DE10302905A1 - Co-surfactants with unsaturated heterocyclic head groups - Google Patents

Abstract

The present invention relates to compounds with unsaturated heterocyclic head groups, processes for the preparation of the compounds according to the invention by reacting aldehydes or carboxylic acids or their derivatives with polyfunctional compounds which have at least one amino function and at least one further function from the group of the hydroxyl, diol, amino Have carboxyl functions, their use as co-surfactants and household detergents, household cleaners, personal cleansers or personal care products containing at least one compound according to the invention.

Description

The present invention relates reaction products of aldehydes or carboxylic acids or their derivatives with polyfunctional compounds that at least an amino function and at least one further function from the Have group of hydroxyl, diol, amino and carboxyl functions as well as their production and use as co-surfactants.

Surfactants are so-called amphiphiles molecules the in their molecular structure have a hydrophobic and a hydrophilic portion. By this property can Surfactant interface films and train so-called micelles. These are aggregates from tensides, which are in aqueous solutions form and can take different forms (balls, sticks, discs). micelles form above a certain concentration, the so-called critical micell educational concentration (KMK). Still own amphiphilic molecules the property of interfacial films between hydrophobic and hydrophilic phases and so for example emulsifying or foaming to act.

Co-surfactants are also amphiphilic Properties that are, however, not sufficient for micelles alone and interfacial films to be able to educate. However, they are stored and act between the surfactants an increase in the packing density of the amphiphiles (surfactants and Co-surfactants) in the structures formed by them, such as micelles or Interfaces. This lowers the critical micelle formation concentration and the surface tension also the interfacial tension between the watery surfactant solution and non-polar substances such as oils, so that the absorption capacity of the surfactant system for this Substances up to the formation of microemulsions increases. The result a higher one Solubilizing and emulsifying power, a higher one cleaning capacity as well as an increased stability of emulsions and foams. When using co-surfactants you can Micelles are already formed at a significantly lower surfactant concentration become.

Other effects which are caused by the use of the co-surfactants and the increased tendency towards aggregation of the amphiphiles are known. On the one hand, this is the aggregation transformation from spherical to anisometric micellar associates. This change in the structure of the micelles affects the rheology of the solutions contained in the micelles, especially in dilute solutions. At the same time, a shift of the present liquid-crystalline structures to lower concentrations occurs in the phase diagram, as a result of which a preferred formation of gel phases with a high packing density can be observed. As a result, lamellar micelle structures already occur at concentrations of significantly <10% by weight, which are otherwise only observed at significantly higher concentrations. Another interesting phenomenon is the formation, in addition to the known liquid-crystalline gel phases, of new superstructures that have interesting application properties. Of particular interest here are vesicular phases and so-called L ₃ phases, which are sponge-like and have microemulsion-like properties. They can be used in dilute concentration ranges to adjust the viscosity.

From the prior art are one Number of connections or connection classes known as Co-surfactants are suitable.

C ₅ -C ₁₀ alcohols have advantageous properties, but are often not used because of their characteristic smell.

Low ethoxylated alcohols such as for example low ethoxylated lauryl alcohol ethoxylates, diethylene glycol monohexyl ether or propylene glycol butyl ether in some surfactant systems to improve emulsification performance or foam stability to lead, point for Surfactant formulations with a high anionic surfactant content are too low polarity the head group.

Fatty acid ethanolamines are, for example to adjust the viscosity used in shampoos. However, you are suspected of nitrosamines train.

G. J. Smith describes in soaps, oils, fats, Wachsen, 105 (1979, pages 319 ff and 345 ff) the use of alkylamine oxides as a co-surfactant in various applications. They are also suspected Contain nitrosamines. Through an elaborate manufacturing technology this can be largely avoided.

Analogous to the amine oxides, too other zwitterionic surfactants, such as. B. sulfo- or carboxylammonio betaine as a co-surfactant be used. The formation of gel phases is very high with these products weakly pronounced. Instead, they have the application advantage that the skin irritation is lowered by appropriate surfactant mixtures.

WO 98/00418 discloses alkylene carbonates and their use as co-surfactants.

In the applications known so far the ratio used fluctuates of co-surfactants to tensides depending on the application from approx. 1:20 to 1: 2. In some cases such as B. alkylamine oxides, the co-surfactant can also be more concentrated his.

