maltodextrins having a DE of from 3 to 20 and dried glucose syrups having a DE of from 20 to 37, as well as so-called yellow and white dextrins having a higher molecular weight of from 2000 to 30 000 g / mol can be used. Preferred dextrins are described in British patent application 94 19 091.

[0166] Oxidized derivatives of such dextrins involve reaction products of dextrins with oxidizing agents which are capable of oxidizing at least the alcohol function of the sugar ring to a carboxylic acid function. Such oxidized dextrins and processes for their preparation are known from, for example, European patent application EP 0 232 202 A1. A product which is oxidized at C6 of the sugar ring is particularly preferred.

[0167] Other suitable co-builders are further derivatives of oxodisuccinates and disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine-N,N'-disuccinic acid (EDDS) is preferably used in the form of the sodium or magnesium salt, the synthesis of which is described in, for example, US 3,158,615. Particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described in US 4,524,009. The addition level is from 3 to 15% by weight in formulations containing zeolites and / or silicates.

[0168] Lactones. Other usable organic auxiliary builders include, for example, acetylated hydroxycarboxylic acids or their salts, optionally in the form of lactones, and containing at least four carbon atoms, at least one hydroxyl group, and at most two acid groups. Such auxiliary builders are described, for example, in International Patent Application WO 95 / 20029 A1.

[0169] Bleach compounds, bleach formulations and bleach activators

[0170] The detergent compositions described herein may optionally contain a bleaching agent or a bleaching composition containing a bleaching agent and one or more bleaching activators. If present, the bleaching agent is typically present in an amount of at least about 1% to about 30% of the detergent composition, more particularly about 5% to about 20%, especially for washing fabrics. If a bleaching activator is contained, its amount is typically present in an amount of about 0.1% to about 60% of the bleaching composition containing the bleaching agent and the bleaching activator, more preferably about 0.5% to about 40%.

[0171] The bleach used herein may be any bleach suitable for cleaning fabrics, cleaning hard surfaces, or other cleaning purposes now known or to be known. These include oxygen bleach as well as other bleaching agents. Perborate bleaching agents, such as sodium perborate (e.g., monohydrate or tetrahydrate), may be used herein.

[0172] Another class of bleaching agents that can be used without restriction includes percarboxylic acid bleaching agents and their salts. Suitable examples of this class of bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, magnesium 4-nonylamino-4-oxoperoxybutyrate, and magnesium disperoxydodecanoate.

[0173] Peroxide bleaching agents can also be used. Suitable peroxide bleaching compounds include sodium carbonate peroxide hydrate and its equivalents, "percarbonate" bleaching agents, sodium pyrophosphate peroxide hydrate, urea peroxide hydrate, and sodium peroxide. Persulfate bleaching agents (e.g., (Commercially manufactured by DuPont).

[0174] Preferred percarbonate bleaching agents comprise dried particles having an average particle size in the range of about 500 to about 1000 micrometers, wherein particles smaller than about 200 micrometers do not exceed about 10% by weight, and particles larger than about 1250 micrometers do not exceed about 10% by weight. Optionally, the percarbonate can be coated with a silicate, borate, or water-soluble surfactant. Percarbonates are available from various suppliers.

[0175] A mixture of bleach can also be used.

[0176] Peroxygen bleaches, perborates, percarbonates and the like are preferably used in combination with bleach activators which result in the in situ generation of a peroxy acid corresponding to the bleach activator in aqueous solution, i.e., during the laundry cycle. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical activators, and mixtures thereof can also be used.

[0177] Preferred amido-derived bleach activators include (6-octanamido- hexanoyl)oxybenzenesulfonate, (6-nonanamido-hexanoyl)oxybenzenesulfonate, (6-decanamido-hexanoyl)oxybenzenesulfonate, and mixtures thereof.

[0178] Another class of bleach activators includes the benzoxazin-type activators disclosed in US 4966723, incorporated herein by reference.

[0179] Very preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecylenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof, optionally adsorbed on a solid support, such as acyl caprolactam, preferably benzoyl caprolactam, adsorbed on sodium perborate.

[0180] Non-oxygen bleaches are also known in the art and can be used herein. One particularly good class of non-oxygen bleaches includes the photosensitized bleaches such as sulfonated zinc and / or aluminum phthalocyanines. If used, the detergent composition will typically contain from about 0.025% to about 1.25% by weight of such bleaches, especially sulfonated zinc phthalocyanine.

[0181] If desired, the bleach compound can be catalyzed by a manganese compound. Such manganese-based catalysts are known in the art and include Mn IV 2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn III 2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)2, Mn IV 4(1,4,7-triazacyclononane)4(ClO4)4, Mn III Mn IV 4(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(ClO4)3, Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6), and mixtures thereof.

[0182] In practical application, without intending to be bound by theory, the compositions and methods of the present application can be adjusted to provide at least about one part per million of active bleach catalyst in the aqueous wash solution, preferably from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm of catalyst material in the wash solution.

[0183] Polymeric soil release agents

[0184] Any polymeric soil release agent known to those skilled in the art can be employed in the detergent compositions and methods of the present application. Polymeric soil release agents are characterized by containing hydrophilic moieties for hydrophilizing the surface of hydrophobic fabrics such as polyester and nylon, and hydrophobic moieties which deposit on the hydrophobic fibers and remain adhered thereto throughout the wash cycle, thereby serving as an anchor for the hydrophilic moieties. This makes stains treated with the soil release agent more readily removable in subsequent cleaning procedures.

