WO2002072535A1 - Modified cyanacrylate esters, nanocapsules or microcapsules produced therefrom and their use in washing and cleaning agents - Google Patents

Abstract

The invention relates to modified cyanacrylate esters, which can be obtained, for example, by esterifying cyanacrylic acid with an aromatic principle comprising at least one OH group, and to compositions, which are active with regard to washing or cleaning and which contain at least one nanocapsule or microcapsule consisting of a capsule enclosure and of a capsule contents, whereby the capsule enclosure contains at least one polycyanacrylate ester. The invention also relates to microcapsules that are produced by using at least one modified cyanacrylate ester.

Description

 Modified cyanoacrylate esters, nano- or microcapsules made from them and their use in detergents or cleaning agents

The present invention relates to modified cyanoacrylate esters which are obtainable, for example, by esterification of cyanoacrylic acid with a fragrance which has at least one OH group, washing- or cleaning-active compositions which contain at least one nano- or microcapsule consisting of a capsule shell and a capsule content, the capsule shell at least contains a polycyanoacrylate ester and microcapsules which have been produced using at least one modified cyanoacrylate ester.

When using detergents and cleaning agents, it is often desirable that certain ingredients of the detergent or cleaning agent are only released after the treatment of a substrate with such a detergent or cleaning agent. For example, ingredients such as fragrances, non-stick agents or antibacterial compounds should have a long-lasting effect even after the actual washing or cleaning process. There is also a corresponding need for personal care products, in particular for products for cleaning and caring for the hair, where a fragrance that lasts as long as possible beyond the actual treatment of the hair is particularly desirable.

If such active ingredients are used in an unprotected form in an appropriate washing or cleaning agent, they act directly on a correspondingly treated substrate, but the majority of the active ingredients are disposed of together with the washing liquor. The same also applies to personal care products that are usually used in aqueous form, for example hair care products such as shampoos or hair rinses. With such agents, a large part of the corresponding active ingredient is often lost through the washing process itself. The smaller part of the active substance originally adhering to the substrate gives it a short time after the end of the washing or cleaning process certain, desired properties, but these are lost very quickly due to the direct influence of environmental factors such as light, air, heat, moisture or friction.

If this effect is to be avoided, it must first be ensured that the largest possible proportion of the active ingredients present in the detergent or cleaning agent on the one hand survives the washing or cleaning process undamaged and on the other hand the highest possible proportion of the active ingredient remains on the treated substrate and after the washing or cleaning process has ended, it loses its effect only within the longest possible period.

It is known from detergent technology to release certain detergent ingredients by encapsulating these substances in microcapsules only after a certain period of time in the course of the washing process. For example, WO 97/24177 describes microcapsules which contain a detergent enzyme and are used in a liquid detergent. However, the capsules described dissolve in the course of the washing process, so that the ingredient is freely available in the washing liquor.

DE-T 691 10 070 relates to a composition for the cosmetic and / or pharmaceutical treatment of the uppermost epidermis layer by topical application on the skin and the corresponding production process. The compositions described contain biodegradable polymer nanoparticles which contain at least one active ingredient in the form of an oil and / or at least one active ingredient contained in a non-active carrier oil or an active oil, the active ingredient being a pharmaceutical manifesting itself in the upper layers of the epidermis Has effect. A detergent or cleaning agent containing nano- or microcapsules or a corresponding personal care agent is not described.

WO 94/17789 relates to nanocapsules which comprise an aqueous phase contained in a polymer capsule, the polymer capsule consisting of a crosslinked Polymers. A detergent or cleaning agent containing nano- or microcapsules or a corresponding personal care agent is not described in the document.

FR-25 15 960 relates to a method for producing biodegradable nanocapsules. The nanocapsules described there are used, for example, to encapsulate perfume, an extension of the fragrance effect being described. However, the publication does not describe the use of modified cyanoacrylates for the production of such nanocapsules or the use of nanocapsules or microcapsules in detergents or personal care products.

Therefore, no satisfactory solution is known from the prior art as to how an active ingredient can be used in a washing or cleaning agent or a personal care agent in such a way that it survives the washing, cleaning or care process essentially undamaged and then a significant amount of Deposits active ingredient on the treated substrate. Furthermore, no satisfactory solution to the problem is known from the prior art that an active substance deposited in this way on a substrate maintains its desired effect for a long period after the treatment of the substrate. Furthermore, no solution is described in the prior art as to how an active ingredient deposited in this way on a substrate only develops its effectiveness when the user so requests.

The present invention is therefore based on the object of providing solutions to the problems mentioned above.

The solution according to the invention is described in the context of the following text.

The present invention therefore relates to a cyanoacrylate ester of the general formula I

wherein R represents a branched, saturated or unsaturated, optionally substituted hydrocarbon radical with at least 6 C atoms or a linear unsaturated, optionally substituted hydrocarbon radical with at least 6 C atoms or an optionally substituted, saturated or unsaturated cyclic hydrocarbon radical with at least 5 C atoms or an aromatic hydrocarbon radical substituted with at least one linear or branched alkyl, alkenyl or alkoxy group and having at least 7 carbon atoms of a cosmetically active ingredient, a care substance, fragrance, lubricant or microbicide R-OH.

The cyanoacrylates designated with the general formula I in the context of the present invention have, for example, an optionally substituted carbon hydrogen radical as the radical R, which originates from an aromatic alcohol R-OH.

In the context of the present text, "fragrance alcohols" are compounds which are usually used to improve the smell of technical products or to improve the smell of products intended for consumers. The term "scented alcohol" includes in particular those compounds which have a boiling point of more than 80 ° C., in particular more than about 90 or more than about 100 ° C., at ambient pressure, in particular at a pressure of 101.3 kPa. In the context of a further preferred embodiment of the present invention, the term “fragrance alcohols” relates to compounds which, under the abovementioned conditions, have a boiling point of more than about 110 ° C., more than 120 ° C. or more than 130 ° C.

