WO2007079849A1

WO2007079849A1 - Multiphase washing, rinsing or cleaning composition with vertical phase boundary

Info

Publication number: WO2007079849A1
Application number: PCT/EP2006/011755
Authority: WO
Inventors: Georg Meine; Hermann Jonke; Thomas FELDBRÜGGE; Piotr Malecki
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-12-21
Filing date: 2006-12-07
Publication date: 2007-07-19
Also published as: DE102005061726A1

Abstract

The application discloses a washing, rinsing or cleaning composition with at least two phases, where the composition, in the storage state of the phases, has at least one essentially vertical phase boundary. The application also describes a dispensing container comprising a multiphase washing, rinsing or cleaning composition with at least one essentially vertical phase boundary, where the dispensing container is designed so that, upon dispensing the washing, rinsing or cleaning composition, dispensing takes place along the phase boundary.

Description

"Multi-phase washing, rinsing or cleaning agent with vertical phase boundary"

The invention relates to a washing, rinsing or cleaning agent containing Tensιd (e) and other conventional ingredients of detergents, wiping or cleaning agents, wherein the agent has at least two phases, and the use of the washing, rinsing or cleaning agent The The invention also relates to a dispensing container comprising a washing, rinsing or cleaning agent which contains surfactants (e) and other customary ingredients of washing, rinsing or cleaning agents, wherein the composition has at least two phases

The incorporation of certain active ingredients (eg bleaches, enzymes, perfumes, dyes, etc.) into liquid washing, rinsing or cleaning agents can lead to problems. For example, incompatibilities between the individual active ingredient components of the liquid washing, rinsing or cleaning agents may occur undesirable discolorations, agglomerations, odor problems and destruction of detergent-active substances

The consumer, however, requires liquid washing, rinsing or cleaning agent), which develop their effect optimally even after storage and transport at the time of use. This requires that the contents of the liquid washing, rinsing or cleaning agent not previously deposited and / or have decomposed

Chemically incompatible components may be stored separately from the remaining components of the liquid washing, rinsing or cleaning agent and then dosed for use or the agent consists of two or more phases, which are stored in the dispensing container in different chambers and only in the dosage in contact come

Another approach is, for example, in immiscible components (= physically incompatible) then to provide a multi-phase detergent, wiping or cleaning agent, which is temporarily converted by the user by rubbing into an emulsion before application by the user in such agents may cause the problem that The user may not sufficiently mix the agent before turning away, and the phases may not be evenly dosed. This can lead to user frustration. Furthermore, the segregation of the two phases can take a long time (up to hours) to produce chemically incompatible ingredients from the different phases are in contact for a long time and interact undesirably Multiphase washing, rinsing or cleaning agents with horizontal phase boundary are well known in the art and are described for example in WO 99/47635 A2.

It is an object of the invention to provide a washing, rinsing or cleaning agent with incompatible ingredients, which is simple and inexpensive to manufacture and can be easily and evenly dosed.

This object is achieved by a washing, rinsing or cleaning agent containing surfactant (s) and other conventional ingredients of washing, rinsing or cleaning agents, wherein the agent has at least two phases, and wherein the agent in the storage state of the phases at least one having substantially vertical phase boundary.

Such a washing, rinsing or cleaning agent has the advantage that incompatible ingredients can be integrated into a washing, rinsing or cleaning agent by incorporation into different phases without expensive packaging technology. The incompatible ingredients of the individual phases can come into contact only in the limited area of the phase boundary and interact undesirably. Thus, only a small portion of the incompatible ingredients are optionally destroyed or deactivated during storage. Furthermore, for the purpose of metering the washing, rinsing or cleaning agent, it is not always necessary first of all to achieve thorough mixing of the phases in which the chemically incompatible ingredients are in contact over a relatively long period of time, but the contact of incompatible ingredients is restricted to the area of the phase boundary ,

It is advantageous that the phase boundary is visible.

By visualizing the phase boundary, the consumer can also visually be made clear that the different phases have different properties.

It is preferred that the density of the at least two phases is substantially equal.

By a substantially same density of the individual phase mixing of the phases with time (storage) is prevented.