[0185] The polymeric soil release agents used herein include, in particular, those soil release agents having (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein said hydrophilic segments do not contain any oxypropylene units unless they are adjacent to the end portions of each end by an ether linkage, or (iii) mixtures of oxyalkylene units containing oxyethylene and from 1 to about 30 oxypropylene units, wherein said mixture contains a sufficient amount of oxyethylene units to impart a sufficient degree of hydrophilicity to the hydrophilic component to enhance the hydrophilic properties of the surface of the common polyester synthetic fiber as measured by the deposition of the soil release agent on the surface of the fiber, said hydrophilic segments preferably contain at least about 25% oxyethylene units and more preferably, especially for those components having from about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobic component also contains oxyethylene terephthalate, the ratio of oxyethylene terephthalate to C3 oxyalkylene terephthalate units is about 2:1 or less, (ii) C4-C6 alkylene or oxyC4-C6 alkylene segments, or mixtures thereof, (iii) poly(vinyl ester) segments, preferably poly(vinyl acetate) having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives or mixtures thereof, wherein the cellulose derivatives are amphoteric, or a combination of (a) and (b) such that they have a sufficient amount of C1-C4 alkyl ether and / or C4 hydroxyalkyl ether units to deposit onto the surface of the common polyester synthetic fiber and retain a sufficient amount of hydroxyl groups, once they are bound to the surface of the common synthetic fiber, to enhance the hydrophilic properties of the surface of the fiber.

[0186] While higher degrees of polymerization can be used, the polyoxyethylene segments of (a)(i) generally have a degree of polymerization of from about 200, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxyC4-C6 alkylene hydrophobic segments include, but are not limited to, end-capped polymeric soil release agents.

[0187] The polymeric soil release agents useful in the present application also include cellulose derivatives such as hydroxy ether cellulose polymers, terephthalic acid monoethylene glycol or terephthalic acid monopropylene glycol block copolymers with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such formulations are commercially available and include hydroxy ether cellulose such as (DOW). The cellulose soil release agents used in the present application also include C1-C4 alkyl and C4 hydroxyalkyl celluloses.

[0188] Soil release agents characterized by poly(vinyl ester) hydrophobic segments include poly(vinyl esters) such as graft copolymers of C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto a polyalkylene oxide backbone such as a poly(ethylene oxide) backbone, see EP 0,219,048, incorporated herein in its entirety. Commercially available soil release agents of this type include Soflame® types, such as Soflame® HP-22 available from BASF. Soflame® HP-22.

[0189] A preferred class of soil release agents is a copolymer having random blocks of monoethylene glycol terephthalate and poly(ethylene oxide) terephthalate. The molecular weight of this polymeric soil release agent is from about 25,000 to about 55,000.

[0190] Another preferred polymeric soil release agent is a polyester with ethylene glycol terephthalate repeat units containing from 10 wt% to 15 wt% ethylene glycol terephthalate units and from 90 wt% to 80 wt% (by weight) poly(ethylene oxide) terephthalate units derived from a poly(ethylene oxide) glycol having an average molecular weight of from 300 to 5,000. Examples of such polymers include commercially available Soflame® 5126 (produced by Dupont) and Soflame® T (produced by ICI).

[0191] Still another preferred polymeric soil release agent is the sulfonated product of an essentially linear ester oligomer containing terephthaloyl and oxyalkyleneoxy repeat units in an oligomeric ester backbone and terminal moieties covalently attached to the backbone. These soil release agents are fully described in US 4,968,451. Other suitable polymeric soil release agents include the terephthalate polyesters of US 4,711,730, the anionically-terminated oligoesters of US 4,721,580 and the block polyester oligomers of US 4,702,857, and the anionic, especially sulfoaroyl-terminated terephthalates of US 4,877,896, all of which patents are incorporated herein in their entirety.

[0192] Another preferred soil release agent is an oligomer having the following repeating units: terephthaloyl units, sulfoisophthaloyl units, oxyethyleneoxy and oxy-1,2- propyleneoxy units. These repeating units make up the backbone of the oligomer and are preferably capped with modified isethionate. A particularly preferred soil release agent of this type contains about one sulfoisophthaloyl unit, five terephthaloyl units, a ratio of about 1.7 to about 1.8 of oxyethyleneoxy and oxy-1,2-propyleneoxy units, and two capping units of sodium 2-(2-hydroxyethoxy)ethane sulfonate. The soil release agent also contains about 0.5 wt% to about 20 wt%, by weight of the oligomer, of a crystallization reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.

[0193] If used, the soil release agent is typically used in amounts of from about 0.01 wt% to about 10.0 wt%, usually from about 0.1 wt% to about 5 wt%, and preferably from about 0.2 wt% to about 3.0 wt%, by weight of the detergent composition of the present application.

[0194] Polymeric dispersing agents

[0195] The polymeric dispersing agent is advantageously used in amounts of from about 0.1 wt% to about 7 wt% in the detergent compositions of the present application, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although other dispersing agents well known in the art can also be used. While not wishing to be bound by theory, it is believed that polymeric dispersing agents enhance the performance of the overall detergent builder, through crystal growth inhibition, particle soil release peptization, and anti-redeposition effects, when used in conjunction with other builders, including low molecular weight polycarboxylates.