The object of the present invention is to provide suitable compounds as co-surfactants which do not have the disadvantages mentioned, in particular show better cost efficiency and are environmentally friendly and free from risks for humans and have a low skin irritation point.

in denen die Symbole X, Y und R¹ bis R⁸ die folgende Bedeutung aufweisen:
R¹ ist eine lineare oder verzweigte, substituierte oder unsubstituierte C₃-C₂₉-Alkylgruppe oder eine lineare oder verzweigte, substituierte oder unsubstituierte C₃-C₂₉-Alkenylgruppe, wobei ein oder mehrere Kohlenstoffatome in der Alkyl- oder Alkenylkette durch -O-, – NR¹⁴, -C(O)NR¹⁵- oder -S- ersetzt sein können und -O-O- und -S-S-ausgeschlossen sind;
R² ist Wasserstoff oder -CH₃;
R³, R⁴, R⁵ und R⁶ sind unabhängig voneinander ausgewählt aus der Gruppe von Substituenten bestehend aus: H; -CN; -C(O)OH; -C(O)OR¹⁸; -C(O)NR¹⁹R²⁰; C₆H₅, bei dem ein oder mehrere Wasserstoffe durch Substituenten ersetzt sein können;

und C₁-C₅-Alkylgruppen, die an einer beliebigen Stelle der Kette 1 bis 4 Substituenten aus der Gruppe -OH; -SH; -CN; NR¹⁶R¹⁷; -OR²²; oder 1 bis 2 Substituenten aus der Gruppe bestehend aus -C(O)OH; -C(O)OR¹⁸; -C(O)NR¹⁹R²⁰; -OSO₃ ^–; -SO₃ ^–; -OPO₃ ^{2 –}; OPO(OR²¹)₂; C₆H₅, bei dem ein oder mehrere Wasserstoffe durch Substituenten ersetzt

aufweisen können;
R⁷ und R⁸ sind unabhängig voneinander ausgewählt aus der Gruppe von Substituenten bestehend aus: H; -CN; -C(O)OH; -C(O)OR¹⁸; -C(O)NR¹⁹R²⁰; C₆H₅, bei dem ein oder mehrere Wasserstoffe durch Substituenten ersetzt sein können;

und C₁-C₅-Alkylguppen, die an einer beliebigen Stelle der Kette 1 bis 4 Substituenten aus der Gruppe -OH; -SH; -CN; NR¹⁶R¹⁷; -OR²²; oder 1 bis 2 Substituenten aus der Gruppe bestehend aus -C(O)OH; -C(O)OR¹⁸; -C(O)NR¹⁹R²⁰; -OSO₃ ^–; -SO₃ ^–; -OPO₃ ^2–; OPO(OR²¹)₂; C₆H₅, bei dem ein oder mehrere Wasserstoffe durch Substituenten ersetzt sein können; und

aufweisen können;
R¹⁴ ist eine lineare oder verzweigte C₁-C₄-Alkylgruppe;
R¹⁵ ist Wasserstoff oder eine lineare oder verzweigte C₁-C₄-Alkylgruppe;
R¹⁶, R¹⁷ sind unabhängig voneinander Wasserstoff oder eine lineare oder verzweigte C₁-C₄-Alkylgruppe;
R¹⁸ ist ausgewählt aus der Gruppe bestehend aus C₁-C₆-Alkylgruppen und Ethylenoxigruppen-(CH₂-CH₂O)_p;
R¹⁹, R²⁰ haben unabhängig die gleiche Bedeutung wie R¹⁶, R¹⁷;
R²¹ ist eine C₁-C₄-Alkylgruppe oder -C₆H₅;
R²² ist ausgewählt aus der Gruppe bestehend aus C₁-C₁₀-Alkylgruppen, Acylgruppen -C(O)R²³ und der Gruppe bestehend aus Ethylenoxigruppen -(CH₂-CH₂O-)_q, Propylenoxigruppen -(CH(CH₃)-CH₂O-)_r, Butylenoxigruppen-(C₄H₉O-)_s, und Alkylenoxigruppen enthaltend mindestens zwei der vorstehend genannten Gruppen in Form von Block- oder statistischen Copolymeren und enthaltend insgesamt maximal 15 Alkylenoxieinheiten;
R²³ ist eine C₁-C₁₈-Alkylgruppe;
X bei Formel I, II und III ist O, S, oder NR²⁴,
Y bei Formel I und II ist N; und Y bei Formel III ist NR²⁴;
R²⁴ ist Wasserstoff oder eine C₁-C₄-Alkylgruppe, die an einer bis drei Positionen (in Abhängigkeit von der Zahl der Kohlenstoffatome der Alkylgruppe) weitere Substituenten auasgewählt aus der Gruppe bestehend aus -OH, -NH₂, -OR²² und NR¹⁶R¹⁷ enthalten kann;
n ist 0 oder 1;
p ist eine ganze Zahl von 1 bis 15;
q ist eine ganze Zahl von 1 bis 15;
r ist eine ganze Zahl von 1 bis 15;
s ist eine ganze Zahl von 1 bis 15;
und wobei der nicht aus dem Einsatzaldehyd oder der Einsatzcarbonsäure bzw. dem Einsatzester stammende aliphatische Teil der Verbindungen der Formel I, II oder III mindestens 3 Kohlenstoffatome aufweisen muss.This object is achieved by unsaturated cyclic compounds of the general formulas