Furthermore, it is preferred that the yield point of the at least two phases is substantially equal. The yield point is the force that has to be expended to make a material flow. A substantially equal yield point of the individual phases ensures that the phases start to flow when the same force is applied and thus the dosage of the washing, winding It can also be advantageous if the yield point of the individual phases is high and the phases start to flow only with targeted application of force. High flow limits of the individual phase can compensate for greater differences in the densities of the individual phases and prevent mixing

It is also preferred that the viscosity of the at least two phases is substantially equal

It is particularly preferred that the at least two phases each have a viscosity in the range of 15,000 mPas to 50,000 mPas (Brookfield Viscometer LVT-II at 20 U / min and 20 ° C, spindle 5)

The viscosity characterizes the flow behavior of a liquid An equal and preferably high viscosity (from 15,000 mPas to 50,000 mPas) of the individual phases prevents mixing of the phases with time (storage). An equal and preferably high viscosity also prevents the occurrence of strong currents the phase boundary on delivery of the washing, rinsing or cleaning agent (dosage), which lead to a mixing of the phases

In a particularly advantageous embodiment, the washing, rinsing or cleaning agent has two phases

A biphasic washing, rinsing or cleaning agent is easier to manufacture and handle compared to multiphase detergents, wipers or cleaners

It may be particularly preferred that one phase contains one or more ingredients that are incompatible with at least one ingredient of the other phase

The invention further relates to a dispenser, comprising a washing, rinsing or cleaning agent containing Tensιd (e) and other conventional ingredients of detergents, wipes or cleaning agents, wherein the agent has at least two phases, the agent in the storage state of the phases has at least one substantially vertically extending phase boundary and the dispensing container is designed so that upon delivery of the washing, rinsing or cleaning agent, the delivery takes place along the phase boundary.

Such a dispensing container has the advantage that for the dosage of the washing, rinsing or cleaning agent not always complete and above all homogeneous mixing of the phases must be achieved in order to ensure a uniform dosage of at least two phases.

In a preferred embodiment, the dispensing container is transparent or translucent. As a result, the consumer can see the different phases and, above all, can follow that a uniform dosage of the different phases takes place.

It is advantageous that the phase boundary is visible, sp so that the consumer can also optically track that there is a uniform metering of the various phases.

Furthermore, it is preferred that the container is deformable. By using a deformable dispensing container, the consumer can also easily dispense or dispense highly viscous multiphase detergents, dishwashing or cleaning agents for use in the dispensing container.

It is particularly preferred that it be dispensers of polyethylene terephthalate (PET), since PET can be made into deformable and / or transparent dispensing containers.

In the storage state of the phases, the multiphase washing, rinsing or cleaning agent according to the invention has at least one essentially vertically extending phase boundary.

The expression "state of storage of the phases" in this context means the usual storage or presentation of the washing, rinsing or cleaning agent, preferably in a dispensing container, wherein it is preferred that the dispensing container has an area that is particularly preferably used as a base ,

As used herein, the term "substantially vertical" means that the phase boundary is substantially vertical in relation to the footprint of a dispensing container containing the detergent, rinse or cleaning agent. limit in relation to the floor space of a containing the detergent, dishwashing or cleaning agent dispenser for the most part at an angle greater than 45 ° and less than 135 °

The term "phase boundary" in this case describes the abrupt change in the properties of two adjoining phases of the washing, rinsing or cleaning agent. The phase boundary is not hard but has mixing conditions over a range. It is preferred that the range of mixing states as small as possible

The washing, rinsing or cleaning agent has at least two different phases, wherein the phases differ in their composition by at least one ingredient. The two or more different phases of a washing, rinsing or cleaning agent have a substantially equal density, one in the Essentially equal means that the three properties mentioned (density, yield point or viscosity) of the individual phases can vary within a certain range, but the variation does not lead to spontaneous mixing preferably that values for one of the mentioned properties of two adjacent phases do not vary more than 30%, preferably not more than 20 and particularly preferably not more than 10%

The viscosity of the individual phases of the washing, rinsing or cleaning agent can be measured by conventional standard methods (in this case Brookfield® / Iskosimeter LVT-II at 20 U / min and 2O ⁰ C, spindle 5) and is for the washing, rinsing or Cleaning agent in each case preferably in the range from 15,000 to 50,000 mPas Preferred washing, rinsing or cleaning agents preferably have viscosities of from 25,000 to 40,000 mPas in the respective phases, with values around 35,000 mPas being particularly preferred

The yield point of the individual phases of the washing, rinsing or cleaning agent is preferably 0.8 Pa (determined on an AR 1000-N rheometer from Texas Instruments at a temperature of 25 ° C.).