[0196] The polymeric polycarboxylate material can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in acid form. Unsaturated monomer acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylene malonic acid. It is suitable for the polymeric polycarboxylate to contain monomeric segments containing non-carboxylic acid groups such as vinyl methyl ether, styrene, ethylene, and the like, provided that these segments do not comprise more than about 40 wt%.

[0197] Particularly suitable polymeric polycarboxylate salts can be prepared from acrylic acid. The acrylic acid based polymers used herein are water soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in acid form is preferably from about 2,000 to about 10,000, more preferably from about 4,000 to about 7,000, and most preferably from about 4,000 to about 5,000. The water soluble salts of these acrylic acid polymers can include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known materials. The use of such polyacrylate salts in detergent compositions is disclosed, for example, in U.S. Patent 3,308,067.

[0198] Acrylic acid / maleic acid based copolymers can also be used as preferred ingredients of the dispersant / anti-redeposition agents. These materials include water soluble salts of acrylic acid and maleic acid copolymers. The average molecular weight of these copolymers in acid form is preferably from about 2,000 to about 100,000, more preferably from about 5,000 to about 75,000, and most preferably from about 7,000 to about 65,000. The ratio of acrylic acid salt segments to maleic acid salt segments in these copolymers is generally from about 30:1 to about 1:1, more preferably from about 10:1 to about 2:1. The water soluble salts of these acrylic acid / maleic acid copolymers can include, for example, alkali metal, ammonium and substituted ammonium salts. Such water soluble acrylic acid / maleic acid copolymers are known materials disclosed in EP 0 193 360 Al which also teaches that such polymers can contain hydroxypropyl acrylate. Other useful dispersants include maleic acid / acrylic acid / vinyl alcohol terpolymers, such as a 45 / 45 / 10 terpolymer of maleic acid / acrylic acid / vinyl alcohol.

[0199] Another polymeric material which can be added is polyethylene glycol (PEG). PEG can exhibit dispersant properties, as well as act as a clay soil removal-anti-redeposition agent. The molecular weight range used for these purposes is generally from about 500 to about 100,000, preferably from about 1,000 to about 50,000, and more preferably from about 1,500 to about 10,000.

[0200] Polyaspartic acid and polyglutamic acid dispersants can also be used, particularly in combination with zeolite builders. The molecular weight (average) of the dispersant, such as polyaspartic acid, is about 10,000.

[0201] Foam inhibitors

[0202] It is especially advantageous to add conventional suds suppressors to the compositions, especially in automatic washing processes. Suitable suds suppressors include, for example, natural or synthetic soaps containing a high proportion of C18-C24fatty acids. Non-surface active types of suds suppressors are, for example, organic polymolecular siloxanes and mixtures thereof with finely divided, optionally silanized, silica, and also paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or distearyl-diphenyl-diamine. Preferably, mixtures of various suds suppressors are used, for example mixtures of silicone, paraffin or wax. Preferably, the suds suppressors, especially those containing silicone and / or paraffin, are loaded onto granules, water-soluble or dispersible carrier materials. Mixtures of paraffin and distearyl-diphenyl-diamine are especially preferred in this case.

[0203] Compounds which reduce or inhibit sudsing can be added to the detergent compositions of the present application. Inhibiting suds is especially important in so-called "high concentration cleaning processes" and in front-loading European-style washing machines.

[0204] Various materials can be used as suds suppressors and are known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One class of suds suppressors of particular interest includes the moncarboxylic fatty acids and their soluble salts. The moncarboxylic fatty acids and their salts useful as suds suppressors generally possess a hydrocarbon chain of from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include the alkali metals such as sodium, potassium, and lithium, as well as ammonium and alkanolammonium salts.

[0205] The detergent compositions of the present application can also contain non-surfactant suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid mono-alcohol esters, fatty alcohols, fatty acid esters of pentaerythritol, and the like. 18 -C 40Ketones (e.g., stearone) and the like. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkyl melamines or di- to tetra-alkyl diamine chlorotriazines formed as the product of cyanuric chloride with 2 to 3 moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, monooctadecyl phosphates such as monooctadecyl phosphoric acid ester, mono- octadecyl di-alkali metal (e.g., sodium, potassium, lithium) phosphate and phosphates. Hydrocarbons such as paraffin and halogenated paraffin can be used in the liquid state. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, have a pour point in the range of about -40°C to about 50°C, and a minimum boiling point of not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point of less than about 100°C. Hydrocarbon foam inhibitors known in the art and include aliphatic, cycloaliphatic, aromatic, and heterocyclic, saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in this foam inhibitor discussion means mixtures of true paraffin and cyclic hydrocarbons.

[0206] Another preferred class of non-surfactant foam inhibitors includes silicone foam inhibitors. Included in this class are the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes with silica gel particles, wherein the polyorganosiloxane is chemisorbed or fused onto the silica gel. Silicone foam inhibitors are known in the art.

[0207] Other silicone foam inhibitors are disclosed in US 3,455,839, which is incorporated herein in its entirety, which relates to a composition and method for defoaming aqueous solutions by the addition of small amounts of polydimethylsiloxane fluid.

