EP0879874A2 - Encapsulated detergent - Google Patents

Abstract

Encapsulated agents for manual cleaning, especially dishwashing, comprise (a) an agent containing 20-100 wt.% alkyl- and/or aryl-polyether sulphate surfactant(s) of formula R<1)<CHR<2>CH2O)xOSO3M (I) and/or alkyl- and/or aryl sulphate surfactant(s) of formula R<3>OSO3M (II) and (b) a water-soluble or water-dispersible encapsulating material (III). In the formulae, R<1>, R<3> = 6-22 carbon (C) aliphatic hydrocarbyl and/or aromatic hydrocarbyl, optionally substituted by 1-18 C alkyl; R<2> = hydrogen (H) and/or 1-4 C alkyl; x = 0.1-6; M = a metal cation or ammonium ion. Also claimed is the use of agents containing anhydrous surfactant, encapsulated in (III), as manual cleaning or dishwashing agents.

Description

The invention relates to manual cleaning agents, in particular hand dishwashing agents (HGSM) and pretreatment agent for softening stubborn dirt. The The invention also relates to the use of a coated active substance, comprising an active substance containing an essentially anhydrous surfactant or surfactant mixture, and an envelope made of water-soluble or water-dispersible material, as a manual cleaning agent, especially HGSM, or pre-treatment agent for Remove stubborn dirt. Furthermore, the invention relates to an encased Active substance.

Conventional cleaning agents are usually as thin to viscous liquids formulated. Such a liquid formulation generally serves on the one hand to to achieve a relatively homogeneous mixing of the active ingredients in the formulation, on the other hand, the liquid formulated agents allow the user to manufacture the actual rinsing or cleaning liquor a dosage of the agent in the rinse or water used for cleaning without coming into contact with the skin. Such skin contact is often undesirable since the agents are often in a concentrated form exert an irritating effect on the skin, which is considered unpleasant by the user is felt. However, there are disadvantages to such a liquid formulation for example, that usually for incorporating solid active ingredients in a As a rule, a not insignificant proportion of water must be added to the agent. A such procedure is, however, in terms of economic and ecological Considerations do not make sense. The presence of water in the middle leads to a reduction of the active substance content, since the water itself does not have the desired cleaning power having. The proportion of active substance per unit weight or unit space of the agent is therefore reduced due to the formulation as a liquid.

Even more concentrated, commercially available liquid products usually have still have a high water content. The consumer also tends to use it such concentrates usually for overdosing.

However, if the appropriate agent is formulated as a solid, the consumer must Dosing cumbersome to use dosing aids. There is a risk of one Skin contact with the concentrated agent, which leads to the above-mentioned consequences can.

Both liquid and solid formulations of manual cleaning agents exhibit thus together the disadvantage that on the part of the user an accurate, ecological tolerable and repeatable dosing is difficult to achieve. This is with Consideration of an environmentally compatible application disadvantageous.

The object of the invention was therefore to provide a dosage form for manual cleaning agents, especially HGSM, or pretreatment to remove stubborn To find dirt that does not have the disadvantages described above. In particular, it was an object of the invention to provide dosage forms for cleaning agents, especially HGSM, or pretreatment agent for removing stubborn dirt to find that allow highly concentrated, essentially anhydrous Cleaning agents, in particular HGSM, or pretreatment agents for removal stubborn dirt, simple and safe for the consumer Way to make usable.

WO 94/14941 relates to aqueous neutral or slightly alkaline, automatic dishwashing detergents, that are free of anionic and cationic surfactants. The machine Dishwashing detergents can be enclosed in water-soluble or water-dispersible containers be made of gelatin, for example. The use of encapsulated Active substances containing a surfactant or a surfactant mixture as a hard dishwashing liquid or cleaning agent is not mentioned in the document.

EP-A 0 261 754 relates to a mixture of amine salts and long-chain alkyl ether sulfates and liquid polyethylene glycols as well as glycerin, encapsulated in an elastic Gelatin capsule. The possibility of an active substance containing a surfactant or a Capsule mixture, encapsulated and filled gelatin capsules as a dishwashing liquid or use cleaning agents is not possible from the document forth.

It has now been found that active substances containing highly concentrated surfactant mixtures such as in liquid formulated manual cleaning agents or HGSM or in pre-treatment agents to remove stubborn dirt occur, are encapsulated in water-soluble or water-dispersible casings and that such coated active substances are suitable for use as manual Cleaning agents, in particular HGSM, or pretreatment agents for removal stubborn dirt, easily suitable.