The density of the individual phases of the washing, rinsing or cleaning agent is preferably between 0.8 g / cm ³ and 1.6 g / cm ³

The individual phases of the washing, rinsing or cleaning agent contain surfactants (e), it being possible to use anionic, nonionic, zwitterionic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of a phase of the liquid washing, rinsing or cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, based on the total phase.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, Taigfett- or Oleylalkohol.i and an average of 2 to 8 EO per mole

Alcohol preferred. Among the preferred alcohols ethoxylierteπ for example, C _12-14 -Al- alcohols containing 3 EO, 7 EO or 4 EO, C _9-11 -alcohol with 7 EO, C _{_13-15} alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _12-1S- AKOCHOIe with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ - ^ - AIkOhOl with 3 EO and C ₁₂ . _18- alcohol with 7 EO. The stated degrees of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated niotic side can be used in which EO and PO units are not distributed blockwise, but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4. Alkyl glycosides are known, mild surfactants and are therefore preferably used in the surfactant mixture.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Also nonionic surfactants of the amine oxide type, for example N-Kokosalky] -N, N-dimethyl amine oxide and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (VII)

R ¹

I R-CO-N- [Z] (VII) in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms, R1 for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (VIII)

R ¹ OR ²

I R-CO-N- [Z] (VIII) in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, where d. ₄ alkyl or phenyl radicals preferred are and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical

[Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be prepared by reaction with fatty acid methyl esters in the presence of an alkoxide be converted as a catalyst into the desired polyhydroxy fatty acid amides

The content of nonionic surfactants in one phase of the washing, rinsing or cleaning agent is preferably 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, in each case based on the particular phase of the washing , Wiping or cleaning agent

In addition to the nonionic surfactants, a phase of the washing, rinsing or cleaning agent may also contain anionic surfactants. Examples of anionic surfactants are those of the sulfonate and sulfates type. The surfactants of the sulfonate type are preferably C ₁₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example ₁₂ -i ₈ monoolefins with a terminal or C obtained from innenstandi- ger double bond by sulfonation with gaseous Jschwefeltπoxid and subsequent alkaline or acidic hydrolysis of the sulfonation products are also suitable Al i kannsulfonate, which are obtained from Ci _Σ -is-alkanes, for example by Sulfochloπerung or sulfoxidation and subsequent hydrolysis or neutralization Likewise, the esters of α-Sulfofettsauren (ester sulfonates), for example the .alpha.-sulfonated Methylester of hydrogenated coconut, palm kernel, or tallow fatty acids ignet ι

Further suitable anionic surfactants are sulfonated fatty acid glycyl esters. Fatty acid glyceryl esters are the mono-, di- and tri-esters and mixtures thereof, as in the preparation by esterification of a monoglycerine with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycene are obtained. Preferred sulfated fatty acid esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caprylic caprylic acid, capric acid, myrotic acid, lauric acid, p-mitic acid, stearic acid or behenic acid Suitable alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid monoesters of C ₁₂ -C ₁₈ -FeUaIkOhOIe, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, Myπ styl, cetyl or stearyl alcohol or the C ₁₀ - C ₂ o-Oxoalcohols and those half-esters of secondary alcohols of these chain lengths are also preferred. Alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous decomposition behavior to those of the adequate compounds based on For the purposes of washing technology, the C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and also C ₁₄ -C ₁₅ -alkyl sulfates are also preferred. 2,3-Alkyl sulfates, which are marketed as commercial products of the Shell Oil Company under the name DAN ^® can be obtained, are suitable anionic surfactants

Also, the sulfuric acid monoesters of the straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂₁ -alcohols, such as 2-methyl-branched C _9-11 -AIkOhOIe with an average of 3.5 moles of ethylene oxide (EO) or C _{12 18} -fatty alcohols with 1 to 4 EO, are suitable They are in detergents due to their high foaming behavior only used in relatively small amounts, for example in amounts of 1 to 5% by weight

Other suitable anionic surfactants are the salts of the Alkylsulfobernsteinsaure, which also sulfosuccinates as sulfonic or be referred to as Sulfobernsteinsaureester and Monoester and / or di- esters of Sulfobemsteinsaure with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent Preferred sulfosuccinates contain C _{8 18} fatty alcohol or mixtures of these particularly preferred sulfosuccinates contain a fatty alcohol radical derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). In turn, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrow homolog distribution are particularly preferred Likewise, it is also possible to use alk (en) ylbernic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof

Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myripic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and in particular derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids soap mixtures The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of a phase of a washing, rinsing or cleaning agent to anionic surfactants is 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the single phase of the wash , Rinsing or cleaning agent.

Furthermore, the phases of the washing, rinsing or cleaning agent may contain softening compounds. The softening compounds include, for example, quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.