in which the symbols X, Y and R ¹ to R ^{8 have} the following meaning:
R ¹ is a linear or branched, substituted or unsubstituted C ₃ -C ₂₉ alkyl group or a linear or branched, substituted or unsubstituted C ₃ -C ₂₉ alkenyl group, one or more carbon atoms in the alkyl or alkenyl chain being denoted by -O- , - NR ¹⁴ , -C (O) NR ¹⁵ - or -S- can be replaced and -OO- and -SS-are excluded;
R ² is hydrogen or -CH ₃ ;
R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group of substituents consisting of: H; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents;

and C ₁ -C ₅ alkyl groups which have 1 to 4 substituents from the group -OH; SH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 to 2 substituents from the group consisting of -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^{2 -} ; OPO (OR ²¹ ) ₂ ; C ₆ H ₅ , in which one or more hydrogens are replaced by substituents

can have;
R ⁷ and R ⁸ are independently selected from the group of substituents consisting of: H; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents;

and C ₁ -C ₅ alkyl groups which have 1 to 4 substituents from the group -OH; SH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 to 2 substituents from the group consisting of -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have;
R ¹⁴ is a linear or branched C ₁ -C ₄ alkyl group;
R ¹⁵ is hydrogen or a linear or branched C ₁ -C ₄ alkyl group;
R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group;
R ¹⁸ is selected from the group consisting of C ₁ -C ₆ alkyl groups and ethylene oxy group (CH ₂ -CH ₂ O) _p ;
R ¹⁹ , R ²⁰ independently have the same meaning as R ¹⁶ , R ¹⁷ ;
R ²¹ is a C ₁ -C ₄ alkyl group or -C ₆ H ₅ ;
R ²² is selected from the group consisting of C ₁ -C ₁₀ alkyl groups, acyl groups -C (O) R ²³ and the group consisting of ethylene oxy groups - (CH ₂ -CH ₂ O-) _q , propylene oxy groups - (CH (CH ₃ ) -CH ₂ O-) _r , butyleneoxy groups (C ₄ H ₉ O-) _s , and alkyleneoxy groups containing at least two of the above-mentioned groups in the form of block or statistical copolymers and containing a maximum of 15 alkyleneoxy units in total;
R ²³ is a C ₁ -C ₁₈ alkyl group;
X in formulas I, II and III is O, S, or NR ²⁴ ,
Y in formula I and II is N; and Y in Formula III is NR ²⁴ ;
R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which, at one to three positions (depending on the number of carbon atoms in the alkyl group), further substituents selected from the group consisting of -OH, -NH ₂ , -OR ²² and May contain NR ¹⁶ R ¹⁷ ;
n is 0 or 1;
p is an integer from 1 to 15;
q is an integer from 1 to 15;
r is an integer from 1 to 15;
s is an integer from 1 to 15;
and wherein the aliphatic part of the compounds of the formula I, II or III not originating from the starting aldehyde or the starting carboxylic acid or the starting ester must have at least 3 carbon atoms.

The compounds of the formulas I, II and III are ideal for use as co-surfactants in the usual, washing and cleaning formulations known to the person skilled in the art. she have a particularly slight skin irritation.