In the context of a preferred embodiment of the present invention, the radical R originates, for example, from a fragrant alcohol selected from the Group of fragrance alcohols consisting of 2,6-dimethyl-2-heptanol, trans-2-hexen-1-ol, cis-3-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol , 10-undecen-1-ol, 3,4,5,6,6-pentamethyl-3-hepten-2-ol, 3,4,5,6,6-pentamethyl-4-hepten-2-ol,

3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, 2-trans-6-cis-nonadien-1-ol, geraniol, nerol, linalool, myrcenol, lavandulol, citronellol, trans-trans-farnesol, trans- nerolidol, dihydromyrcenol, tetrahydrogeraniol, tetrahydrolinalool, 3,7-dimethyl-7-methoxyoctan-2-ol, (-) - menthol, (+) - neomenthol, (+) - isomenthol, (+) - neoisomenthol, (- ) -lsopulegol, (+) - neoisopulegol, (+) - isoisopulegol, (+) - neoisoisopulegol, α-terpineol, 1-terpinen-4-ol, (-) - borneol, (+) - isobomeol, 2-methyl- 4- (2,2,3-trimethyl-3-cyclopenten-1-yl) butanol, 2, methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1 -ol, 5- (2,2,3-trimethyl-3-cyclopenten-1-yl) -3-methylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten- 1-yl) -2-buten-1-ol, 3-methyl-5- (2,2,3-trimethyl-3-cyclopenten-1-yl) -4-penten-2-ol, 3,3-dimethyl -5- (2,2,3-trimethyl-3-cyclopenten-1-yl) -4-penten-2-ol, 3-trans-isocamphylcyclohexanol, 1- (2,2,6-trimethylcyclohexyl) hexan-3- oI, 2,5,5-trimethyl-1, 2,3,4,4a, 5,6,7-octahydronaphthalen-2-ol, benzyl alcohol, 2-Phe nylethyl alcohol, 1-phenylethyl alcohol, 3-phenylpropanol, 2,2-dimethyl-3- (3-methylphenyl) propanol, 1-phenyl-2-methyl-2-propanol, 4-phenyl-2-methyl-2-butanol , 2-methyl-5-phenylpentanol, 3-methyl-5-phenylpentanol, 1-phenyl-3-methyl-3-pentanol, 3-phenyl-2-propen-1-ol, phenoxyacetic acid 2-propenyl ester, 2nd -Isopropyl-5-methylphenol, 2-methoxy-4- (1-propenyl) phenol, 2-methoxy-4-allylphenol, 4-methoxybenzyl alcohol, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4- (4-hydroxyphenyl) -2-butanone, methyl salicylate, isoamylsalicylate, hexylsalicylate, cis-3-hexenylsalicylate, cyclohexylsalicylate, benzylsalicylate, phenethylsalicylate, ethylvanillin, hexahydromethyljonon, hydroxymethylaldylhexyl, hydroxylmethylpentyl, hydroxyl methylpentyl, hydroxyl methylpentyl iso, hydroxyl methylpentyl, hydroxyl methyl pentyl loxo, methyl hydroxyl methyl pentyl loxamethyl hexyl lamylo, methyl hydroxyl methyl pentyl,

In a further embodiment of the present invention, the radical R comes from a lubricant of the general formula R-OH. In the context of the present text, "lubricants" are compounds that show a non-stick effect on a surface. Such compounds are useful, for example, in detergents, for example when they are in use Ironing a textile after washing results in an improved gliding ability of the iron.

Lubricants of the general formula R-OH which are suitable in the context of the present invention are suitable, for example, silicone alcohols.

In a further embodiment of the present invention, the radical R comes from a microbicide of the general formula R-OH. Suitable microbicides are, for example, thymol or menthol or mixtures thereof.

The cyanoacrylate esters according to the invention can in principle be prepared by customary acidic esterification or transesterification methods, as are generally known to the person skilled in the art. However, the cyanoacrylate esters according to the invention are preferably obtained by particularly gentle, transition metal-catalyzed transesterification methods. For example, the one described by Seebach et al. transesterification described in Synthesis, Communications, February 1982, pp. 138-141. The subject of the described literature is considered part of the disclosure of the present text.

The abovementioned compounds of the general formula I are suitable for the preparation of polymers. Cyanoacrylates usually polymerize in the presence of nucleophilic compounds. The polymerization mechanism of cyanoacrylates is known to the person skilled in the art. In principle, however, all other radical or anionic polymerization processes which can usually be used for the polymerization of compounds having at least one olefinic unsaturated double bond are also suitable for the preparation of polymers from the compounds of the general formula I.

The present invention therefore also relates to a polymer produced using a compound of the general formula I. A polymer according to the invention can be, for example, a polymer that was only produced using a single type of compound of the general formula I, that is to say a homopolymer. However, it is also provided in the context of the present invention that a polymer according to the invention was produced using two or more different monomers of the general formula I. The different monomers can be arranged randomly or in blocks within the polymer chain.

In addition, it is provided in the context of the present invention that a polymer according to the invention using a monomer according to general formula I or a mixture of two or more such monomers and a further monomer which does not fall under general formula I, or a mixture from two or more such monomers. In principle, all compounds with at least one olefinically unsaturated double bond which are suitable for copolymerization with a monomer of the general formula I or a mixture of two or more such monomers are suitable as further monomers. In a preferred embodiment of the present invention, further monomers are, for example, cyanomethyl acrylate, cyanoethyl acrylate,

Cyanopropyl acrylate, cyanobutyl acrylate or cyanoisobutyl acrylate are used.

The polymers or copolymers according to the invention can be used in a wide variety of possible uses both on their own and in a mixture with another polymer or a mixture of two or more further polymers.

The present invention therefore also relates to a polymer mixture comprising a polymer according to the invention and at least one further polymer.

Suitable further polymers are basically all polymers with a polymer according to the invention or a mixture of two or more thereof are suitable for achieving the intended purpose. In the context of a preferred embodiment, a polymer mixture according to the invention contains a mixture of one or more polymers according to the invention and one or more further polymers which are essentially compatible with one another, ie which give essentially domain-free blends.

The monomers according to the invention according to general formula I are particularly suitable for the production of nano- or microcapsules. The present invention therefore also relates to nano- or microcapsules, obtainable by interfacial polymerization of at least one monomer of the general formula I according to the invention.

The subject of the present invention therefore relates not only to nano or microcapsules which have been produced exclusively using a monomer according to the invention. The present invention also relates to nano- or microcapsules which are produced using a mixture of two or more monomers of the general formula I according to the invention or using a mixture of one or more monomers of the general formula I and at least one further monomer which is not general Formula I falls were obtained.