Suitable examples of quaternary ammonium compounds are shown, for example, in the formulas (I) and (II):

₍ ||)

wherein in (I) R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{1 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ² and R ^{3 are} either R or R ¹ or are an aromatic radical , X ^" is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof Examples of cationic compounds of the formula (I) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (II), (III) and (IV) are so-called ester quats. Esterquats are characterized by excellent biodegradability. In formula (II) R ^{4 is} an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents; R ⁵ is H, OH or O (CO) R ⁷ , R ⁶ is, independently of R ^5, H, OH or O (CO) R ⁸ , where R ⁷ and R ⁸ are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with O, 1, 2 or 3 double bonds, m, n and p may each independently have the value 1, 2 or 3 have. X ^" can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these be an ion. Preference is given to compounds in which R ^{5 represents} the group 0 (CO) R ⁷ . Particular preference is given to compounds in which R ^{5 is} the group O (CO) R ⁷ and R ⁴ and R ^{7 are} alk (en) yl radicals having 16 to 18 carbon atoms. Particularly preferred are compounds in which R ^{6 is} also OH. Examples of compounds of the formula (I) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulphate, bis (palmitoyloxyethyl) -hydroxyethylmethylammonium methosulphate, I Bis-tallowacyloxyl-S-trimethylammonium propane chloride or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.

If quaternized compounds of the formula (II) are used which have unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine number between 1 and 100, preferably between 5 and 80, more preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular equal to or greater than 60:40. Commercial examples are sold by Stepan under the tradename Stepantex ^® Methyihydroxyalkyldialkoyloxyalkylammoniummethosulfate or those known under Dehyquart ^® products from Cognis or under the known Rewoquat® products from Degussa or those known under Tetranyl® products of Kao. Further preferred compounds are the diester quats of the formula (III) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.

R ²¹ and R ²² are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

Instead of the ester group 0 (CO) R, where R is a long-chain alk (en) yl radical, it is possible to use softening compounds which have the following groups: RO (CO), N (CO) R or RN (CO), where of these groups, N (CO) R groups are preferred.

In addition to the quaternary compounds described above, it is also possible to use other compounds as the softening compound, for example quaternary imidazolinium compounds of the formula (IV),

where R ^{9 is} H or a saturated alkyl radical having 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ independently of one another may each be an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ^{10 may} alternatively also be 0 (CO) R ²⁰ where R ^{20 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^"is an anion, q can have integer values between 1 and 4.

Further particularly preferred plasticizing compounds are described by formula (V),

R13 H

R12 N- (CH ₂₎ r CO (CO) R15 X ^'(V);

R ^{14 is} CH ₂ -O (CO) R ¹⁶ where R ¹² , R ¹³ and R ¹⁴ independently of one another are a C _1-4 -alkyl, alkenyl or hydroxyalkyl group, R ¹⁵ and R ^{16 are} each independently selected C ₈ - ₂₈ -alkyl, X ^"is an anion and r is a number between 0 and 5. A preferred example of a cationic Abscheidungshilfe according to formula (V) is 2,3-bis [tallowacyloxy] -3-trimethylammoniumpropanchlorid.

Further plasticizing compounds which can be used according to the invention are quaternized protein hydrolyzates or protonated amines.

Furthermore, cationic polymers are also suitable softening compounds. Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats. 10 polymers (Polymer JR, LR and KG series from Amerchol), polyquaternium-4 copolymers, such as graft copolymers having a cellulose backbone and quaternary ammonium groups, which are bonded via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar hydro- xypropyl triammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar from Cognis or the Jaguar series from Rhodia), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg the commercial product Glucquat® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ", copolymers of PVP and dimethylamino methacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers

It is also possible to use polyquaternized polymers (for example Luviquat® Care from BASF) and also cationic biopolymers based on chitin and derivatives thereof, for example the polymer available under the trade name Chitosan® (manufacturer Cognis)

Also usable are compounds of the formula (VI)

R ¹⁷ can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds s can assume values between 0 and 5 R ¹⁸ and R ¹⁹ independently of one another in each case represent H, C _1-4 Alkyl or hydroxyalkyl and X ^" is an anion

Other suitable plasticizing compounds include protonated or quaternized polyamines

Particularly preferred plasticizing compounds are alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group. Very particular preference is given to N-methyl-N- (2-hydroxyethyl) -N, N- (dicycloacyloxyethyl) -ammonium compounds. methosulfate or bis (palmιtoyloxyethyl) -hydroxyethyl-methyl-ammonium-methosulfate

Further preferred softening compounds are nonionic softening compounds, in particular polyoxyalkylene glycol alkanoates, polybutylenes, long-chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglucosides, in particular sorbitan mono-, di- and n-esters, and fatty acid esters of polycarboxylic acids,