The compounds of the formulas I, II or III can in principle be prepared in various ways. In general, the compounds of formulas I, II or III can be prepared by the following methods:
"Aldehyde" path

The compounds of the formulas I, II or III can can be obtained by a reaction in two steps ((a) and (b)):

Step a):

Reaction of an aldehyde or of an aldehyde mixture and a polyfunctional compound to be reacted therewith containing at least one primary amino function (when preparing compounds of the formulas I or II) or a primary or secondary amino function, R ^{4 is} hydrogen (when preparing compounds of the formula III) and at least one second functional group selected from hydroxyl, diol, carboxyl and primary and secondary amino functions or a mixture of polyfunctional compounds, optionally in the presence of a suitable acid, in a condensation reaction. Suitable conditions of the condensation reaction are known to the person skilled in the art.

Step b):

Heating the one obtained in step a) Reaction product in the presence of a basic compound. there may additionally evacuated and / or an alkylene oxide added. This is preferred Product from step a) first with a basic compound, preferably NaOH or KoH, particularly preferred in the form of an aqueous Solution, offset and then heated to a temperature> 50 ° C, preferred at a pressure less than atmospheric pressure. Then will the resulting reaction mixture preferably with alkylene oxides basic catalysis implemented. The conditions when implementing with Alkylene oxides are known to the person skilled in the art.

• – Zugabe eines basischen Katalysators zum Produkt aus Schritt a). Dies ist bevorzugt NaOH oder KOH, besonders bevorzugt eine wäßrige Lösung dieser Verbindungen, ganz besonders bevorzugt eine wäßrige KOH-Lösung.
• – Erwärmen des erhaltenen Gemisches bei gleichzeitiger Evakuierung. Die Temperatur wird auf > 50 °C, bevorzugt auf > 80 °C, besonders bevorzugt auf 80–150 °C, ganz besonders bevorzugt auf 80–130 °C angehoben. Man evakuiert dabei bevorzugt gleichzeitig auf einen Druck unterhalb Atmosphärendruck, bevorzugt < 100 mbar, besonders bevorzugt < 50 mbar, ganz besonders bevorzugt 5–30 mbar.
• – Nachdem alle flüchtigen Bestandteile evaporiert wurden, kann man erfindungsgemäße Produkte ohne weitere Addition von Alkylenoxiden erhalten, indem man den Druck z. B. durch Zugabe von Stickstoff auf Atmosphärendruck bringt, das Produkt abkühlen läßt und ausfüllt.
• – Will man zusätzlich alkoxylieren, kann man nun nach dem Fachmann bekannten Verfahren mit z. B. Ethylenoxid, Propylenoxid oder Butylenoxid umsetzen.

Step b) preferably comprises the following steps:

• - Add a basic catalyst to the product from step a). This is preferably NaOH or KOH, particularly preferably an aqueous solution of these compounds, very particularly preferably an aqueous KOH solution.
• - Heating the mixture obtained while evacuating. The temperature is raised to> 50 ° C, preferably to> 80 ° C, particularly preferably to 80-150 ° C, very particularly preferably to 80-130 ° C. It is preferably evacuated to a pressure below atmospheric pressure, preferably <100 mbar, particularly preferably <50 mbar, very particularly preferably 5-30 mbar.
• - After all volatile components have been evaporated, products according to the invention can be obtained without further addition of alkylene oxides by reducing the pressure, for. B. brings nitrogen to atmospheric pressure, allows the product to cool and fills.
• - If you want to alkoxylate additionally, you can now by known methods with z. B. implement ethylene oxide, propylene oxide or butylene oxide.

Without being bound by any theory, this reaction in step a) initially involves a condensation reaction of the aldehyde with the polyfunctional compound which has at least one amino group. First, a saturated nitrogen heterocycle is formed in step a), which - with formation of an unsaturated compound according to formulas I, II or III - eliminates an alcohol, preferably CH ₃ OH, in step b).

However, compounds of the formulas I and II can only be formed if the polyfunctional compound has at least one primary amino group, so that the nitrogen heterocycle initially formed has an NH group. The formation of compounds according to formula III is also possible if the polyfunctional compound has no primary amino group. In order to enable elimination, however, the R ⁴ radical must then be hydrogen.

Compounds are preferred by the "aldehyde" route of formula II obtained - in Dependence on their substitution pattern - too Isomerize compounds of formula I.