The nano- or microcapsules according to the invention can in principle be produced by any interfacial polymerization process. A particularly suitable polymerization process is described, for example, in FR 2 515 960, to which particular reference is made here and whose disclosure relating to the production of nano- or microcapsules is considered to be part of the disclosure of the present text.

The nano- or microcapsules according to the invention have a capsule wall thickness of approximately 20 to approximately 200 nm, preferably approximately 50 to approximately 100 nm.

The nano- or microcapsules according to the invention have the advantage that if they are used, for example, as a carrier for a fragrance, they are due to their content of modified cyanoacrylates can release fragrances without destroying the capsule and or completely releasing the capsule contents. Fragrances are released, for example, by ester hydrolysis, in which the esters of a fragrance alcohol bound to the polycyanoacrylate prepared using a compound of the general formula I are released. Corresponding advantages also result from the use of cyanoacrylates modified with microbicides or lubricants.

Such an effect is particularly desirable when the nano- or microcapsules according to the invention are used in detergents or cleaning agents or in personal care products.

Typical examples of detergents, dishwashing detergents and cleaning agents that can be considered in the context of the invention are solid detergents in powder, granule or extrudate form, liquid detergents, fabric softeners, hand dishwashing detergents, machine dishwashing detergents, rinse aids and universal, household and sanitary cleaners. In the context of the present invention, however, the terms washing, rinsing and cleaning agents also include those compositions which are used, for example, after a washing, rinsing or cleaning process for textile or surface care. Such compositions are, for example, fabric softener, rinse aid or polish.

Typical examples of personal care products are soaps, shower gels or hair treatment agents, in particular shampoos, hair rinses, hair treatments, hair tip fluids, colorants or wave lotions.

In the context of the present invention, a “nano- or microcapsule” is understood to mean a capsule which consists of a capsule shell and a capsule content. The capsule shell of a nano- or microcapsule according to the invention contains at least one polycyanoacrylate, which was produced using a compound of general formula I. A nano- or microcapsule according to the invention preferably has a particle size which is in the With regard to human optical or sensory perception lies below the visibility or tactility threshold. Suitable here are, for example, nano or microcapsules, the size of which is approximately 0.01 to approximately 40 μm, in particular approximately 0.05 to approximately 10 μm. In the context of a preferred embodiment of the present invention, the particle size of a nano- or microcapsule according to the invention is approximately 0.1 to approximately 5 μm, in particular approximately 0.3 to approximately 3 or approximately 0.5 to approximately 1.5 μm.

For the entirety of the nano- or microcapsules according to the invention, the average particle size, measured as a value usually denoted by d50, is within one of the above-mentioned ranges. Suitable measurement methods for the average particle size in the nano- or microcapsules according to the invention are the measurement methods usually used for particles within this size range, for example dynamic light scattering, laser diffractometer or Coulter Counter.

While the use of the nano- or microcapsules according to the invention in detergents or cleaning agents or in personal care products has the advantages mentioned above, advantages can be achieved within the scope of the present invention if nano- or microcapsules are present in a washing or cleaning agent or in a personal care product whose capsule shell contains at least one polycyanoacrylate ester. Such nano- or microcapsules, which are filled with an active ingredient, in particular with a fragrance, show an extended effectiveness with regard to the action of the ingredient compared to detergents, cleaning agents or personal care products which contain the active ingredient in non-encapsulated form. In addition, it has been shown that the yield of active substance with regard to adherence to the treated substrate is considerably increased in comparison with non-encapsulated active substances.

An active substance according to the invention, nano- or microcapsules, can be in the form of a liquid, for example. If in a nano or micro capsule according to the invention or in a nano or Microcapsule, as described below as part of a composition according to the invention, if an active ingredient is to be used in solid form, such an active ingredient can be dissolved in a carrier oil, for example. Suitable carrier oils are, for example, triglycerides such as Miglyol 812 N, silicone oils or paraffin oils.

The present invention therefore also relates to a composition which is active in washing or cleaning or a composition for body care, at least comprising an anionic surfactant or a mixture of two or more such surfactants or a cationic surfactant or a mixture of two or more such surfactants and a nano- or microcapsule, consisting of a capsule shell and a capsule content, or a mixture of two or more such nano- or microcapsules, wherein the capsule shell contains at least one polycyanoacrylate ester and the capsule content contains at least one active ingredient.

In the context of the present invention, the term “active substance” is understood to mean a substance or a mixture of two or more substances which do not or not exclusively develop their effect during the washing, cleaning or care process. For example, a nano- or microcapsule , as used in the context of the present invention, contain a compound which is also present in non-encapsulated form in the washing, cleaning or care agent, but does not have any action directly associated with the washing or cleaning action which can be present in encapsulated as well as in non-encapsulated form in a washing, cleaning or care agent, but which have no direct washing, cleaning or care effect. This is not prevented by the fact that such an active ingredient may be dissolved in a carrier oil is present, which in turn plays an active role in a washing, cleaning or nursing process plays.

A washing or cleaning active composition according to the invention or a composition for personal care contains within the scope of a special one Embodiment of the present invention at least one anionic surfactant. In the process according to the invention, anionic surfactants can be the only constituent of the compositions according to the invention in addition to the nano- or microcapsules. However, it is also possible within the scope of the present invention that the compositions according to the invention contain an anionic surfactant or a mixture of two or more anionic surfactants together with one or more nonionic surfactants.

Suitable anionic surfactants in the context of the present invention are in principle all anionic surfactants which are usually used in detergents or cleaning agents or in personal care products. These compounds include, for example, anionic surfactants such as alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates and alk (en) ylsulfates.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C ₂₀ oxo alcohols and the half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred for washing technology reasons. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable as components of the compositions of the invention.

It can also be particularly advantageous and particularly advantageous for machine detergents to use C ₆ -C ₈ -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a low power point and at relatively low Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.

In a preferred embodiment of the present invention, in particular when the compositions according to the invention are to be used as detergents, the anionic surfactants used contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁ -C ₂ fatty alkyl sulfates or C 1 -C ₂ C ₄ fatty alkyl sulfates and C ₆ C ₈ fatty alkyl sulfates and in particular C ₂ -C ₆ fatty alkyl sulfates and C ₁ -C ₆ fatty alkyl sulfates.