In addition to the surfactants and / or softening compounds, the individual phases of the washing, rinsing or cleaning agent may contain further ingredients which further improve the performance and / or aesthetic properties of the washing, rinsing or cleaning agent individual phases of the washing, rinsing or cleaning agent preferably additionally one or more substances from the group scaffolds, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, color transfer inhibitors, antimicrobial agents, Germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, Bugelhilfsmittel, repellents and impregnating agents, swelling and anti-sliding agents, neutral full salts and UV absorbers

As scaffolds which may be contained in the phases of the washing, rinsing or cleaning agents, particular mention may be made of silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances

Suitable crystalline, layered Natπumsilikate have the general formula NaMSi _x O _{2x + I} H ₂ O, wherein M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x , 3 or 4 are Preferred crystalline sheet silicates of the formula given are those in which M is Natminum and x assumes the values 2 or 3. In particular, both β- and δ-Natπumdisilikate Na ₂ Si ₂ O ₅ • yH ₂ O are preferred

It is also possible to use amorphous sodium silicates having a modulus Na ₂ O SiO ₂ of 1 2 to 1 3,3, preferably of 1 2 to 1 2,8 and in particular of 1 2 to 1 2,6, which are loosely delayed and have secondary washing properties Compared to conventional amorphous Natπumsilikaten can thereby be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term "amorphous" is also "X-ray amorphous" means This means that the silicates in Rontgenbeugungsexpeπmenten provide no sharp X-rays, as they are typical for crystalline substances, but at best one or more maxima of the scattered X-rays, which have a width of several degrees of the diffraction angle However, it may well lead to particularly good builder properties, if the silicate particles in electron diffraction This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to 50 nm and in particular up to a maximum of 20 nm being preferred. Particularly preferred are compacted / compacted ones amorphous silicates, compounded amorphous silicates and dried X-ray amorphous silicates The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X), which is sold by SASOL under the brand name VEGOBOND AX ^® and by the formula

n Na ₂ O (1-1I) K ₂ O Al ₂ O ₃ (2 to 2.5), SiO ₂ (3.5 to 5.5) H ₂ O n = 0.90 - 1. can be described 0th The zeolite can be used as a spray-dried powder or else as an undried, stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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

Organic builders which may be present in the textile treatment agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents, dishwashing detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular form of acidic acid which were determined in principle by means of gel permeation chromatography (GPC), in which case a UV detector was used. The measurement was carried out against an external Polyac'rylsäure standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol The (co) polymeric polycarboxylates can be used either as an aqueous solution or preferably as a powder

To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer

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

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

Also to be mentioned as further preferred skeletons polymeric aminodicarboxylic acids, their salts or their precursors Substances are particularly preferred polyaspartic acids or their salts and derivatives which have not only builder properties but also a bleach-stabilizing effect

Other suitable skeletons are polyacetals, which can be obtained by reacting dialdehydes with Polyolcarbonsauren which have 5 to 7 C-atoms and at least 3 hydroxyl groups. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polycarbonsauren such as gluconic acid and / - or glucoheptonic acid

Other suitable organic scaffolds are dextrins, for example, oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, the hydrolysis products have average molecular weights in the range of 400 up to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide in comparison with dextrose, Useful are both Maltodextπne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g / mol The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Also suitable is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also other suitable builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Other useful organic builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactic form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Among the compounds which serve as bleaching agents in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxy pyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or, more preferably, phthalimidoperoxycarboxylic acids, such as 6-phthalimidoperachexanoic acid (6-phthaloylimidopercapric acid, PAP). Preferably, organic peracids, alkali metal perborates and / or alkali metal percarbonate, in amounts of 0.1 to 40% by weight, preferably 3 to 30 wt .-%, in particular 5 to? 5 wt .-% based on a phase of a washing, Rinsing or cleaning agent used.

Alternatively, a light-active bleaching agent which comprises titanium dioxide, preferably modified titanium dioxide, in particular carbon-modified titanium dioxide, may also be used. For example, these bleaches absorb in the visible region of the spectrum and form hydroxy radicals with water.

In order to achieve an improved bleaching effect during washing at temperatures of 60 ° C. and below, compounds which under perhydrolysis conditions are peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted Perbenzoic acid, are used. Suitable are substances which contain O- and / or N-acyl groups of the stated C atom number and / or optionally substituted Wear etched benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3 , 4,6-tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid hydrides, in particular phthalic anhydride, isoic anhydride and / or succinic anhydride, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diace- toxy-2,5-dihydrofuran, enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG ), Pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and the like d / or particulate caprolactam derivatives and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, undeceloyl oxybenzenesulfonate (UDOBS) ₁ sodium dodecanoyloxybenzenesulfonate (DOBS) ₁ decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12). Such bleach activators are optionally in the usual amount range of 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15 wt .-%, in particular 1 wt .-% to 10 wt .-%, based on a phase of Washing, rinsing or cleaning agent.