The invention therefore relates to the use of a water-soluble or water-dispersible material-coated active substance containing in essential water-free surfactant or surfactant mixture, as a manual cleaning agent, especially hand dishwashing liquid (HGSM) or pretreatment agent for removal stubborn dirt.

In the context of the invention, “active substance” includes the entire content of the water-soluble or water-dispersible coating understood. This can be, for example can be a single surfactant, but it can also, as will be explained below a mixture of one or more surfactants and, if necessary, another Sequestering agents and other additives. The term "active substance" therefore also contains substances that have no or only an indirect contribution to the cleaning effect afford (for example perfume or dyes).

A “manual cleaning agent” is used in the context of the present invention understood a cleaning agent that the user acquired in concentrated form is dissolved in water at a temperature of up to about 60 ° C for use becomes. With this cleaning liquor, hard surfaces such as glass, Ceramics, concrete, metal, as well as painted or polished surfaces can be cleaned. Of the The cleaning process is carried out manually by the user. Under "manual Cleaning "is understood in the sense of the present invention to be a cleaning process where the user is in manual contact with the object to be cleaned. Under "Manual contact" is also understood to mean a contact that can be established with the help of a mechanical aids, for example a rag, a sponge, a brush or a scrubber.

The HGSM are a sub-group of manual cleaning agents. For use the HGSM are usually in water with a temperature up to about 50 ° C dissolved, and the resulting rinse liquor for manual cleaning of Eß- and Cookware used. With regard to the term "'manual cleaning"', the above apply made comments.

Under "Pre-treatment agents for removing stubborn dirt" in the Within the scope of the invention understood means that to solve stubborn dirt serve on hard surfaces, especially on tableware or cookware. For These agents are used in water with a temperature of up to about 70 ° C dissolved and the surface to be cleaned with the resulting pretreatment liquor treated. the term encompasses the rest of the text "manual cleaning agent" also the pretreatment agent for removing stubborn Soiling, unless otherwise stated.

Insofar as it is in the use according to the invention or in the invention Agent is a pretreatment agent, can with the pretreatment agent performed treatment step even without manual contact on the part of the user expire. For this purpose, the goods to be treated (e.g. tableware or cookware) are placed in the pretreatment liquor introduced and left standing. Alternatively, it is possible to bring the material to be treated into water, followed by the pretreatment agent is added.

Under an "essentially anhydrous surfactant or surfactant mixture" is in the frame the present application understood a surfactant or surfactant mixture that is less than about 10% by weight, preferably less than about 5% by weight and particularly preferred contains less than about 3% by weight of free water. The term "free water" stands for water that is not in one of the active ingredients existing components in the form of water of crystallization or bound by adsorption is.

The active substance, containing the essentially anhydrous surfactant or surfactant mixture, can as a liquid, as a highly viscous paste or preferably as a solid in the Containers are available.

The casing can basically have any shape, being rational and forms which can be produced inexpensively are generally preferred. These include, for example all shapes that are rotationally symmetrical with respect to at least one axis, for example the spherical shape, elliptical shapes or cylindrical shapes, where as Wrapping a capsule in the form of a hemispherical shell at both ends closed cylinder is preferred. The covering can be in one part or in several parts be formed, the one-part or the two-part, openable and closable Shape, is preferred.

The envelope has a volume of about 0.5 to about 300 ml. In this Range is the usual dosage amounts, such as for manual cleaning agents, HGSM, in particular, are used in the private or industrial sector. Preferably the envelope has a volume of about 0.8 to about 30 ml, especially preferably about 1 to about 20 ml. Have an application for HGSM Envelopes with a volume of approximately 1 to 5 ml have been particularly proven. For one Use as a cleaning agent can make more sense, for example about 5 to about 30 ml. If large amounts of a detergent liquor to be produced, for example in an application in the industrial sector, if necessary, volumes of more than 300 ml may also be useful.

The envelope used in the present invention is water-soluble, or at least water dispersible. That is, the material from which the wrapping exists, at least partially dissolves or at least dissolves in water forms a dispersion so that the coating becomes permeable and a mass transfer between the water surrounding the container and the water enclosed by the container Ingredients.

The time it takes for the container to at least partially dissolve is in about 35 ° C warm water at about 10 to 50 seconds, preferably at about 20 to 40 seconds. The dissolution process can be supported by stirring.