The compounds of the formulas I, II and III are prepared by conventional condensation reactions known to the person skilled in the art. The aldehyde and the polyfunctional compound to be reacted with it, if appropriate in the presence of a suitable acid, are reacted with one another in a suitable solvent such as, for example, toluene, chloroform or methylene chloride. The process is preferably carried out without a solvent. Suitable acids are the usual Lewis and Brönsted acids known to the person skilled in the art, which can be used in gaseous, liquid or solid form. Examples include HCl, sulfuric acid, p-toluenesulfonic acid, p-toluenesulfonic acid-pyridinium salt and acidic ion exchanger, for example Amberlyst ^® 15 and Serdolit Red. Alternatively to the presented aldehyde, which may be dissolved in a solvent (reaction is preferably performed again without solvent ), the starting material to be reacted with it is added. This is particularly advantageous in the case of hydroxycarboxylic acids, which can be added to the reaction mixture as an aqueous solution. The water formed during the condensation is preferably separated off by distillation. It is preferred to work without a solvent. If a solvent is used, the water can be separated off by azeotropic distillation, for example using a water separator.

The aldehydes to be used are linear or branched aliphatic C ₄ -C ₃₀ aldehydes, preferably C ₆ -C ₁₈ aldehydes, particularly preferably C ₆ -C ₁₆ aldehydes, very particularly preferably C ₇ or C ₈ aldehydes , These aldehydes have an average degree of branching from 0 to 2.5, preferably 0.2 to 1.6. The degree of branching is defined as (number of methyl groups per molecule) -1. Since the aliphatic chain residue of the aldehyde associated with the carbonyl function corresponds to the residue R ¹ in the formulas I and II, this latter residue also has a corresponding degree of branching. The alkyl chain can have further substituents which increase the suitability of the molecule as co-surfactant, but at least do not negatively influence it. Such substituents are known to the person skilled in the art. There are preferably no further substituents on the alkyl chain. Examples of usable aldehydes include butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal and hexadecanal. Of all the aldehydes mentioned above, both the unbranched n form and branched isomers can be used. In general, mixtures of isomers of the aldehydes used are used which have the desired average degree of branching.

It is also possible to use mixtures of aldehydes with different C numbers and to use the resulting product mixtures as co-surfactants. This embodiment is preferred according to the invention. It is particularly preferred to use a mixture of C ₁₂ - / C ₁₄ aldehydes or C ₁₃ / C ₁₅ aldehydes, ie mixtures of aldehydes with 12 and 14 carbon atoms or mixtures of aldehydes with 13 and 15 carbon atoms.

Furthermore, the use of so-called Guerbet aldehydes and their unsaturated Analogs according to the invention prefers. These are aldehydes with one branch in 2 position. Examples include 2-ethylhexanal, 2-ethylhex-2-enal, 2-propylhexanal, 2-propylheptanal, 2-propylhept-2-enal, 2-butyloctanal, 2-butyloct-2-enal, 2-pentylnonanal and 2-pentylnon-2-enal. saturated Aldehydes are preferred.

"Carboxylic acid" path:

The compound of formula I can can be obtained in a condensation reaction known per se a carboxylic acid their derivative, e.g. an ester, amide, cyanide, or a mixture of different carboxylic acids or their derivatives with a polyfunctional compound or containing a mixture of several polyfunctional compounds at least one primary each and at least one second functional group selected from Hydroxyl, diol, carboxyl and primary and secondary amino functions.

The condensation reaction can optionally be carried out in the presence of an acid or base. However, the reaction is preferably carried out without the addition of a further acid or base. The reaction is preferably carried out by combining the carboxylic acid or its derivative or mixtures thereof and then heating the mixture to temperatures of generally 100 to 300 ° C., preferably 150 to 250 ° C, over a period of generally more than 2 hours, preferably 4 to 48 hours, water of reaction formed is preferably distilled off continuously during the reaction.

wobei R¹ bereits vorstehend definiert wurde und Z ein Halogen-Atom, bevorzugt Cl, ein Alkoxid-Rest der Formel -OR²², wobei R²² bereits vorstehend definiert wurde oder ein Aminrest-NR¹⁶R¹⁷ ist.The carboxylic acids or their derivatives to be used are compounds of the general formula

where R ^{1 has} already been defined above and Z is a halogen atom, preferably Cl, an alkoxide radical of the formula -OR ²² , where R ^{22 has} already been defined above or an amine radical NR ¹⁶ R ¹⁷ .

Furthermore, a carboxylic acid derivative of the structure R1-CN can be used, where R ^{1 has} already been defined above.