[0208] Mixtures of silicones and silylated silica gel are described, for example, in DE-OS 2 124 526, which is incorporated herein in its entirety. Silicone defoamers and foam control agents in granular detergent compositions are disclosed in US 4,652,392, which is incorporated herein in its entirety.

[0209] In preferred silicone foam inhibitors for use in the present application, the solvent of the continuous phase is comprised of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone foam inhibitor is branched / crosslinked, preferably not linear.

[0210] The silicone foam inhibitors of the present application preferably contain polyethylene glycol and polyethylene / polypropylene glycol copolymers, which have an average molecular weight of less than about 1,000, preferably from about 100 to 800. The polyethylene glycol and polyethylene / polypropylene glycol copolymers used in the present application have a solubility in water at room temperature of greater than about 2% by weight, preferably greater than about 5% by weight.

[0211] The preferred solvents used herein are polyethylene glycols having an average molecular weight of less than about 1,000, more preferably from about 100 to about 800, most preferably from about 200 to about 400, and polyethylene glycol / polypropylene glycol copolymers, preferably PPG 200 / PEG 300. The weight ratio of polyethylene glycol to polyethylene glycol / polypropylene glycol copolymer is preferably from about 1:1 to about 1:10, most preferably from about 1:3 to about 1:6.

[0212] The preferred silicone foam inhibitors used herein are free of polypropylene glycol, particularly polypropylene glycol having a molecular weight of 4000. They are also preferably free of block copolymers of ethylene oxide and propylene oxide, such as L101.

[0213] Other foam inhibitors used herein contain secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of these alcohols with silicone oils. Secondary alcohols include C6-C 16 alkyl alcohols having a C1-C 16 chain. The preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark 12. Mixtures of secondary alcohols are available from Enichem under the trademark 123. The mixed foam inhibitors generally contain a mixture of alcohol + silicone in a weight ratio of from 1:5 to 5:1.

[0214] The compositions of the present application generally contain from 0% to about 5% of a foam inhibitor. When used as a foam inhibitor, the monofatty acid and its salts are generally used in amounts up to about 5% by weight of the detergent composition. Preferred are the use of from about 0.5% to about 3% of a monofatty acid foam inhibitor. The silicone foam inhibitors are generally used in amounts up to about 2% by weight of the detergent composition, although greater amounts can be used. The upper limit of the amount used is determined by practical considerations, primarily the desire to minimize cost and the effectiveness of lower amounts in controlling foaming. Preferred are the use of from about 0.01% to about 1% of a silicone foam inhibitor, more preferably from about 0.25% to about 0.5%. As used herein, these weight percent values include any silica used in the polyorganosiloxane mixture, as well as any additives which can be used. The monostearate foam inhibitors are generally used in amounts from about 0.1% to about 2% by weight of the composition. The hydrocarbon foam inhibitors are generally used in amounts from about 0.01% to about 5.0% by weight, although greater amounts can be used. The alcohol foam inhibitors are generally used in amounts from 0.2% to 3% by weight of the finished composition.

[0215] Chelants

[0216] Polyphosphates can be considered to be chelating or stabilizing agents, particularly for peroxide compounds and enzymes which are sensitive to heavy metal ions. For example, 1-hydroxyethane-1,1-diphosphonic acid sodium salt, diethylene triamine penta methylene phosphonic acid sodium salt or ethylene diamine tetra methylene phosphonic acid sodium salt can be used in amounts of from 0.1 to 5% by weight.

[0217] The detergent compositions of the present application can also optionally contain one or more iron and / or manganese chelating agents. These chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures thereof, all as defined herein below. Without intending to be bound by theory, it is believed that the benefit of these materials is due, at least in part, to their exceptional ability to sequester iron and manganese ions by formation of soluble chelates, thus rendering them unavailable to contribute to discoloration or to support microbial growth in the work or wash solutions. Some of the detergent builders described hereinabove can function as chelating agents and, if such builders are present in sufficient quantities, can provide both functions.

[0218] Aminocarboxylates useful as optional chelating agents include ethylenediaminotetracetates, N-hydroxyethylethylenediaminetetracetates, nitrilotriacetates, ethylenediaminotetraproprionates, triethylenetetraminehexacetates, diethylenetriaminepentaacetates and ethanoldiglycines, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof.

[0219] Aminophosphonates are also suitable for use as chelating agents for the compositions of the present application when present at least at low total levels, including ethylenediaminetetrakis (methylenephosphonic acid), DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups of greater than 6 carbons.

[0220] Polyfunctionally-substituted aromatic chelating agents are also suitable for use in the compositions of the present application. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5- disulfobenzene.

[0221] A preferred biodegradable chelant for use in the present application is ethylenediamine disuccinic acid salt ("EDDS"), particularly the [S,S] isomer.

[0222] If used, these chelating agents are generally present in the detergent compositions at levels of from about 0.1% to about 10% by weight. More preferably, if used, such compositions contain from about 0.1% to about 3.0% by weight of chelating agents.

[0223] Clay soil removal agents / anti-redeposition agents

[0224] The detergent compositions of the present application can also optionally contain water-soluble ethoxamined amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds generally contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxamined amine; liquid detergent compositions typically contain from about 0.01% to about 5%.