In a further preferred embodiment of the invention, the compositions according to the invention not only contain saturated alkyl sulfates but also a proportion of unsaturated alkyl sulfates with a chain length of about 12 to about 22 carbon atoms. Mixtures are particularly preferred which contain saturated, sulfated C ₆ fatty alcohols and unsaturated, sulfated C ₈ fatty alcohols, for example those mixtures which differ from liquid fatty alcohol mixtures such as, for example, under the name HD-Ocenol® from Henkel KGaA are available. The anionic surfactants preferably have a weight ratio of alkyl sulfates to alkenyl sulfates of about 10: 1 to about 1: 2 or about 5: 1 to about 1: 1.

Other anionic surfactants that are suitable for the purposes of the present invention are, for example, other anionic surfactants of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C9.13-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C ₂ -C ₈ -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is obtained. Also suitable are alkanesulfonates, which are for example obtained from Cι _ _{2 18} alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Also suitable as anionic surfactants are the esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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

The sulfuric acid monoesters of the straight-chain or branched C ₇ .2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ . ₁ 1-alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι ₂ _ι ₈ fatty alcohols with 1 to 4 EO, are suitable according to the invention as part of the compositions of the invention. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other anionic surfactants suitable as part of the compositions according to the invention are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -i ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are special prefers. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other suitable anionic surfactants suitable as part of the compositions according to the invention in the context of the present invention are, in particular, soaps. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The above-mentioned anionic surfactants, including the soaps, can be present in the compositions according to the invention 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 mentioned are preferably present in the compositions according to the invention in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a further embodiment of the invention, the compositions according to the invention contain the surfactants in the form of their magnesium salts.

When selecting the anionic surfactants that can be used in the compositions according to the invention, there are essentially no restrictions in the way of freedom from formulations. Relevant formulations in the field of detergents, cleaning agents or care products are known to the person skilled in the art.

In the context of a further preferred embodiment of the present invention, a composition for washing or cleaning according to the invention or a composition for personal care contains at least one cationic surfactant. In the process according to the invention, cationic surfactants can be the only constituent of the compositions according to the invention in addition to the nano- or microcapsules. However, it is also possible within the scope of the present invention that the compositions according to the invention are a cationic surfactant or a Contain a mixture of two or more cationic surfactants together with one or more nonionic surfactants.

Suitable cationic surfactants for the purposes of the present invention are, for example, the esterquats as a constituent of the compositions according to the invention. The term "esterquats" is generally understood to mean quaternized fatty acid triethanolamine ester salts. These are known substances which can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91/01295 (Henkel) , after which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. Representative of the extensive state of the art at this point is the documents US 3,915,867, US 4,370,272, EP-A2 0 239 910, EP-A2 0 293 955 A2, EP-A2 0 295 739 and EP-A2 0 309 052 A2.Overviews on this topic are, for example, from O.Ponsati in CR CED Congress, Barcelona, 1992, p.167, R.Puchta et al. In Tens.Surf.Det, 30, 186 (1993), M. Brock in Tens. Surf. Det. 30, 394 (1993) and R. Lagerman et al. In J.Am.Oil. ch em.Soα, 71, 97 (1994).

The quaternized fatty acid triethanolamine ester salts follow the formula (II)

R ⁴ ι-

[R ¹ CO- (OCH ₂ CH2) _m OCH2CH2-N-CH2CH2θ- (CH2CH2θ) _n R ² ] X ^" (II)

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ 0) _q H group , m, n and p in total stand for 0 or numbers from 1 to 12, q stands for numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _{2 /} i ₈ coconut fatty acids and in particular partially hardened Ciβ tallow or palm fatty acids and high-elicid Ci _6/18 fatty acid cuts are preferably used.

The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the esterquats. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1, 5-1, 9 and are derived from technical C1 ₆ / 18- Talgbzw. Palm fatty acid (iodine number 0 to 40).

From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (II) have proven to be particularly advantageous in which R CO for an acyl radical having 16 to 18 carbon atoms, R ² for R CO, R ³ for hydrogen, R ⁴ for a methyl group, m , n and p is 0 and X is methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (III) are also suitable as esterquats,

R ⁴ r

[R ¹ CO- (OCH ₂ CH2) _m OCH ₂ CH2-N-CH ₂ CH ₂ 0- (CH ₂ CH ₂ 0) _n R ² ] X ^" (III)

I

R ⁵ in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IV) should be mentioned as a further group of suitable ester quats.

R ⁶ 0- (CH ₂ CH ₂ 0) _m OCR ¹

[R ⁴ -N-CH ₂ CHCH ₂ 0- (CH ₂ CH ₂ 0) _n R ² ] X ^" (IV)

IR ⁷

19 in the R 'CO for an acyl radical with 6 to 22 carbon atoms, R ^ for hydrogen or R CO, R, R and R independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers of 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimum degree of esterification, the examples given for (II) also apply to the esterquats of the formulas (IM) and (IV). The esterquats are usually commercially available in the form of 50 to 90% by weight alcoholic solutions, which can be diluted with water if required.

Further examples of the cationic surfactants which can be used in the compositions according to the invention are in particular quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldi methylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and AbilR-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego AmidRS 18, are particularly notable for their good biodegradability.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ^R 100, according to the CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The proportion of cationic surfactants in the compositions according to the invention is, for example, up to approximately 30% by weight, for example approximately 1 to approximately 20.0% by weight.

Ampholytic surfactants or betaines are also suitable as part of the compositions according to the invention.

Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids such as acrylic acid possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U. Ploog in Seifen-Öle-Fette-Wwachs, 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).

Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (V)

R ² I

R ¹ -N- (CH ₂ ) _n COOX (V)

in which R ¹ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ² for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³ 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 or ammonium.

Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Cι _{2 /} ι -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethyl- methyl amine, oleyl dimethyl amine, Ci _6/18 tallow alkyl dimethyl amine and technical mixtures thereof.

Carboxyalkylation products of amidoamines which follow the formula (VI) are also suitable,

R ² R ⁴ CO-NH- (CH ₂ ) _m -N- (CH ₂ ) _n COOX (VI) in which R ⁴ 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 ² , R ³ , n and X have the meanings given above.

Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and 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. Preference is given to using a condensation product of Cs _/ i ₈ coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Also suitable as suitable starting materials for the betaines to be used in accordance with the invention are imidazolines which follow the formula (VII)

in which R ^{5 is} an alkyl radical having 5 to 21 carbon atoms, R ^{6 is} a hydroxyl group, an OCOR ⁵ or NHCOR ⁵ 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 1} coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

In cases where the compositions according to the invention are detergents, the compositions according to the invention in their entirety usually contain one or more of the above-mentioned surfactant (s) in a total amount of 5 to 50% by weight, preferably in amounts of 10 up to 35% by weight.

In the cases where the compositions according to the invention are cleaning agents, in particular dishwashing detergents, they usually contain a surfactant or a mixture of two or more surfactants in a total amount of about 0.1 to about 10% by weight, preferably in amounts of about 0.5 to about 5% by weight

In addition to an anionic surfactant or a mixture of two or more anionic surfactants or a cationic surfactant or a mixture of two or more cationic surfactants or a mixture of one or more anionic and one or more cationic surfactants still contain a nonionic surfactant or a mixture of two or more nonionic surfactants.

Suitable nonionic surfactants are, for example, alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, the alcohol residue of which may or may not be methyl-branched linearly or preferably in the 2-position can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates are part of the compositions according to the invention linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₂ -alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C ₁₃ . ₁₅ - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ _ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of Cι ₂ .ι alcohol with 3 EO and Cι ₂ .i ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of nonionic surfactants preferably used as part of the compositions according to the invention, which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can advantageously be used as a constituent of the compositions according to the invention are the alkyl polyglycosides (APG). Usable alkyl polyglycosides satisfy the general formula R0 (G) ₂ , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The compositions according to the invention can contain alkyl polyglycosides, an APG content of the compositions according to the invention of more than 0.2% by weight, based on the total composition according to the invention, being preferred. Compositions suitable as washing or cleaning-active compositions contain, for example, APG in amounts of 0.2 to 10% by weight or from 0.2 to 5% by weight or in amounts of 0.5 to 3% by weight.

Anionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides are also suitable as constituents of the washing or cleaning-active compositions according to the invention. The total proportion of these nonionic surfactants in the compositions according to the invention is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other surfactants suitable as part of the compositions according to the invention are polyhydroxy fatty acid amides of the formula (VIII),

I

R-CO-N- [Z] (VIII)

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

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

R ¹ -0-R ²

I

R-CO-N- [Z] (IX)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C ₄ alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this rest.

The residue [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331 ', be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In addition to the above-mentioned surfactants, a composition according to the invention, if it is a washing or cleaning agent, can also contain builders.

The builders that can be used in the context of the present invention include, for example, zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, phosphates. Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ 0 yH ₂ 0 are preferred, β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.

As part of the compositions according to the invention, provided they are detergents or cleaning agents, amorphous sodium silicates with a modulus Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2, are also included , 8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compacting or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to the conventional ones Have water glasses are described for example in the German patent application DE-A-44 00 024. Particularly preferred for use in the context of the present invention are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

Zeolites, preferably finely crystalline, synthetic and bound water-containing zeolites such as zeolite A and / or P, can also be used as builders as constituents of the compositions according to the invention. Zeolite MAP (e.g. commercial product: Doucil A24 from Crosfield) is used as the P-type zeolite ) particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 ^• (1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^• (3.5 - 5.5) H ₂ 0

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

The generally known phosphates can also be used in the context of the present invention. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Examples of suitable organic builders and thus also as a constituent of the compositions according to the invention are the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that their use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergent and cleaning agent portions. In this context, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Polymeric polycarboxylates are also suitable as part of the compositions according to the invention. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of the present invention, the molecular weights stated for polymeric polycarboxylates are the weight-average molecular weight (M _w ) of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.

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 can again be selected from this group be preferred, the molar masses from 2,000 to 10,000 g / mol, particularly preferably from 3,000 to 5,000 g / mol.

Also suitable as constituents of the compositions according to the invention are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or 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 relative molar mass, based on 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 content of the compositions according to the invention is preferably about 0.5 to about 20% by weight, in particular about 3 to about 10% by weight.

To improve water solubility, suitable polymers can also have been prepared using allylsulfonic acids as monomer components, as described, for example, in EP-B 0 727 448, or using allyloxybenzenesulfonic acid and methallylsulfonic acid as monomer components.

Also biodegradable polymers made from more than two different monomer units, for example those which, according to DE-A 43 00 772, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or, according to DE-C 42 21 381, as monomer salts acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives are suitable as constituents of the compositions according to the invention.

Other copolymers suitable as constituents of the compositions according to the invention are those which are described in German patent applications DE-A 43 03 320 and DE-A 44 17 734 and as monomer units preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Polymeric aminodicarboxylic acids, their salts or their precursors should also be mentioned as suitable constituents of the compositions according to the invention. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A 195 40 086 that, in addition to co-builder properties, they also have a bleach-stabilizing effect.

Further suitable constituents of the compositions according to the invention are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A 0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other organic builder substances suitable as constituents of the compositions according to the invention 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 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 compared to dextrose, which is a DE of 100 owns. Both maltodextrins 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 molar masses in the range from 2,000 to 30,000 g / mol can be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known in particular from European patent applications EP-A 0 232 202, EP-A 0 427 349, EP-A 0 472 042 and EP-A 0 542 496 and from international patent applications WO 92/18542 , WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A 196 00 018 is also suitable. A product oxidized at C ^{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also suitable co-builders and thus other suitable constituents of the compositions according to the invention. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009 and 4,639,325, in European patent application EP-A 0 150 930 and in Japanese patent application JP-A 93 / 339,896 to be discribed.

If formulations containing zeolite and / or silicate are used in the compositions according to the invention, their content of the abovementioned compounds is from about 3 to about 15% by weight.

Further useful organic co-builders and thus other suitable constituents of the compositions according to the invention are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in international patent application WO 95/20029.