The casing preferably consists of a material that is at least one natural or synthetic polymer or a mixture of two or more thereof contains. The material from which the covering consists preferably contains gelatin, Polyvinyl alcohol, polyethylene glycol, cellulose ether, alginic acid and / or alginates or Pectic acid or a mixture of two or more thereof. Furthermore, the material, from which the covering is made, contain additives which increase the elasticity and Affect water solubility. Preferably contains the material from which the wrapper is made consists of gelatin and a plasticizer, for example glycol, glycerin or Sorbitol. The proportion of plasticizers in the material from which the casing is made is usually about 10 to about 40% by weight.

The coating contains an active substance with a content of essentially anhydrous surfactant or surfactant mixture, essentially for the rinsing or cleaning effect responsible for. The essentially anhydrous surfactant or Surfactant mixture contains at least one anionic surfactant, and optionally also at least one nonionic surfactant and / or at least one amphoteric surfactant. The Active substance can optionally in addition to the surfactant or surfactant mixture Sequestering agents or other additives, or mixtures of two or more of which, included.

Typical examples of anionic surfactants that can be used in the context of the invention are Alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, Glycerol ether sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, Fatty acid amide (ether) sulfates, dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isothionates, Fatty acid sarcosinates, fatty acid taurides, acyl lactinates, acyl oligoglycoside sulfates, Protein fatty acid condensates (especially vegetable products based on soy) or Alkyl (ether) phosphates or mixtures of two or more thereof.

The anionic surfactant or surfactants are essentially the same anhydrous surfactant mixture usually in a proportion of about 5 wt .-% to about Contain 100 wt .-%. The proportion of anionic surfactants in HGSM is usually at about 5 to about 100% by weight. In manual cleaners are common contain different proportions of anionic surfactants, but usually less than about 90% by weight.

und die Tenside der allgemeinen Formel II

worin R¹ und R³ jeweils unabhängig voneinander für aliphatische, lineare und/oder verzweigte C_6-22-Alkylreste und/oder für aromatische, gegebenenfalls mit C_1-18-Alkylgruppen substituierte Kohlenwasserstoffreste stehen, R² für Wasserstoff und/oder einen oder mehrere C_1-4-Alkylrest(e) steht, x für Zahlen von 0,1 bis 6 steht und M für Metallkationen oder Ammoniumionen steht.Anionic surfactants from the group of alkyl sulfates and alkyl ether sulfates are particularly preferred in the context of the present invention. These include, for example, surfactants of the general formula I.

and the surfactants of the general formula II

wherein R ¹ and R ³ each independently represent aliphatic, linear and / or branched C _6-22 alkyl radicals and / or aromatic, optionally substituted with C _1-18 alkyl groups, R ^{2 represents} hydrogen and / or one or several C _1-4 alkyl radicals, x stands for numbers from 0.1 to 6 and M stands for metal cations or ammonium ions.

If the radical R ^{2 is} hydrogen and / or one or more C _1-4 alkyl radicals, the compounds of the general formula I are sulfates of mixed ethers, such as those obtained by alkoxylation of alcohols with ethylene oxide and a C _{1- 4} alkylene oxide and / or a mixture of several C _1-4 alkylene oxides are available. Such a mixed alkoxylation can also be carried out sequentially, producing block copolyethers (x = 2 or more). For the sake of clarity, a formula for each possible form of the polyether has been omitted.

a) mindestens eines Tensids der allgemeinen Formel I

oder

b) mindestens eines Tensids der allgemeinen Formel II

worin R¹ und R³ jeweils unabhängig voneinander für aliphatische, lineare und/oder verzweigte C_6-22-Alkylreste und/oder für aromatische, gegebenenfalls mit C_1-18-Alkylgruppen substituierte Kohlenwasserstoffreste stehen, R² für Wasserstoff und/oder einen oder mehrere C_1-4-Alkylrest(e) steht, x für Zahlen von 0,1 bis 6 steht und M für Metallkationen oder Ammoniumionen steht,

oder ein Gemisch aus zwei oder mehr davon, enthält.It is therefore preferred to use an active substance in the manual cleaning agent according to the invention, in particular in the HGSM, which as an essentially anhydrous surfactant or surfactant mixture comprises about 20 to 100% by weight, preferably about 40 to about 100% by weight,

a) at least one surfactant of the general formula I.

or

b) at least one surfactant of the general formula II

wherein R ¹ and R ³ each independently represent aliphatic, linear and / or branched C _6-22 alkyl radicals and / or aromatic, optionally substituted with C _1-18 alkyl groups, R ^{2 represents} hydrogen and / or one or several C _1-4 alkyl radicals, x stands for numbers from 0.1 to 6 and M stands for metal cations or ammonium ions,

or a mixture of two or more thereof.