[0225] The most preferred clay soil removal and anti-redeposition agents are ethoxylated tetraethylene pentamine. Exemplary ethoxylated amines are further described in US 4,597,898. Another preferred class of clay soil removal-anti-redeposition agents are the cationic compounds disclosed in EP 111,965, the ethoxylated amine polymers disclosed in EP 111,984 Al, the zwitterionic polymers disclosed in EP 112,592 Al, and the amine oxides disclosed in US 4,548,744. Another preferred class of anti-redeposition agents includes the carboxymethylcellulose (CMC) materials. These materials are well known in the art.

[0226] Tannish inhibitors

[0227] The task of the brown stain inhibitors is to keep the soil which has been detached from the fibers in suspension in the cleaning liquid and thus to avoid re-adsorption of the soil. For this purpose most organic natural water-soluble sols, such as (co)poly carboxylic acids, gums, salts of gelatin, ether carboxylic or ether sulfonic acid salts of starch or cellulose, or acid sulfate ester salts of cellulose or starch, are suitable. Also suitable for this purpose are water-soluble polyamides which contain acid groups. In addition, soluble starch preparations, such as hydrolyzed starch, aldehyde starch, etc., can be used as the above-mentioned starch products. Also polyvinylpyrrolidone can be used. However, preferred are cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, as well as polyvinylpyrrolidone, in amounts of 0.1 to 5% by weight, based on the composition.

[0228] Optical brighteners and UV-absorbers

[0229] Any fluorescent whitening agent or other brightening or whitening agent known in the art can generally be incorporated into the detergent compositions of the present application in amounts of from about 0.05 wt % to about 1.2 wt %. Commercially available fluorescent whitening agents which can be used in the present application can be divided into subgroups including, but not limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methane blue, diphenylthiophene-5,5-dioxide, azole, 5- and 6-membered heterocyclic derivatives, and other miscellaneous agents.

[0230] Preferred brighteners include the Unipointm series of brighteners from UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic CC and Artic White CWD, available from Hilton-Davis; 2-(4-styryl-phenyl)-2H- naphthol[l,2-d]triazoles; 4,4'-bis-(l,2,3-triazol-2-yl)-stilbenes; 4,4' bis(styryl)diphenyls; and aminocoumarins. Specific examples of these whitening agents include 4-methyl-7-diethyl-amino coumarin, 1,2-di(benzimidazol-2-yl)ethene, 1,3-diphenyl-pyrazolines, 2,5-di(benzoxazol-2-yl)thiophene, 2-styryl-naphtho[l,2-d]oxazole, and 2-(diphenylstilbene-4-yl)-2H-naphtho[l,2-d]triazole. Anionic whitening agents can be preferred for use in the compositions of the present application.

[0231] The compositions can contain, for example, a diaminostilbene disulfonic acid derivative and alkali metal salts thereof as fluorescent whitening agents. Suitable fluorescent whitening agents are, for example, 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6- amino)stilbene-2,2'-disulfonic acid or compounds of analogous structure which carry a diethanolamino, methylamino, phenylamino or 2-methoxyethylamino group instead of the morpholino group. In addition substituted diphenylstyryl whitening agents such as alkali metal salts of 4,4'-bis(2-sulfo-styryl)diphenyl, 4,4'-bis(4-chloro-3-sulfo-styryl)diphenyl or 4-(4-chlorostyryl)-4'-(2-sulfo-styryl)diphenyl can be present. Mixtures of the above-mentioned fluorescent whitening agents can also be used.

[0232] In addition, UV absorbers can be added. UV absorbers are compounds which have excellent adsorbing properties for UV radiation and which, as UV stabilizers, can also improve the light stability of pigments and dyes used in textile fibers and protect the skin of the wearer of the fiber product from penetration of UV radiation by wave protection. Generally highly effective radiation-inert compounds are derivatives of benzophenone substituted by hydroxy and / or alkoxy, in particular in the 2 and / or 4 position. Also suitable are substituted benzotriazoles, acrylates (cinnamic acid derivatives) which are phenyl-substituted in the 3 position and optionally cyano-substituted in the 2 position, salicylates, organic Ni complexes, and natural substances such as umbelliferone and also bulk urocanic acid. In a preferred embodiment the UV absorbers absorb UV-A and UV-B radiation and possibly UV-C radiation and radiate light of blue wavelength again, so that they additionally have an optical brightening effect. Preferred UV absorbers contain triazine derivatives, such as hydroxyaryl-1,3,5-triazines, sulfonated 1,3,5-triazines, o-hydroxyphenylbenzotriazoles and 2-aryl-2H-benzotriazoles and also bis(anilinotriazinyl-amino)stilbene disulfonic acid and derivatives thereof. As UV absorbers it is also possible to use ultraviolet-absorbing dyes such as titanium dioxide.

[0233] Dye transfer inhibitors

[0234] The detergent compositions of the present application can also contain one or more materials effective for preventing the transfer of dyes from one fabric to another during the cleaning process. Typically, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2% by weight of the composition.

[0235] More specifically, the polyamine N-oxide polymers preferred for use in the present application are described in US 6,491,728, incorporated herein in its entirety.