Another class of substances with co-builder properties and thus other suitable constituents of the compositions according to the invention are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt alkaline (pH = 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral reacting sodium salts, e.g. used as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced

Heavy metal binding capacity. Accordingly, in particular if the detergent or cleaning agent portions according to the invention also contain bleach, it may be preferred to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds which are capable of forming complexes with alkaline earth metal ions can be used as co-builders and thus as further suitable constituents of the compositions according to the invention.

In addition to the surfactant and builder constituents mentioned, the compositions according to the invention can, for example, contain other ingredients from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, which are customary in detergents or cleaning agents and contain corrosion inhibitors. The connections mentioned can be in the frame of the present invention, insofar as the state of matter and the chemical nature permit this, are used, for example, individually in the context of the method according to the invention. However, it is preferred according to the invention if the compositions according to the invention contain the compounds mentioned as a mixture with one or more of the substances or substance types mentioned above.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. If cleaning or bleaching preparations for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamido operadipic acid and N-nonenyl amide; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassyl acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1, 4-diacid, N, N-di-tere (6-aminopercaproic acid).

Substances which release chlorine or bromine can also be used as bleaching agents in compositions which are said to be suitable for machine dishwashing. Among the appropriate chlorine or bromine releasing materials For example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are suitable. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

If the compositions according to the invention are used in the production of a detergent, the compositions can have ingredients which have an influence on the bleaching effect. In order to achieve an improved bleaching effect, for example when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the compositions.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetine, diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the compositions according to the invention. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also with Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes Tripod ligands containing nitrogen and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.

According to a particularly preferred embodiment, the compositions according to the invention also contain further additives as are known from the prior art as additives for detergent or cleaning agent preparations.

Optical brighteners are an example of additives which can be used as a constituent of the compositions according to the invention, provided they are used as detergents or cleaning agents. Here, for example, the optical brighteners customary in detergents can be used. Examples of such optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4, 4'-bis (2-anilino-4-morpholinol, 3,5-triazinyl-6-amino-) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyryl type can be contained in the compositions according to the invention, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl-) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl-) diphenyl or 4- (4-chlorostyryl-) 4 '- (2nd -sulfostyryl-) biphenyl. Mixtures of the aforementioned brighteners can also be included.

Another group of suitable additives that can be used according to the invention are UV protection substances. These are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect. Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb are suitable.

Another group of additives which can be used in the compositions according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes are preferred here, as are usually used to improve the visual appearance of products in detergents and cleaning agents or in personal care products. The choice of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a high storage stability and insensitivity to the other ingredients of the detergent preparations and to light and have no pronounced substantivity to the uppermost layer of skin, textile fibers or keratin fibers, so as not to stain them. The dyes are present in the washing or cleaning agents or in the personal care products according to the invention in amounts of less than 0.01% by weight.

Another group of additives that can be contained in the washing or cleaning compositions according to the invention are bleaching catalysts, in particular bleaching catalysts for automatic dishwashing detergents or detergents. Complexes of manganese and cobalt are used here, especially with nitrogen-containing ligands. Another group of additives which can be contained in the compositions according to the invention, provided that these are compositions which come into contact with silver, for example dishwashing detergents, are silver protection agents. These are a large number of mostly cyclic organic compounds which are likewise familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process. Specific examples are triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

Soil repellents, that is to say polymers which absorb fibers or hard surfaces (for example on porcelain and glass), have a positive influence on the ability to wash oil and fat out of textiles and thus counteract re-soiling as further additives according to the invention may be present in the washing or cleaning compositions according to the invention , This effect is particularly evident when a textile or a hard object (porcelain, glass) is soiled that has already been washed several times beforehand with a washing or cleaning agent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also the Polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The additives mentioned are contained in the compositions according to the invention in amounts of at most 30% by weight, preferably 2 to 20% by weight. The washing or cleaning agents according to the invention or the personal care agents according to the invention can also contain fragrances. In principle, all fragrances which can usually be used in washing or cleaning agents are suitable as fragrances. If a washing or cleaning agent according to the invention or a personal care product according to the invention contains nano- or microcapsules, as have already been described in the context of the above text, and if such nano- or microcapsules already contain a fragrance or a mixture of two or more fragrances, then A washing or cleaning agent according to the invention or a personal care agent according to the invention can nevertheless contain a further fragrance or a mixture of two or more further fragrances which are not in encapsulated form. Such fragrances can be fragrances which are identical to the fragrance or fragrances present in encapsulated form. However, these can also be fragrances that differ from the fragrances present in encapsulated form. For example, it can be achieved that a substrate treated with a washing or cleaning agent according to the invention has a certain smell immediately after the treatment, while it shows a different smell after prolonged storage or use.

Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenylglycinate, allylcyclohexylpropylate propylate allyl propylate propionate. The ethers include, for example, benzyl ethyl ether. The aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionones, α-isomethyl ionone and methyl cedryl ketone. Alcohols include anethole, citronellol, eugenol, geraniol, linalool, Phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. If necessary, mixtures of different fragrances are used, which are coordinated so that they together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The content of non-encapsulated fragrances in the compositions according to the invention can be, for example, up to 2% by weight.

If a composition according to the invention is a personal care product, in particular a hair care product, such a preparation according to the invention can contain, in addition to one or more of the compounds already mentioned, one or more further compounds typical of such preparations.

Such preparations can contain, for example, a vitamin and / or a vitamin derivative in addition to or instead of one or more of the further compounds already listed. In principle, natural, synthetic, water-soluble or oil-soluble vitamins and vitamin derivatives are suitable.

Particularly suitable vitamins and vitamin derivatives are, for example, vitamin A, vitamin E, vitamin E acetate, vitamin E nicotinate, vitamin F, vitamin B ₃ , vitamin B ₆ , nicotinamide, vitamin H, vitamin C, vitamin B ₅ and its derivatives, in particular Panthenol, panthotenic acid, calcium panthotenate, panthotenyl ethyl ether, panthenyl hydroxypropyl steardimonium chloride (Panthequat®, Innovachem), panthetine and panthenyl triacetate. Analog derivatives, for example panthotenyl propyl ether, panthotenyl butyl ether and further branched or linear, saturated or unsaturated homologs, can of course also be used. The same applies to the salts of pantothenic acid, the possible counterions of which are not only limited to calcium, but also include all physiologically acceptable metal cations, for example the alkali and alkaline earth metals, in particular magnesium, sodium or potassium. The invention also encompasses the use of all possible stereoisomers of the different vitamins, it being possible in particular for the vitamin B ₅ and its derivatives to use both the D and the L form and all mixtures of the two forms according to the invention.