The radicals R ¹ and R ³ each particularly preferably independently of one another stand for aliphatic, linear C _8-16 hydrocarbon radicals which preferably derive from oleochemical raw materials. In the latter case, the anionic surfactants are called fatty alcohol ether sulfates.

Fatty alcohol ether sulfates are anionic surfactants which are produced on an industrial scale by SO ₃ or chlorosulfonic acid (CSA) sulfation of fatty alcohol polyalkylene ethers and subsequent neutralization. Typical examples are the sulfates of addition products with an average of 1-10 and in particular 2-5 mol ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotri-decyl alcohol, myristyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elayl alcohol, elaalyl alcohol, ela Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and brassidyl alcohol and their technical mixtures, the sulfates generally being used in the form of their alkali metal salts, preferably as the sodium salt, or in the form of their alkaline earth metal salts, preferably magnesium salts, or as mixtures of two or more of the latter salts will. For example, the commercially available types Texapon N or Texapon K14 (from Henkel, Düsseldorf) are particularly preferred.

The essentially water-free surfactant or surfactant mixture is used in one application used as a hand dishwashing detergent, it is preferred if at least one surfactant of general formula I and at least one surfactant of general formula II is. The ratio between the surfactant or the mixture of surfactants general formula I and the surfactant or the mixture of surfactants of the general Formula II is about 0.2: 1 to about 5: 1, preferably about 1: 1 to about 4: 1 and more preferably about 1.5: 1 to about 2.5: 1.

A pH value is usually required for the cleaning effect of a pretreatment agent strongly alkaline range (greater than about pH 9) makes sense. Surfactants practice mainly a function as a wetting agent for better wetting of the treated Surfaces with the cleaning liquor, which is why all surfactants usually with sufficient network effect are suitable for this purpose.

When using the essentially water-free surfactant mixture in one It is therefore a pretreatment agent for removing stubborn dirt sufficient if only a surfactant of the general formula II is present.

If necessary, the essentially water-free surfactant mixture can still be nonionic Contain surfactants. Here, strongly foaming or weakly foaming non-ionic Surfactants are used.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol esters, fatty acid amide polyglycol ethers, Fatty acid amine polyglycol ethers, alkoxylated triglycerides, alkyl oligoglycosides, fatty acid N-alkyl glucamides, Polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates.

The manual cleaning agents or HGSM according to the invention preferably contain addition products of alkylene oxides to linear, aliphatic C _8-16 alcohols in the active substance as nonionic surfactant or as nonionic surfactants. Preferred alkylene oxides are ethylene oxide and propylene oxide. Ethylene oxide is particularly preferred. Typical examples of fatty alcohols are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, high pressure alcohols, bheylyl alcohol alcohol, brasso alcohol alcohol, brass oil alcohol, biol alcohol alcohol, alcohol blends, bruyl alcohol alcohol, brass bleaches, bruyl alcohol alcohols, and their mixtures, petroselyl alcohol, brass, alcoholic alcohols, bruyl alcohol alcohols, and mixtures thereof, for example, petroselyl alcohol, brass, alcoholic alcohols, benzoyl alcohol alcohols, and mixtures thereof, and methyl alcohols, petroselyl alcohol, and mixtures of them with alcohols, petroselyl alcohol; technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Technical fatty alcohol mixtures are particularly preferred, the fatty alcohols contained having about 12 to about 18 carbon atoms, for example coconut, palm, palm kernel or tallow fatty alcohols.

The ethoxylation product of coconut fatty alcohols is particularly preferred, the Alcohols have an average of about 7 ethylene oxide units.

The amides of alkylcarboxylic acids, preferably of alkylcarboxylic acids having about 6 to about 24 carbon atoms, with alkanolamides, preferably monoalkanolamides, can likewise be used as nonionic surfactant or as nonionic surfactants. The amides which are obtainable from natural or synthetically produced fatty acids and fatty acid cuts with aminoethanol are particularly preferred; the monoethanolamides from coconut fatty acid cuts, in particular the C _8-14 fatty acid cuts and ethanolamine, are very particularly preferred.

The alkyl polyglycosides or the fatty acid glucamides can also be used as nonionic surfactants. The non-ionic surfactant or the non-ionic surfactants can serve in the manual cleaning agent or in the HGSM, for example as a wetting agent or for better detachment of fatty substances. For example, the so-called alkyl polyglycosides of the general formula R ¹⁰ O- (Z) _x can also be used as the nonionic surfactant or as nonionic surfactants.