[0236] Any polymeric backbone can be used so long as the resulting amine oxide polymer is water soluble and has dye transfer inhibition properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. These polymers include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of from 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by the appropriate degree of N-oxidation. The polyamine oxide can be obtained in almost any degree of polymerization. The average molecular weight is typically from 500 to 1,000,000; more preferably from 1,000 to 500,000; and most preferably from 5,000 to 100,000. The preferred class of materials can be referred to as "PVNO".

[0237] The most preferred polyamine N-oxide for use in the detergent compositions of the present application is poly(4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.

[0238] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPVI") are also preferred for use in the present application. The average molecular weight of the PVPVI is preferably from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, and most preferably from 0.6:1 to 0.4:1. These copolymers can be linear or branched.

[0239] The compositions of the present application can also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, PVP being known to those skilled in the detergent art. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. The ratio of PEG to PVP provided in the wash solution is from about 2:1 to about 50:1, more preferably from about 3:1 to about 10:1.

[0240] The detergent compositions of the present application can also optionally contain from about 0.005% to about 5% by weight of certain hydrophilic optical brighteners which can provide dye transfer inhibition. If used, the compositions of the present application preferably contain from about 0.01% to about 1% by weight of such fluorescent brighteners.

[0241] A preferred brightener is 4,4'-bis[(4-anilino-6-(N-2-di-hydroxyethyl)-s-triazine-2- yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is available from Ciba-Geigy Corporation under the tradename Tinopal UNPA-GX is the preferred hydrophilic fluorescent brightener for use in the detergent compositions of the present application.

[0242] Another preferred brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)- s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is available from Ciba-Geigy Corporation under the tradename Tinopal UNPA-GX is the preferred hydrophilic fluorescent brightener for use in the detergent compositions of the present application.

[0243] Another preferred brightener is 4,4'-bis[(4-anilino-6-morpholino-s-triazine-2-yl)amino]- 2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is available from Ciba-Geigy Corporation under the tradename Tinopal UNPA-GX is the preferred hydrophilic fluorescent brightener for use in the detergent compositions of the present application.

[0244] The particular optical brighteners selected for use in the present application provide especially effective dye transfer inhibition performance when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of such selected polymeric materials (e.g., PVNO and / or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better inhibition of dye transfer in an aqueous wash solution than either of these two detergent composition components used alone. Without intending to be bound by theory, it is believed that the mode of action of such brighteners is that they deposit relatively rapidly onto fabrics in the wash solution due to their high affinity for such substrates. The extent to which a brightener deposits onto fabrics in a wash solution is defined by a parameter known as the "exhaustion coefficient". This exhaustion coefficient refers generally to the ratio of a) the amount of brightener material which deposits onto fabrics to b) the initial brightener concentration in the aqueous wash solution. Brighteners having relatively high exhaustion coefficients are most suitable for use in the dye transfer inhibition aspect of the technology of the present application.

[0245] It will of course also be appreciated that other types of conventional optical brighteners can optionally be used in the compositions of the present application to provide the conventional fabric "whitening" benefit, but which do not in fact have any effect on inhibiting dye transfer. Such use is conventional and well known in detergent formulation.

[0246] Thickeners

[0247] The compositions can also contain conventional thickeners and anti-settling compositions as well as viscosity modifiers such as polyacrylates, polycarboxylic acids, polysaccharides and derivatives thereof, polyurethanes, polyvinylpyrrolidone, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamine and mixtures thereof. Preferred compositions have a viscosity of less than 10,000 mPa*s, measured at a temperature of 20°C and a shear rate of 50 min -1 measured at a temperature of 20°C and a shear rate of 50 min

[0248] Inorganic salts

[0249] Further suitable ingredients of the composition are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; in particular alkali metal carbonates and amorphous silicates, mainly sodium silicates with a molar ratio Na2O:SiO2 of from 1 :1 to 1 :4.5, preferably from 1 :2 to 1 :3.5. Preferred compositions contain alkali metal salts, builders and / or co-builders, preferably sodium carbonate, zeolite, crystalline layered sodium silicates and / or trisodium citrate, in an amount of from 0.5 to 70 wt.%, preferably from 0.5 to 50 wt.%, in particular from 0.5 to 30 wt.% of anhydrous material.

[0250] Perfumes and colorants

[0251] The composition can comprise other typical detergent and cleaning composition ingredients, such as perfume and / or colorant, wherein preferably such colorants leave no or negligible color on the fabrics being laundered. Preferred amounts of total colorant added are below 1 wt.%, preferably below 0.1 wt.%, based on the composition. The composition can also comprise a white pigment, such as Ti02.

[0252] Industrial applications

[0253] Another object of the present application relates to a process for manufacturing a liquid detergent composition, comprising the steps of:

[0254] (i) providing the components for manufacturing the composition, optionally in aqueous solution;

[0255] (ii) providing a microcapsule dispersion according to the present application or obtained according to the process of the present application;

[0256] (iii) mixing the components and the dispersion to obtain the final composition.

[0257] Finally, the present application also encompasses the use of the microcapsules for manufacturing a liquid detergent composition. Examples

[0258] Example 1

[0259] Using guanidine carbonate as a multifunctional nucleophile and Capsul TM Starch as a capsule-forming aid to prepare the microcapsules of the present application.