The carboxylic acids or their derivatives to be used are preferably linear or branched aliphatic C ₄ -C ₃₀ carboxylic acids, preferably C ₆ -C ₁₈ carboxylic acids, particularly preferably C ₆ -C ₁₆ carboxylic acids, very particularly preferably C ₇ - or C ₈ carboxylic acids. These carboxylic acids have an average degree of branching from 0 to 2.5, preferably 0.2 to 1.6. The degree of branching is defined as (number of methyl groups per molecule) -1. Since the aliphatic chain radical of the carboxylic acids associated with the carbonyl function corresponds to the radical R ¹ in the formulas I, II and III, this latter radical also has a corresponding degree of branching. The alkyl chain can have further substituents which increase the suitability of the molecule as co-surfactant, but at least do not negatively influence it. Such substituents are known to the person skilled in the art. There are preferably no further substituents on the alkyl chain. Examples of carboxylic acids that can be used include butyric acid (butanoic acid), valeric acid (pentanoic acid), caproic acid (hexanoic acid), heptanoic acid, caprylic acid (octanoic acid), nonanoic acid, capric acid (decanoic acid), undecanoic acid, lauric acid (dodecanoic acid), tridecanoic acid, tetradecic acid (hexadanoic acid) and palmitic acid (palmitic acid). Of all carboxylic acids, both the unbranched n form and branched isomers can be used. Isomer mixtures of the carboxylic acids used are generally used which have the desired average degree of branching. Instead of the carboxylic acids mentioned, their corresponding esters, amides or cyanides can also be used. So you can in the condensation reaction z. B. instead of n-nonanoic acid, use n-octyl cyanide and receives the same product from the structural formula.

It is also possible to use mixtures of carboxylic acids and / or carboxylic acid derivatives of different carbon numbers and to use the resulting product mixtures as co-surfactants. This embodiment is preferred according to the invention. The use of a mixture of C ₁₂ - / C ₁₄ carboxylic acids or C ₁₃ / c ₁₅ carboxylic acids is particularly preferred.

Furthermore, the use of carboxylic acids and their derivatives with a branch in the 2-position preferred. Examples include 2-ethylhexanoic acid, 2-Ethylhex-2-enoic, 2-propylhexanoic acid, 2-propylheptanoic acid, 2-propylhept-2-enoic acid, 2-butyloctanoic acid, 2-butyloct-2-enoic acid, 2-pentylnonanoic acid and 2-Pentylnon-2-enoic. saturated carboxylic acids are preferred.

For those with the aldehyde or the carboxylic acid or their derivatives to be converted polyfunctional starting materials it is the substances listed below, the polyfunctional connection in the manufacture of connections of formulas I or II according to a method according to the "aldehyde" route at least one primary. amino group having.

alkanolamines:

Linear and branched aliphatic C ₃ -C ₆ alkanolamines with at least one primary or secondary amino function and one hydroxyl function are suitable. A maximum of 4 further hydroxyl or amino functions can be present, preferably the alkanolamine has exactly one amino function. There may be further substituents from the group: -SH; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; -OR ²² ; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

Examples of suitable alkanolamines include trimethylolmethylamine, diethanolamine, propanolamine, dipropanolamine, 2-amino-2-alkyl-propanediol, where "alkyl" is preferably "methyl" or "ethyl", aminozu cker, amino acids such as sarcosine, serine and threonine.

diamines:

Linear and branched aliphatic C ₃ -C ₆ diamines with 2 to 6 primary or secondary amino functions can be used. The diamines preferably have 2 to 4 primary or secondary amino functions. There may be further substituents from the group: -OH; SH; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ -; -SO ₃ -; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; -OR ²² ; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

Examples of suitable diamines include propylene diamine, diethylenetriamine, triethylenetetramine, N-aminopropylethylenediamine (N ₃ -amine), and N, N'-bis (aminopropyl) ethylenediamine _(N4 amine), hydroxyethylethylenediamine.

aminothiols:

Linear and branched aliphatic C ₃ -C ₆ aminothiols with at least one primary or secondary amino function and one thiol function are suitable. The aminothiol used preferably has exactly one primary or secondary amino function and exactly one thiol function. There may be further substituents from the group: -OH; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ^3– ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; -OR ²² ; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

Examples include cysteine and tyrosine and mercaptopropylamine.