The phases of the washing, rinsing or cleaning agents may each contain a thickener. The thickener may include, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, carrageenan, carboxymethyl cellulose, bentonites, wellan gum, locust bean gum, agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein include. However, modified natural substances such as modified starches and celluloses, examples which may be mentioned here include carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and core flour ethers, can be used as thickeners.

The polyacrylic and polymethacrylic thickeners include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to "International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA): Carbomer), also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from the company 3V Sigma under the trade name Polygel®, for example Polygel DA, and from the company BF Goodrich under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (Molecular weight about 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore, these include the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), to which approx the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-J69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and the example of the company. Rohm & Haas under the trade names Aculyn® and Acusol®, as well as from Degussa (Goldschmidt) under the trade name Tego® Polymer, for example the atpionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 81 Ö, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Cio ₃ o-alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably C- _M alkanols formed esters (INCI Acrylates / Cio ₃₀ alkyl acrylate crosspolymer) include and which are available, for example, from the company. BF Goodrich under the trade name Carbopol®, eg the hydrophobic Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C _{1o -3} o alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).

Another preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

As thickening agent, a fatty alcohol is also suitable. Fatty alcohols may be branched or unbranched, of native origin or of petrochemical origin. Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preferred Mixtures of different C-chain lengths, such as Taigfettalkohol or coconut oil, used. Examples are Lorol® Spezial (C12- ₁₄ -ROH) or Lorol® Technical (C ₁₂ -i ₈ -ROH) (both ex Cognis).

One phase of the washing, rinsing or cleaning agent may contain 0.01 to 3% by weight and preferably 0.1 to 1% by weight of thickener. The amount of thickener used depends on the type of thickener and the desired degree of thickening.

The phases of the washing, rinsing or cleaning agent may contain enzymes. Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, β-glucanases, oxidases, peroxidases, perhydrolases and / or laccases and mixtures of said enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ in their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities. The enzymes may be encapsulated or adsorbed to carriers to protect against premature degradation. The proportion of the enzymes, the enzyme liquid formulation (s) or the enzyme granules in one phase of a washing, rinsing or cleaning agent may be, for example, about 0.01 to 5% by weight, preferably 0.12 to about 2.5% by weight. be.

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

Non-aqueous solvents that can be used in the phases of the washing, rinsing or cleaning agent, for example, come from the; Group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol , 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents. Non-aqueous solvents can be used in one phase of the washing, rinsing or cleaning agent in amounts of between 0.5 and 15% by weight, but preferably below 12% by weight and in particular below 9% by weight.

In order to bring the pH of the phases of the washing, rinsing or cleaning agent in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation of one phase.

The pH of a phase of the washing, rinsing or cleaning agent is preferably between 4 and 10 and preferably between 5.5 and 8.5. In a preferred embodiment, a phase of the washing, rinsing or cleaning agent contains one or more perfumes in an amount of usually up to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.3 to 3 wt. -%.

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources.

In order to improve the aesthetic impression of the washing, rinsing or cleaning agents, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the textile treatment agents and to light and no pronounced substantivity to textile fibers so as not to stain them. It is particularly preferred that the respective phases of the washing, rinsing or cleaning agent contain different dyes, so that the phase boundary and thus the multiphase nature of the washing, rinsing or cleaning agent is visually more pronounced.

As foam inhibitors which can be used in the phases of the washing, rinsing or cleaning agent, for example, soaps, paraffins or silicone oils come into consideration, which may optionally be applied to support materials.

Suitable soil release polymers, also referred to as "anti-redeposition agents", include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30 wt% and hydroxypropyl groups of 1 to 15 wt%, respectively based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers. Optical brighteners (so-called "whiteners") can be added to textile treatment agents to eliminate graying and yellowing of treated flat textile fabrics which will attract the fiber and cause lightening and fake bleaching by turning invisible ultraviolet radiation into visible longer wavelength convert light, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white. Suitable compounds originate for example from the substance classes of the 4,4 ^'-Diamino- ^2,2' stilbenedisulfonic acids (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and the heterocycle-substituted pyrene derivatives. the optical brighteners are usually in Amounts between 0% and 0.3 wt .-%, based on the total amount of a phase of the washing, rinsing or cleaning agent used.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose ¹ and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the total amount of one phase the washing, Spüloder cleaning agent used.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, squeezing and squeezing across the grain, the detergents, rinse or cleaning agents may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester. For controlling microorganisms, the textile treatment agents may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, with the washing, rinsing or cleaning agents according to the invention also being entirely based on these compounds can be waived.