[0260] More specifically, 196 g of perfume W-Cap (Symrise, Teterboro, NJ) was weighed out in a 250 ml beaker and mixed with 10.4 g of hexamethylene diisocyanate (Desmodur N-3400, Covestro Corporation) to form the oil phase. In a separate 800 ml beaker, an aqueous solution (375 g) containing 2% Capsul starch (commercially available from Ingredion Inc.) formed the water phase. The oil phase was then emulsified into the water phase to form a perfume emulsion under shear (Ultra Turrax, T-50, commercially available from IKA Werke) at 3500 rpm for between 20 and 60 seconds.

[0261] The perfume emulsion was placed in an overhead mixer and stirred at 600 rpm while 25 g of a 15% guanidine carbonate solution was gradually added. The capsule slurry was heated to cure for at least 3 hours at 70 °C.

[0262] The capsule slurry of this embodiment was dispensed at a dosage of 0.3% w / w into a commercially available fragrance-free liquid laundry detergent until homogeneous. The liquid laundry detergent does not contain any structure-forming agents. The sample was aged in an oven at 40°C for 7 days to simulate long-term stability. Figure 2 As shown.

[0263] Example 2

[0264] Using guanidine carbonate as a multifunctional nucleophile and Capsul TM Starch was used as an encapsulation aid to prepare the microcapsules of this invention.

[0265] More specifically, 98g of flavoring Tomcap (Symrise, Teterboro, NJ) was weighed into a 250ml beaker and mixed with a mixture of 98g of vegetable oil triglycerides and 10.4g of hexamethylene diisocyanate and diphenylmethane diisocyanate (Desmodur N-3400 and Mondur M, both purchased from Covestro Corporation) to form the oil phase. In a separate 800ml beaker, 2% Capsul TM An aqueous solution (375 g) of starch (available from Ingredion Inc.) was used to form the aqueous phase. The oil phase was then emulsified into the aqueous phase under shear at 3500 rpm (Ultra Turrax, T-50, commercially available from IKA Werke) for 30 to 60 seconds to form a fragrance emulsion. Particle size was measured on a 3000 (Malvern Instruments | 117 Flanders Road, Westborough, MA) particle size analyzer to produce the desired median particle size of 5 to 50 micrometers.

[0266] The fragrance emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 25 g of a 15% guanidine carbonate solution. The capsule slurry was then heated and cured at 70°C for at least 3 hours.

[0267] The capsule slurry of this embodiment was dispensed at a dosage of 0.3% w / w into a commercially available unscented liquid laundry detergent until homogeneous. The liquid laundry detergent does not contain any structure-forming agents. The sample was aged in an oven at 40°C for 7 days to simulate long-term stability. Figure 3 As shown.

[0268] Example 3

[0269] Using guanidine carbonate as a multifunctional nucleophile and Hi-Cap TM Starch was used as an encapsulation aid to prepare the microcapsules of this invention.

[0270] More specifically, 98g of flavoring Red Berry (Symrise, Teterboro, NJ) was weighed into a 250ml beaker and mixed with 98g of vegetable oil triglycerides and a mixture of 10.4g of hexamethylene diisocyanate and diphenylmethane diisocyanate (Desmodur N-3400 and Mondur M, both purchased from Covestro Corporation) to form the oil phase. In a separate 800ml beaker, 2% HI-Cap was added. TM A 375g aqueous solution of 100g starch (available from Ingredion Inc.) was used to form the aqueous phase. The oil phase was then emulsified into the aqueous phase under shear at 3500rpm (Ultra Turrax, T-50, commercially available from IKA Werke) for 30 to 60 seconds to form a fragrance emulsion. Particle size was measured on a 3000 (Malvern Instruments | 117 Flanders Road, Westborough, MA) particle size analyzer to produce the desired median particle size of 5 to 50 micrometers.

[0271] The fragrance emulsion was placed in a top-mounted mixer and stirred at 600 rpm while gradually adding 25 g of a 15% guanidine carbonate solution. The capsule slurry was then heated and cured at 70°C for 3 hours.

[0272] The capsule slurry of this embodiment was dispensed at a dosage of 0.3% w / w into a commercially available unscented liquid laundry detergent until homogeneous. The liquid laundry detergent does not contain any structure-forming agents. The sample was aged in an oven at 40°C for 7 days to simulate long-term stability. Figure 4 As shown.

[0273] Example 4

[0274] Using guanidine carbonate as a multifunctional nucleophile and Capsul TM Starch was used as an encapsulation aid in the preparation of the microcapsules of this invention. A cationic quaternary ammonium salt was added in the final processing step.

[0275] More specifically, 98g of flavoring Red Berry (Symrise, Teterboro, NJ) was weighed into a 250ml beaker and mixed with 98g of vegetable oil triglycerides and a mixture of 10.4g of hexamethylene diisocyanate and diphenylmethane diisocyanate (Desmodur N-3400 and Mondur M, both purchased from Covestro Corporation) to form the oil phase. In a separate 800ml beaker, 2% HI-Cap was added. TM100 Aqueous solution (375 g) of starch (available from Ingredion Inc.) forms the water phase. The oil phase is then emulsified into the water phase under shear (Ultra Turrax, T-50, available from IKA Werke) at 3500 rpm for between 30 and 60 seconds to form a perfume emulsion. In 3000 (Malvern Instruments | 117 Flanders Road, Westborough, MA) particle size analyser to produce the required median particle size of 5 to 50 microns.