Amino acids:

Linear and branched aliphatic C ₃ -C ₆ amino acids with at least one primary or secondary amino function and one carboxyl function are suitable. The amino acids used according to the invention preferably contain a primary or secondary amino function. Examples include iminodiacetic acid HN (CH ₂ CO ₂ H) ₂ and ethylenediaminetriacetic acid, as well as the amino acids alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine Threonine, tryptophan, tyrosine, valine, and N-phosphonomethylglycine.

Particularly preferred polyfunctional Compounds are the alkanolamines mentioned.

The alkyleneoxy substituents which may be present in the cosurfactants of the formulas I, II and III used according to the invention (see for example the definition of R ²² ) can be pure ethyleneoxy, propyleneoxy or butyleneoxy substituents. In the case of butyleneoxy substituents, they can be those derived from 1-butene, 2-butene or isobutene. Within the group of butyleneoxy substituents, the group derived from 1-butene is - (CH ₂ CH (C ₂ H ₅ ) -O). However, these substituents can also consist of mixtures of ethyleneoxy, propyleneoxy or butyleneoxy units, for example as a statistical oligomer / polymer or as a block copolymer. The alkyleneoxy substituents mentioned are preferably pure ethyleneoxy groups or end-capped ethyleneoxy groups.

If there is a single connection, contains the alkyleneoxy substituents, it contains an integer amount on alkyleneoxy units, in those specified in the description Amounts. If there are mixtures of different compounds with alkyleneoxy substituents, this is often the case mixtures in which the amount of alkyleneoxy substituents on average no longer is an integer.

-C ₆ H ₅ denotes a phenyl group.

und C₁-C₅-Alkylgruppen, die an einer beliebigen Stelle der Kette 1 oder 2 Substituenten aus der Gruppe -OH; -CN; NR¹⁶R¹⁷; -OR²²; oder 1 Substituent aus der Gruppe bestehend aus -C(O)OH; -C₆H₅, bei dem ein oder mehrere Wasserstoffe durch Substituenten ersetzt sein können; und

aufweisen können;
R⁷ und R⁸ sind unabhängig voneinander ausgewählt aus der Gruppe bestehend aus: -H; -C(O)OH; -C(O)OR¹⁸;

und C₁-C₅-Alkylgruppen, die an einer beliebigen Stelle der Kette 1 oder 2 Substituenten aus der Gruppe -OH; -CN; NR¹⁶R¹⁷; -OR²²; oder 1 Substituent aus der Gruppe bestehend aus -C(O)OH; -C₆H₅, bei dem ein oder mehrere Wasserstoffe durch Substituenten ersetzt sein können; und

aufweisen können;
R¹⁴ ist eine lineare oder verzweigte C₁-C₄-Alkylgruppe;
R¹⁶, R¹⁷ sind unabhängig voneinander Wasserstoff oder eine lineare oder verzweigte C₁-C₄-Alkylgruppe;
R¹⁸ ist ausgewählt aus der Gruppe bestehend aus C₁-C₆-Alkylgruppen und Ethylenoxigruppen -(CH₂-CH₂O-)_p;
R²² ist ausgewählt aus der Gruppe bestehend aus C₁-C₄-Alkylgruppen, Acylgruppen -C(O)R²³ und der Gruppe bestehend aus Ethylenoxigruppen -(CH₂-CH₂O-)_q, Propylenoxigruppen -(CH(CH₃)-CH₂O-)_r und Butylenoxigruppen -(C₄H₉O-)_s sowie gemischten Alkylenoxigruppen;
R²³ ist eine C₁-C₁₈-Alkylgruppe;
X bei Formel I, II und III ist O oder NR²⁴,
Y bei Formel I und II ist N; und Y bei Formel III ist NR²⁴;
R²⁴ ist Wasserstoff oder eine C₁-C₄-Alkylgruppe, die an ein bis zwei Positionen (in Abhängigkeit von der Zahl der Kohlenstoffatome in der Alkylkette) weitere Substituenten aus der Gruppe bestehend aus -OH, -NH₂, -OR²² und NR¹⁶R^{1 7} enthalten kann;
n ist 0 oder 1;
p ist eine ganze Zahl von 1 bis 15;
q ist eine ganze Zahl von 1 bis 10;
r ist eine ganze Zahl von 1 bis 10;
s ist eine ganze Zahl von 1 bis 10;
und wobei der nicht aus dem Einsatzaldehyd oder der Einsatzcarbonsäure bzw. dem Einsatzester stammende aliphatische Teil der Verbindungen der Formel I, II oder III mindestens 3 Kohlenstoffatome aufweisen muss.Preferred molecules of the general formulas I, II and III are those in which one or more of the symbols X and Y, one or more of the substituents R ¹ to R ⁸ and n have the following meaning:
R ¹ is a linear or branched C ₅ -C ₁₇ alkyl group or a linear or branched C ₃ -C ₁₇ alkenyl group, where one or more carbon atoms in the alkyl chain can be replaced by O or NR ¹⁴ and -OO- is excluded;
R ² is -H;
R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of: -H; -C (O) OH; -C (O) OR ¹⁸ ;