The textile treatment agents according to the invention may contain preservatives, it being preferred to use only those which have no or only a slight skin-sensitizing potential. Examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl-butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof , A suitable preservative is the solvent-free, aqueous combination of diazolidinyl urea, sodium benzoate and potassium sorbate (available as Euxyl® K 500 ex Schuelke & Mayr), which can be used in a pH range up to 7.

In order to prevent undesirable changes to the textile treatment agents and / or the treated fabrics caused by the action of oxygen and other oxidative processes, the washing, rinsing or cleaning agents may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.

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

Rinsing behavior of the washing, rinsing or cleaning agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C., the silicones being used in amounts of between 0.2 and 5% by weight, based on the total amount of one phase of the washing, rinsing or cleaning agent can.

Finally, a phase of the washing, rinsing or cleaning agent can also contain UV absorbers, which are absorbed by the treated textile fabrics and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of the benzophenone having substituents in the 2- and / or 4-position which are active by radiationless deactivation. Also suitable are substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.

In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex Schwerrnetalle can be used. Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) i or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates, which in one phase of the washing, rinsing or cleaning agent in amounts of from 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular of 0 , 03 to 1, 5 wt .-% are included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane -1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. The washing, rinsing or cleaning agents according to the invention can be used for cleaning and / or conditioning of textile fabrics.

The washing, rinsing or cleaning agents according to the invention can furthermore be used for cleaning hard surfaces.

The invention also relates to a dispensing container which comprises a washing, rinsing or cleaning agent which contains surfactant (s) and other customary ingredients of washing, rinsing or cleaning agents, wherein the agent has at least two phases, and the agent in the Storage state of the phases has at least one substantially vertically extending phase boundary, is designed such that upon delivery of the washing, rinsing or cleaning agent, the delivery along the phase boundary.

In a preferred embodiment of the dispensing container, for this purpose, it has a dispensing device extending the substantially vertical phase boundary of the washing, rinsing or cleaning agent. The dispensing device is, for example, a cap with a concentric opening, wherein the latter is preferably also arranged in extension of the substantially vertical phase boundary of the washing, rinsing or cleaning agent.

A dispensing container is transparent or translucent when the light transmission of a dispensing container wall at a wavelength of 410 to 800 nm is greater than 25%.

The dispensing container preferably has a surface which is preferably suitable as a base.

The dispensing container is preferably made of metal, glass, polyethylene terephthalate (PET) or a textile-based base body. In this case, the dispensing container can be flexible and, for example, have the shape of a bottle or a tube. The dispensing container may be emptied and present, for example, in the form of a dispenser system.

The dispensing container may be, for example, a polyethylene terephthalate (PET) bottle.

To prepare the individual phases of the washing, rinsing or cleaning agent, a base formulation is first prepared by means of customary and known methods and processes, in which For example, the ingredients of the base formulation are simply mixed in stirred tanks, water, non-aqueous solvents and surfactants are conveniently presented and the other ingredients are added in portions. Separate heating in the preparation is not required, if desired, the temperature of the mixture should not exceed 80 ^° C. To set the desired viscosities of the phases, it may be necessary initially to introduce only a portion of the surfactants and to add a surfactant which adjusts the viscosity to the desired value only at the end.

Subsequently, further compounds are added to parts of the base formulation. It is important to ensure that the densities, the viscosities and / or the yield points of the parts of the base formulation continue to be substantially the same by addition of the further compounds, so that it is used in the production and / or storage of the multiphase washing, rinsing or cleaning agent does not come to a thorough mixing of the phases.

To prepare the washing, rinsing or cleaning agents according to the invention, at least two differently modified base-formulation parts are filled into a transparent or translucent dispensing container. The filling process of the respective base formulation parts takes place in parallel and sufficiently slowly, so that no mixing of the resulting phases takes place.

Examples

example 1

Preparation of a basic recipe

Table 1 shows the composition of a base formulation. Table 1 :

Base formulation [% by weight]

C ₁₃ . ₁₅ fatty alcohol with 7 EO 24.0

Sodium lauryl ether sulfate with 2 EO 7.5

Citric acid 0.1

Propylene glycol 5.0

Isoparaffins 5.0

Preservative 0.1

Water Ad 100

To prepare the base formulation, the ingredients listed in Table 1 were presented with the exception of the ethoxylated fatty alcohol and stirred at a temperature between 35 and 45 ⁰ C. Upon obtaining a homogeneous mixture, the ethoxylated fatty alcohol was added.