In the compounds designated in this way, the alkyl radical R ^{10 contains} 6 to 22 carbon atoms and can be either linear or branched. Primary linear or methyl branched methyl in the 2-position are preferred. Such alkyl radicals R ¹⁰ are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl radicals. 1-Octyl, 1-decyl, 1-lauryl or 1-myristyl radicals are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used in the active substance according to the invention can contain, for example, only a certain alkyl radical R ¹⁰ . Usually, however, the alkyl polyglycosides are produced from natural fats and oils or mineral oils. In this case, the alkyl radicals R ^{10 are} mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

• im wesentlichen für C₈- und C₁₀-Alkylgruppen,
• im wesentlichen für C₁₂- und C₁₄-Alkylgruppen,
• im wesentlichen für C₈- bis C₁₆-Alkylgruppen oder
• im wesentlichen für C₁₂- bis C₁₆-Alkylgruppen steht.

Alkylpolyglycosides in which R ¹⁰

• essentially for C ₈ and C ₁₀ alkyl groups,
• essentially for C ₁₂ and C ₁₄ alkyl groups,
• essentially for C ₈ - to C ₁₆ -alkyl groups or
• essentially represents C ₁₂ - to C ₁₆ -alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Usually sugar with 5 or 6 carbon atoms and the corresponding Oligosaccharides used. Examples of such sugars are glucose, fructose, galactose, Arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, Talose and sucrose. Preferred sugar components are glucose, fructose, galactose, Arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 Sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. All alkylpolyglycosides in which x is 1.1 to 1.4 are particularly preferred.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention be used. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Also for use in the manual cleaning agents or HGSM are suitable surfactants from the family of glucamides, for example alkyl-N-methylglucamides, where the term alkyl refers to alkyl residues with a chain length of about 6 to about 14 carbon atoms. It can be beneficial if the described nonionic surfactants not as the sole nonionic surfactant or as sole nonionic surfactants but in a mixture with at least one other nonionic surfactant is used, e.g. in combination with fatty alcohol ethoxylate, Alkyl polyglycoside, or in combination with fatty alcohol ethoxylate and glucamide or in Combination with glucamide and alkyl polyglycoside. Where appropriate, are also quaternary or even higher combinations of the nonionic surfactants disclosed here are possible.

The nonionic surfactants, especially the monoethanolamides, are in the invention Detergents, especially in the HGSM, in an amount of up to about 60% by weight, but preferably in smaller amounts, about 40% by weight, 30 % By weight or 20% by weight. In a special embodiment, the detergent according to the invention in the active substance about up to 10 wt .-% of a nonionic surfactant or a mixture of two or more nonionic surfactants.

The ratio of anionic to nonionic surfactants in the active substance of manual cleaning agent according to the invention or HGSM is about 99: 1 to about 30: 1, preferably about 95: 5 to about 50:50.

The betaines are, for example, as amphoteric surfactant or as amphoteric surfactants applicable. Betaines are predominantly preferred by carboxyalkylation Carboxymethylation, made from amino compounds. Preferably the Starting materials with halogen carboxylic acids or their salts, especially with sodium chloroacetate specializes, forming one mole of salt per mole of betaine. It is also the addition of unsaturated carboxylic acids such as acrylic acid possible. On the nomenclature and in particular on the distinction between betaines and "real" Amphoteric surfactants are based on the contribution by U. Ploog in Soap-Oil-Fat-Waxes, 198, 373 (1982). Further overviews on this topic can be found, for example, by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Det. 23, 309 (1986), R. Bibo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) and P. Ellis et al. in Euro cosm. 1, 14 (1994).

in der R⁴ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R⁵ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R⁶ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetallion oder ein Ammoniumion steht. Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which correspond to the general formula ( III )

in which R ⁴ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁶ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal ion or an ammonium ion.

Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C _12-14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C _16-18 tallow alkyl dimethyl amine and technical mixtures thereof.

in der R⁷CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R⁵, R⁶, n und X die oben angegebenen Bedeutungen haben.Carboxyalkylation products of amidoamines which correspond to the general formula ( IV ) are also suitable,

in which R ⁷ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ⁵ , R ⁶ , n and X have the meanings given above.

Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, steaic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaostearic acid, garbic acid, arachic acid, arachic acid, arachic acid, arachic acid, arachic 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. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylammopropylamide with sodium chloroacetate.

in der R⁸ für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R⁹ für eine Hydroxygruppe, einen OCOR⁸- oder NHCOR⁸-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar.Furthermore, suitable starting materials for the betaines to be used in accordance with the invention are also imidazolines which correspond to the general formula ( V )

in which R ^{8 is} an alkyl radical having 5 to 21 carbon atoms, R ^{9 is} a hydroxyl group, an OCOR ⁸ or NHCOR ⁸ radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines.

Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12-14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Suitable sequestrants are those from the class of aminopolycarboxylic acids and polyphosphonic acids. About the aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetracetic acid, diethylenetriaminepentaacetic acid as well as their higher homologues. Suitable polyphosphoric acids are 1-hydroxyethane-1,1-diphosphonic acid, Aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologues, such as diethylenetetraminetetra (methylenephosphonic acid). The acids mentioned usually come in the form of their Alkali salts, in particular the sodium or potassium salts for use. Prefers Sodium nitrilotriacetate is used in proportions of up to 10% by weight, preferably 2% by weight 6% by weight, based on the manual cleaning agent.

Suitable sequestrants also include monomeric polycarboxylic acids or hydroxypolycarboxylic acids, especially in the form of the alkali salts, for example Sodium citrate and / or sodium gluconate.

The preferred sequestering agents include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, with the sodium or potassium salts being preferred. Particularly suitable are polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight (M _n ) of at least about 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, for example oxidized polysaccharides in accordance with WO-A 93/08251 , Polyacrylates, polyhydroxyacrylates, polymethyacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in EP-A 022 551. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.

Particularly preferred acrylic acid-maleic acid copolymers have a relative molecular weight from 50,000 to 100,000.

Suitable, albeit less preferred, compounds of this class are copolymers acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, Ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight is.

Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as polymeric carboxylates or carboxylic acids. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, preferably a C ₄ -C ₈ dicarboxylic acid, maleic acid being preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ -carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight. %, preferably 10 to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular between 2: 1 are very particularly preferred and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives, is substituted.

Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55 % By weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or Acrylate, 10 to 30% by weight, preferably 15 to 25% by weight of methallylsulfonic acid or Methallylsulfonate and as a third monomer 15 to 40 wt .-%, preferably 20 to 40 % By weight of a carbohydrate. This carbohydrate can be a mono-, Be di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides preferred are, sucrose is particularly preferred. By using the third monomer predetermined breaking points are built into the polymer which are responsible for the degradability of the polymer are responsible. Let the terpolymers used produce themselves according to the known and usual methods. Are also preferred terpolymers are used which are either completely or at least partially, neutralized in particular to more than 50%, based on the carboxyl groups present are.

Also useful are polyacetal carboxylic acids, such as those obtained by polymerization of esters of glycolic acid, introduction of stable terminal end groups and Saponification to which sodium or potassium salts are obtained. Are also suitable polymeric acids by polymerization of acrolein and disproportionation of the Polymers according to Canizzaro can be obtained using strong alkalis. They are essentially from acrylic acid units and vinyl alcohol units or acrolein units built up.

The proportion of organic, carboxyl-containing structural substances in the invention manual detergent or HGSM can be up to 10% by weight, preferably 1% by weight to 7.5% by weight and in particular 2% by weight to 5% by weight, the content of Polyphosphonic acids up to 3% by weight, preferably 0.05% by weight to 1.5% by weight, in particular 0.1% by weight to 1% by weight. These substances mentioned are used in anhydrous form.

Crystalline alkali silicates, for example sodium water glass (module 2), and finely divided alkali alumosilicates, in particular zeolites of the NaA type, can also be regarded as useful sequestering agents in the sense of the present invention. Suitable zeolites have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE-C 24 12 837). Their particle size is usually in the range from 1 µm to 10 µm. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case. Crystalline layered silicates of the formula NaMSi _x O _{2x + 1} + Yh ₂ O, in which M represents sodium, x is a number from 1.9 to 4, are preferably used as crystalline silicates, which may be present alone or in a mixture with the aluminosilicates mentioned and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in EP-A 0 164 514. In particular, both β- and α-sodium disilicate Na ₂ Si ₂ O ₅ .Yh ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in WO-A 91/08171. Usable crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhône-Poulenc). The content of inorganic builder substances in the manual cleaning agent or HGSM can be up to about 80% by weight or less, for example 60% by weight, preferably up to about 25% by weight and in particular about 10% by weight to about 25% by weight .-%.