The use of vitamin C, vitamin H, vitamin E and its derivatives and vitamin B ₅ and its derivatives is preferred, the use of vitamin H, vitamin E acetate, panthenol, Panthequat® and vitamin B _{6 being} particularly preferred.

As a rule, the vitamins or vitamin derivatives are used in the preparations according to the invention intended for body care, in particular for hair care, in amounts of from 0.01 to 30% by weight, based on the preparation as a whole. Usually 0.02 to 15, in particular 0.02 to 8% by weight are particularly advantageous for the production of aqueous, ready-to-use preparations. In many cases, amounts between 0.05 and 5% by weight are sufficient. For concentrates, it can be advantageous to use vitamins and / or vitamin derivatives in amounts of 0.05 to 30% by weight, in particular 1 to 25% by weight and particularly preferably 3 to 20% by weight.

In addition to the components, the personal care products according to the invention can also contain protein hydrolyzates. Protein hydrolyzates are understood to be a mixture of amino acids, oligopeptides and polypeptides and their derivatives.

Amino acids which can be used according to the invention are, for example, arginine, lysine, cysteine, glutamine, asparagine and valine. Amino acid mixtures which can be obtained by largely completely basic, acidic or enzymatic hydrolysis of animal or vegetable proteins have also proven suitable. Oligopeptides and polypeptides which can be used according to the invention are, for example, animal or vegetable proteins or their (partial) hydrolysates obtained by acidic, basic or enzymatic means. Suitable proteins are, for example, keratin, collagen, elastin, soy protein, milk protein, casein, fibroine, sericin, wheat protein, silk protein and almond protein. Keratin and the vegetable proteins can be preferred according to the invention. The hydrolysis produces mixtures of substances with average molecular weights in the range from approximately 400 to approximately 50,000 Daltons. Usual average molecular weights are in the range from about 500 to about 8000 daltons. Hydrolysates of keratin and of vegetable proteins are preferred according to the invention.

Derivatives of amino acids, oligopeptides and polypeptides are understood according to the invention to mean their cationic derivatives and their condensation products with fatty acids.

Cationic derivatives are obtained by reaction with compounds which usually carry quaternary ammonium groups or by reaction with corresponding amines and subsequent quaternization.

A number of such quaternary protein hydrolyzates are available as commercial products, for example:

cationic collagen hydrolyzate, for example that under the name

Lamequat®L product on the market (INCI name: Lauryl-dimonium hydroxypropyl hydrolyzed collagen; Chemische Fabrik Grünau), cationic keratin hydrolyzate, for example the one under the name

Croquat® product on the market (CTFA name:

Cocodimonium Hydroxypropyl Hydrolyzed Keratin; Croda) cationic wheat hydrolyzate, available under the name Hydrotriti- cum®QL (CTFA name: Lauryldimonium Hydroxypropyl Hydrolyzed

Wheat protein; Croda) the product available under the name Crotein®Q, according to INCI

"Hydroxypropyltrimonium Hydrolyzed Collagen" (Croda) as well the quaternized protein hydrolyzate available as Lexein®QX 3000 (Inolex).

To produce the condensation products of protein hydrolyzates with fatty acids, oleic acid, myristic acid, undecylenic acid, coconut fatty acid and abietic acid are preferably used as the acid component. These condensation products can also be in the form of salts, in particular sodium, potassium and triethanolamine salts.

The condensation products based on collagen hydrolyzate also carry the CTFA names Oleoyl Hydrolyzed Collagen, Myristoyl Hydrolyzed Collagen, Oleoyl Hydrolyzed Animal Collagen, Potassium Coco Hydrolyzed Animal Protein, TEA Abietoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and TEA Coco Hydrolyzed Collagen. Commercial products include Lamepon®LPO, Lamepon®4 SK, Lamepon®UD, Lamepon®460, Lamepon®PA TR, Lamepon®ST 40 and Lamepon®S (Grünau) as well as Lexein®A 240, Lexein®S 620 and Lexein®A 520 (Inolex).

Condensation products of elastin hydrolyzates with fatty acids, for example lauric acid (CTFA name: Lauroyl Hydrolyzed Elastin), can also be used. Crolastin®AS (Croda) is a corresponding market product.

A Potassium Cocoyl Hydrolyzed Wheat Protein (Seiwa) is available under the name Promois EGCP.

Other commercial products that can be used according to the invention are Lexein®A 200 (Inolex), Lamepon®PO-TR, Lamepon®PA-K, Lamepon®S-MV and Lamepon®S-TR (Grünau) and Crotein®CCT (Croda).

A composition according to the invention, such as used as a personal care product, in particular as a hair care product, can also contain further, conventional additives.

Examples of such customary additives are: amphoteric surfactants, for example N-alkylglycines, N-alkylpropionic acids, N-

Alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the

Alkyl group, zwitterionic surfactants, for example the so-called betaines and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines, nonionic polymers, for example vinylpyrrolidoneΛ / inylacrylate copolymers,

Polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers,

Thickeners such as agar agar, guar gum, alginates, cellulose ethers, gelatin,

Pectins and / or xanthan gum,

Structurands such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example

Soy lecithin, egg lecithin and cephaline, as well as silicone oils,

Perfume oils, dimethyl isosorbitol and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol,

Glycerin and diethylene glycol,

dyes,

Anti-dandruff agents such as climbazole, piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as bisabolol, allantoin and plant extracts,

Light stabilizers,

Fats and waxes, such as walrus, beeswax, montan wax, paraffins, esters,

Glycerides and fatty alcohols,

fatty acid,

Swelling and penetration substances such as PCA, glycerin, propylene glycol monoethyl ether,

Carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex or styrene / acrylamide copolymers,

Pearlescent agents such as ethylene glycol mono- and distearate or PEG-3 distearate,

Blowing agents such as propane-butane mixtures, N ₂ 0, dimethyl ether, CO ₂ and air as well

Antioxidants. The compositions according to the invention can also have a proportion of water. The water content can be, for example, up to about 95% by weight.