The viscosity of the base formulation was 30,000 mPas.

The pH of the base formulation was 6.2. This may, depending on the ingredients of the later phases of a washing, rinsing or cleaning agent, for example by adding acids such as citric acid, sulfamic acid, D-lactic acid, L-lactic acid, formic acid, maleic acid, a mixture of dicarboxylic acids (for example Sokalan DCS ex BASF), monoethanolamine, diethanolamine, triethanolamine, KOH, NaOH, LiOH, Mg (OH) ₂ or Al (OH) ₃ can be adjusted to a desired value.

Example 2

To prepare a two-phase washing, rinsing or cleaning agent, a first portion of the base formulation taken with citric acid was brought to a pH of 3. Then, to this mixture was added 6-phthalimidoperoxohexanoic acid (PAP) in an amount such that the later phase 1 of the washing, rinsing or cleaning agent contained 3% by weight of PAP. To prepare the second phase, a second part of the base formulation was taken, admixed with a liquid enzyme formulation containing cellulase and amylase and a perfume. The amounts were such that the later phase 2 of the washing, rinsing or cleaning agent contained 0.7% by weight of the enzyme liquid formulation and 1.5% by weight of the perfume. Subsequently, the two modified base formulations were transferred to PET bottles in a parallel filling process.

The washing, rinsing or cleaning agent had a clearly visible, substantially vertical phase boundary even after 4 weeks of standing storage and showed no mixing of the two phases.

Examples 3 to 9

Several biphasic washing, rinsing or cleaning agents were prepared analogously to Example 2, except that instead of the bleach, enzymes and the perfume, other partially incompatible compounds of the base formulation were admixed. The amounts in wt .-% in the table refer to the amount of ingredient in each phase of the washing, rinsing or cleaning agent:

^* Repellotex® SRP 6 ex Rhodia

^* * N-Methyl-N- (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) ammonium methosulfate

The washing, rinsing or cleaning agents 3 to 9 had a clearly visible, essentially vertical phase boundary after 4 weeks of storage and showed no mixing of the two phases.

Claims

Claims Washing, dishwashing or cleaning agents containing tensιd(s) as well as other common ingredients of washing, dishwashing or cleaning agents, the agent having at least two phases, characterized in that the agent in the storage state of the phases has at least one essentially vertical has a running phase boundary

Detergent, dishwashing or cleaning agent according to claim 1, characterized in that the phase boundary is visible

Detergent, dishwashing or cleaning agent according to claim 1 or 2, characterized in that the density of the at least two phases is essentially the same

Detergent, dishwashing or cleaning agent according to one of claims 1 to 3, characterized in that the yield point of the at least two phases is essentially the same

Washing, dishwashing or cleaning agent according to one of claims 1 to 4, characterized in that the viscosity of the at least two phases is essentially the same

Detergent, dishwashing or cleaning agent according to one of claims 1 to 5, characterized in that the at least two phases each have a viscosity in the range from 15,000 mPas to 50,000 mPas (Brookfield viscometer LVT-II at 20 rpm and 2O ⁰ C, spindle 5).

Washing, dishwashing or cleaning agent according to one of claims 1 to 6, characterized in that the agent has two phases

Detergent, dishwashing or cleaning agent according to claim 7, characterized in that a phase contains one or more ingredients which is/are incompatible with at least one ingredient of the other phase

Use of the washing, spooling or cleaning agent according to one of claims 1 to 8 for cleaning and/or conditioning textile fabrics

Use of the washing, dishwashing or cleaning agent according to one of claims 1 to 8 for cleaning hard surfaces

Dispensing container, comprising a washing, dishwashing or cleaning agent which contains tensιd(s) as well as other common ingredients of washing, dishwashing or cleaning agents, the agent having at least two phases, characterized in that the agent is in storage state of the phases has at least one essentially vertical phase boundary and the dispensing container is designed so that when the detergent, dishwashing or cleaning agent is dispensed, the dispensing takes place along the phase boundary.

12. Dispensing container according to claim 11, characterized in that the dispensing container is transparent or translucent.

13. Dispensing container according to claim 11 or 12, characterized in that the phase boundary is visible.

14. Dispensing container according to one of claims 11 to 13, characterized in that the dispensing container is deformable.

15. Dispensing container according to one of claims 11 to jl3, characterized in that the dispensing container can be completely emptied.

16. Dispensing container according to one of claims 1 1 to 15j, characterized in that the dispensing container is made of metal, glass, polyethylene terephthalate (PET) or a textile-based base body.