[0276] The perfume emulsion is placed in an overhead mixer and stirred at 600 rpm while 25 g of 15% guanidine carbonate solution is added gradually. The capsule slurry is heated to solidify for at least 1 hour at 70°C. Cationic polymer (Salcare SC-60, BASF) is added as a solid powder or as an aqueous solution during the final solidification period. BRIEF DESCRIPTION OF DRAWINGS

[0277] Figure 1

[0278] Symcap G type (polyurea) microcapsules show agglomeration in unstructured liquid laundry base.

[0279] Figure 2

[0280] Example 1 (right) Capsules prepared, dispersed in unstructured laundry liquid after 1 week at 40°C Figure 3

[0281] Example 2 (right) Capsules prepared, dispersed in unstructured laundry liquid after 1 week at 40°C Figure 4

[0282] Example 3 (right) Capsules prepared, dispersed in unstructured laundry liquid after 1 week at 40°C Consumer product formulations

[0283] Table 1 Cleaning agent. APC liquid. Alkaline pH 8-10 (amount in wt%)

[0284]

[0285] Table 2 Fabric softener (amount in wt%)

[0286]

[0287] Table 3 Liquid detergent (amount in wt%)

[0288]

[0289] Table 4 Liquid detergent concentrate (amounts in wt%)

[0290]

[0291] Table 5 Toilet bowl cleaner (amounts in wt%)

[0292]

[0293] Table 6 Dishwashing concentrate (amounts in wt%)

[0294]

[0295] Table 7 Dishwashing concentrate (amounts in wt%)

[0296]

[0297] Table 8 Solution for wet wipes (amounts in wt%)

[0298]

Claims

1. Polyurea microcapsules obtained according to the following steps: (a) providing an oil phase comprising at least one aliphatic and / or aromatic di- and / or polyisocyanate, and optionally one or more actives for encapsulation and / or at least one oil component; (b) providing a first water phase comprising at least one modified biopolymer colloid protector and optionally at least one non-interfering emulsifier; (c) providing a second water phase comprising guanidinium carbonate and optionally at least one cationic surfactant; (d) mixing the oil phase and the first water phase to form an emulsion; (e) adding the second water phase to the emulsion formed in step (d) to form a dispersion of crude microcapsules (d); (f) curing the dispersion, and optionally (g) removing the solvent to obtain the microcapsules, wherein the colloid protector is an octenyl succinic anhydride (OSA) chemically modified starch.

2. A process for the preparation of polyurea microcapsules comprising or consisting of the following steps: (a) providing an oil phase comprising at least one aliphatic and / or aromatic di- and / or polyisocyanate, and optionally at least one oil component; (b) providing a first water phase comprising at least one modified biopolymer colloid protector; (c) providing a second water phase comprising guanidinium carbonate; (d) mixing the oil phase and the first water phase to form an emulsion; (e) adding the second water phase to the emulsion formed in step (d) to form a dispersion of crude microcapsules (d); (f) curing the dispersion, and optionally (g) removing the solvent to obtain the microcapsules, wherein the colloid protector is an octenyl succinic anhydride (OSA) chemically modified starch.

3. The process according to claim 2, wherein the di- and / or polyisocyanate is selected from the group consisting of • diphenylmethane diisocyanate (MDI); • toluene diisocyanate (TDI); • hexamethylene diisocyanate (HDI); • isophorone diisocyanate (IPDI); • 4,4-dicyclohexylmethane diisocyanate (H12MDI) and mixtures thereof.

4. The process according to claim 2, wherein the oil phase further contains one or more actives for encapsulation.

5. The process according to claim 4, wherein the active is a perfume or fragrance oil.

6. The method of claim 2, wherein the chemically modified starch is CAPSUL TM starch or HI-CAP TM 100.

7. The process according to claim 2, wherein the first water phase further contains at least one non-interfering emulsifier.

8. The process according to claim 7, wherein the emulsifier is selected from the group consisting of non-ionic, anionic, amphoteric and cationic surfactants and mixtures thereof.

9. The process according to claim 2, wherein the emulsion is formed by subjecting a mixture consisting of the oil phase and the first water phase to high shear.

10. The process according to claim 2, wherein the emulsion is mixed with the second water phase and the mixture thus obtained is subjected to high shear.

11. The process according to claim 2, wherein the second water phase further contains at least one surfactant.

12. The process according to claim 2, wherein the curing is carried out at an elevated temperature of 50 to 90 °C for 1 to 12 hours.

13. A liquid surfactant system comprising the microcapsules according to claim 1 or the microcapsules obtained according to the method of any one of claims 2 to 12.

14. The liquid surfactant system according to claim 13 which is a liquid detergent composition.

15. A method for manufacturing a liquid surfactant system comprising the steps of: (i) providing components for manufacturing a composition, optionally in an aqueous solution; (ii) providing a dispersion of microcapsules according to claim 1 or obtained according to the method of any one of claims 2 to 12; (iii) mixing the components and the dispersion to obtain a final composition.

16. The method according to claim 15 wherein the liquid surfactant system is a liquid detergent composition.

17. Use of the microcapsules according to claim 1 or the microcapsules obtained according to the method of any one of claims 2 to 12 for manufacturing a liquid surfactant system.

18. The use according to claim 17 wherein the liquid surfactant system is a liquid detergent composition.

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