The compositions according to the invention can contain the nano- or microcapsules provided in the context of the present invention in an amount of up to about 30% by weight, in particular in an amount of about 0.1 to about 25% by weight or about 0.5 to contain about 20% by weight or about 1 to about 15% by weight or about 5 to about 10% by weight. A composition according to the invention can contain, for example, only one type of microcapsule. However, it is also provided in the context of the present invention that a composition according to the invention contains a mixture of two or more different microcapsules, wherein the different microcapsules can differ, for example with regard to the composition of the capsule shell, the capsule content or both.

The compositions according to the invention are suitable as detergents, for example as heavy duty detergents, mild detergents, color detergents, wool detergents, fabric softeners, cleaning agents, for example

Dishwashing detergents, machine dishwashing detergents, rinse aids, cleaning agents for hard surfaces, in particular floors, soaps, shower gels or hair treatment agents, in particular shampoos, hair rinses, hair treatments, hair tints, hair tip fluids, colorants or wave lotions.

A powdery composition according to the invention that can be used as a detergent can have, for example, the following composition:

about 2 to about 12% by weight of a Na polycarboxylate about 13 to about 25% by weight of an alkylbenzenesulfonate about 0.5 to about 5% by weight of a phosphonate about 1 to about 8% by weight sodium sulfate about 30 to about 70% by weight of a zeolite about 0.1 to about 5 weight percent Na soap about 0.1 to about 6 weight percent ethoxylated tallow alcohol (5 EO) about 5 to about 15 weight percent water about 0.2 to about 20 weight percent. -% nano or micro capsules with

Fragrances.

is explained in more detail below with examples.

Examples

1. Preparation of modified cyanoacrylate esters

Modified cyanoacrylate esters were prepared as follows:

125 g of ethyl cyanoacrylate were heated with 100 g of cis-hexenol with 1% by weight of tetrabutyl titanate in the presence of 0.1 g of trifluoromethanesulfonic acid until no more elimination of ethanol was observed. The reaction mixture was quenched with 1.5 g of 85% phosphoric acid and the product was isolated from the mixture by fractional distillation.

2. Production of microcapsules

The following solutions were first prepared to prepare the microcapsules according to the invention:

a) 0.5 g Synperonic PE / F68, a low-foaming, nonionic surfactant, which is obtained by copolymerization of propylene oxide and ethylene oxide (manufacturer: ICI) was mixed with 95 ml of distilled water and with 5 ml of phosphate buffer to a pH value set from 7.

b) 95 ml of absolute ethanol were mixed with 0.25 ml of 0.1 N HCl.

c) 1.89 g of Miglyol 812 N (C12-18 triglyceride, manufacturer: Condea) were made up to 12.5 ml with solution b).

d) 0.25 g of cis-hexenylcyanoacrylate from Example 1 were made up to 12.5 ml with solution b).

Solution b) and c) were then pumped through the mixing chamber of a rotor-stator stirrer into the aqueous solution a) at a conveying speed of 0.5 ml / min. The aqueous solution was stirred at a speed stirred from 400 rpm. After solutions b) and c) had been completely introduced, the resulting milky suspension was stirred for a further hour. The resulting capsules had an average particle diameter of 1.7 μm.

3. Manufacture of microcapsules

The procedure was as in Example 2, but instead of Miglyol 812 N, 1.9 g of cis-hexenol were used.

4. Production and application of a fabric softener formulation

16% by weight of esterquat were mixed with 80% by weight of water and 4% by weight of cyanoacrylate capsules from Example 3. A mixture of 16% by weight of esterquats and 84% by weight of water served as a comparative example.

Cotton fabrics were treated with the fabric softener thus obtained, the quantity ratio of fabric softener to dry laundry being 10 g / kg, the liquor ratio being 1: 5 and the treatment time being 5 minutes.

Both the treated fabric sample according to the invention and the comparison sample had an essentially neutral odor immediately after washing.

Both samples were divided, one part being ironed and the other part being tumble dried. In both cases, a fresh, "green" fragrance could be perceived in the sample treated according to the invention. The comparison sample showed no changes in smell.

The microcapsules were used in the following formulations:

Softener formulations:

Example hair conditioner formula:

Sample powder detergent recipe:

Claims

claims

1. Cyanoacrylate esters of the general formula I

wherein R represents a branched, saturated or unsaturated, optionally substituted hydrocarbon radical with at least 6 C atoms or a linear unsaturated, optionally substituted hydrocarbon radical with at least 6 C atoms or an optionally substituted, saturated or unsaturated cyclic hydrocarbon radical with at least 5 C atoms or an aromatic hydrocarbon radical substituted with at least one linear or branched alkyl, alkenyl or alkoxy group and having at least 7 carbon atoms of a cosmetically active ingredient, a care substance, fragrance, lubricant or microbicide R-OH.

2. Polymer made using a compound according to claim 1.

3. polymer mixture containing a polymer according to claim 2 and at least one further polymer.

4. washing or cleaning-active composition or composition for personal care, at least containing an anionic surfactant or a mixture of two or more such surfactants or a cationic surfactant or a mixture of two or more such surfactants and a nano- or microcapsule consisting of a capsule shell and a capsule content, or a mixture of two or more such nano- or microcapsules, wherein the capsule shell contains at least one polycyanoacrylate ester and the capsule content contains at least one non-washing-active ingredient.

5. washing or cleaning active composition or composition for personal care according to claim 4, characterized in that it contains at least one nonionic surfactant.

6. washing or cleaning-active composition or composition for personal care according to claim 4 or 5, characterized in that it contains as capsule content at least one fragrance or an anti-adhesive or a mixture thereof.

7. washing or cleaning active composition or composition for personal care according to one of claims 4 to 6, characterized in that the capsule shell contains at least one polymer according to claim 2.

8. washing or cleaning active composition or composition for personal care according to one of claims 4 to 7, characterized in that it contains at least one builder substance.

9. washing or cleaning active composition or composition for personal care according to one of claims 4 to 8, characterized in that it contains the nano or microcapsules in an amount of up to about 30 wt .-%.

10. nano or microcapsules obtainable by interfacial polymerization of at least one monomer according to claim 1.

11. Use of nano- or microcapsules according to claim 10 as a component of washing or cleaning active compositions or compositions for personal care.