The manual cleaning agents or HGSM according to the invention are preferred phosphate free. If a phosphate content is ecologically harmless (for example at waste water purification eliminating phosphates), polymeric alkali phosphates, such as sodium tripolyphosphate, especially in pre-treatment agents for removing stubborn dirt. Your share can be up to about 50% by weight, preferably up to about 45% by weight, based on the total agent, amount, the proportion of the other solids, for example the alkali silicate and / or aluminosilicate, is reduced accordingly.

The cleaning agents according to the invention generally have a pH of about 5 to about 14.

For example, HGSM can be formulated in the neutral to slightly acidic pH range. Such cleaning agents have, for example, a pH of approximately to approximately 8, preferably about 5.5 to about 7.5.

Manual cleaning agents are preferably in a pH range of about 7 to formulated about 10.

To remove stubborn dirt, the pretreatment agents, can also be formulated in the higher alkaline range, i.e. then they can pH values from about 9 to about 14, preferably from about 10 to about 13.5.

In addition, minor amounts of Dyes, perfume oils, enzymes, bleaches, activators, complexing agents and The like can be contained in substances that are common in detergents and / or cleaning agents.

The active substance used in the context of the present invention contains the nonionic Surfactants, the amphoteric surfactants, the sequestering agents or the other additives, or mixtures of two or more thereof, in a proportion of 0 to about 60% by weight, preferably in total in a proportion of about 8 to about 40% by weight

A) die Wirksubstanz etwa 20 bis etwa 100 Gew.-%, vorzugsweise etwa 40 bis etwa 100 Gew.-%

a) mindestens eines Tensids der allgemeinen Formel I

und/oder

b) mindestens eines Tensids der allgemeinen Formel II

worin R¹ und R³ jeweils unabhängig voneinander für aliphatische, lineare und/oder verzweigte C_6-22-Kohlenwasserstoffreste und/oder für aromatische, gegebenenfalls mit C_1-18-Alkylgruppen substituierte Kohlenwasserstoffreste stehen, R² für Wasserstoff und/oder einen oder mehrere C_1-4-Alkylrest steht, x für Zahlen von 0,1 bis 6 steht und M für Metallkationen oder Ammoniumionen steht,

enthält, und

B) die Umhüllung wasserlöslich oder wasserdispergierbar ist.

The invention also relates to a coated active substance for a manual cleaning agent, in particular for an HGSM, comprising an active substance and a coating, wherein

A) the active substance is about 20 to about 100% by weight, preferably about 40 to about 100% by weight

a) at least one surfactant of the general formula I.

and or

b) at least one surfactant of the general formula II

wherein R ¹ and R ³ each independently represent aliphatic, linear and / or branched C _6-22 hydrocarbon radicals and / or aromatic hydrocarbon radicals which are optionally substituted by C _1-18 alkyl groups, R ^{2 represents} hydrogen and / or one or several C _1-4 alkyl radicals, x stands for numbers from 0.1 to 6 and M stands for metal cations or ammonium ions,

contains, and

B) the coating is water-soluble or water-dispersible.

The active substance preferably contains about 0 to about 80% by weight of nonionic surfactants or amphoteric surfactants or sequestering agents or additives, or a mixture of two or more of them, and in a particularly preferred case, the envelope contains Gelatin.

The invention is illustrated below by examples, but is not restricted.

EXAMPLES Example 1: Hand dishwashing liquid:

58,8 Gew.-% C_12-14-Fettalkoholether (2EO) Sulfat Natriumsalz

29,4 Gew.-% C_12-14-Fettalkoholsulfat Natriumsalz

7,8 Gew.-% Kokosamidopropylbetain

3,9 Gew.-% Kokosfettsäuremonoalkanolamid.

A hand dishwashing detergent of the following composition was placed in a gelatin capsule:

58.8% by weight of C _12-14 fatty alcohol ether (2EO) sulfate sodium salt

29.4% by weight of C _12-14 fatty alcohol sulfate sodium salt

7.8% by weight coco amidopropyl betaine

3.9% by weight of coconut fatty acid monoalkanolamide.

After dissolving the gelatin capsule in 10 l of water (content of the capsule: 4.2 g), Typical stains on glasses, dishes and cutlery are easily removed. The Cleaning performance is a liquid-formulated product with the cleaning performance comparable composition comparable.

Example 2: Cleaning supplies:

28,5 Gew.-% C_11-13-Alkylbenzolsulfonat Natriumsalz

47,1 Gew.-% Sasil^® (Fa. Henkel, Düsseldorf)

9,4 Gew.-% Kokosfettalkoholsulfat-Na-Salz

5,6 Gew.-% Kokosfettsäure-Na-Salz

9,4 Gew.-% Kokosfettalkoholethoxylat mit durchschnittlich 7 Ethylenoxid-Einheiten

A detergent of the following composition was encapsulated in gelatin capsules:

28.5% by weight of C _11-13 alkyl benzene sulfonate sodium salt

47.1 wt .-% Sasil ^® (Messrs. Henkel, Dusseldorf)

9.4% by weight coconut fatty alcohol sulfate Na salt

5.6% by weight of coconut fatty acid Na salt

9.4% by weight coconut fatty alcohol ethoxylate with an average of 7 ethylene oxide units

With a cleaning liquor made by dissolving the gelatin capsule in water were able to achieve comparable performance to a cleaning fleet in the Gardner test according to IPP can be achieved by adding a liquid product of identical composition was obtained.

Example 3:

27,3 Gew.-% Natriumwasserglas (Modul 2)

61,4 Gew.-% Natriumtripolyphosphat

6,8 Gew.-% Dodecylalkohol mit 6 Ethylenoxideinheiten

4,1 Gew.-% Natriumdodecylsulfat

0,4 Gew.-% Protease

A pretreatment agent of the following composition was encapsulated in gelatin capsules:

27.3% by weight sodium water glass (module 2)

61.4% by weight sodium tripolyphosphate

6.8% by weight of dodecyl alcohol with 6 ethylene oxide units

4.1% by weight sodium dodecyl sulfate

0.4 wt% protease

Example 4:

Experiments on the dissolution behavior of the gelatin capsules in water:

The capsules were filled with an HGSM, according to Example 1, and with stirring (50 rpm) in a beaker with 200 ml water at different temperatures given. Then the time was visually determined until the HGSM was released.

The results are shown in the following compilation:

Capsule 1: 30 mm long, 16 mm in diameter, filled with 0.8 g

Release the detergent

at 35 ° C: after 20 s
40 ° C: after 20 s
45 ° C: after 10 s

Capsule 2: 15 mm in length, 6 mm in diameter, filled with 0.4 g

Release the detergent

35 ° C: after 35 s
40 ° C: after 10 s
45 ° C: after 10 s

Capsule 3: 20 mm in length, 12 mm in diameter, filled with 0.6 g

Release the detergent

35 ° C: after 40 s
40 ° C: after 20 s
45 ° C: after 15 s

Claims (9)

Use of a water soluble or water dispersible material coated active substance with a content of essentially anhydrous surfactant, as a manual cleaning agent or hand dishwashing liquid (HGSM). Use according to claim 1, characterized in that the covering is made of water-soluble or water-dispersible material has a volume of 0.5 to 300 ml. Use according to claim 1 or 2, characterized in that the material contains at least one natural or synthetic polymer. Use according to one of the preceding claims, characterized in that the material contains gelatin. Use according to one of the preceding claims, characterized in that the active substance is 20 to 100% by weight. a) at least one surfactant of the general formula I.

and or b) at least one surfactant of the general formula II

wherein R ¹ and R ³ each independently represent aliphatic, linear and / or branched C _6-22 alkyl radicals and / or aromatic, optionally substituted with C _1-18 alkyl groups, R ^{2 represents} hydrogen and / or one or several C _1-4 alkyl radicals, x stands for numbers from 0.1 to 6 and M stands for metal cations or ammonium ions, contains. Use according to one of the preceding claims, characterized in that the active substance 0 to 60 wt .-% nonionic surfactants, amphoteric surfactants, sequestering agents or other additives, or a mixture of two or more of which contains. Enveloped active substance for a manual cleaning agent, in particular for a hand dishwashing detergent (HGSM), comprising an active substance and a covering, wherein A) the active substance 20 to 100 wt .-% a) at least one surfactant of the general formula I.

and or b) at least one surfactant of the general formula II

wherein R ¹ and R ³ each independently represent aliphatic, linear and / or branched C _6-22 hydrocarbon radicals and / or aromatic hydrocarbon radicals which are optionally substituted by C _1-18 alkyl groups, R ^{2 represents} hydrogen and / or one or several C _1-4 alkyl radicals, x stands for numbers from 0.1 to 6 and M stands for metal cations or ammonium ions, contains, and B) the coating is water-soluble or water-dispersible. Enveloped active substance according to claim 7, characterized in that the Active substance 0 to 60 wt .-% nonionic surfactants or amphoteric surfactants or Sequestering agents or additives, or a mixture of two or more thereof, contains. Enveloped active substance according to one of claims 7 or 8, characterized in that that the coating contains gelatin.