and C ₁ -C ₅ alkyl groups which have 1 or 2 substituents from the group -OH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 substituent from the group consisting of -C (O) OH; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have;
R ⁷ and R ⁸ are independently selected from the group consisting of: -H; -C (O) OH; -C (O) OR ¹⁸ ;

and C ₁ -C ₅ alkyl groups which have 1 or 2 substituents from the group -OH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 substituent from the group consisting of -C (O) OH; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have;
R ¹⁴ is a linear or branched C ₁ -C ₄ alkyl group;
R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group;
R ¹⁸ is selected from the group consisting of C ₁ -C ₆ alkyl groups and ethylene oxy groups - (CH ₂ -CH ₂ O-) _p ;
R ²² is selected from the group consisting of C ₁ -C ₄ alkyl groups, acyl groups -C (O) R ²³ and the group consisting of ethylene oxy groups - (CH ₂ -CH ₂ O-) _q , propylene oxy groups - (CH (CH ₃ ) -CH ₂ O-) _r and butylene oxy groups - (C ₄ H ₉ O-) _s and mixed alkylene oxy groups;
R ²³ is a C ₁ -C ₁₈ alkyl group;
X in formula I, II and III is O or NR ²⁴ ,
Y in formula I and II is N; and Y in Formula III is NR ²⁴ ;
R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which, at one or two positions (depending on the number of carbon atoms in the alkyl chain), contains further substituents from the group consisting of -OH, -NH ₂ , -OR ²² and May contain NR ¹⁶ R ^{1 7} ;
n is 0 or 1;
p is an integer from 1 to 15;
q is an integer from 1 to 10;
r is an integer from 1 to 10;
s is an integer from 1 to 10;
and wherein the aliphatic part of the compounds of the formula I, II or III not originating from the starting aldehyde or the starting carboxylic acid or the starting ester must have at least 3 carbon atoms.

It is preferred if all of the substituents R ¹ to R ¹⁸ and symbols X and Y and n have the meaning given above.

aufweisen können;
R⁷ und R⁸ sind unabhängig voneinander ausgewählt aus der Gruppe bestehend aus: -H; und C₁-C₃-Alkylgruppen, die an einer beliebigen Stelle der Kette 1 oder 2 Substituenten aus der Gruppe -OH; NR¹⁶R¹⁷; oder 1 Substituent aus der Gruppe bestehend aus

aufweisen können;
R¹⁶, R¹⁷ sind unabhängig voneinander Wasserstoff oder eine lineare oder verzweigte C₁-C₄-Alkylgruppe;
R²² ist ausgewählt aus der Gruppe bestehend aus C₁-C₄-Alkylgruppen, Acylgruppen -C(O)R²³ und der Gruppe bestehend aus Ethylenoxigruppen -(CH₂-CH₂O-)_q, Propylenoxigruppen -(CH(CH₃)-CH₂O-)_r und Butylenoxigruppen -(CH₂CH(C₂H₅-O-)_s- sowie gemischten Alkylenoxigruppen;
R²³ ist eine C₁-C₁₈-Alkylgruppe;
X bei Formel I, II und III ist O oder NR²⁴,
Y bei Formel I und II ist N; und Y bei Formel III ist NR²⁴;
R²⁴ ist Wasserstoff oder eine C₁-C₄-Alkylgruppe, die an ein bis zwei Positionen (in Abhängigkeit von der Zahl der Kohlenstoffatome der Alkylgruppe) weitere Substituenten aus der Gruppe bestehend aus -OH, NH₂, -OR²² und NR¹⁶R¹⁷ enthalten kann;
n ist 0 oder 1;
q ist eine ganze Zahl von 1 bis 10;
r ist eine ganze Zahl von 1 bis 10;
s ist eine ganze Zahl von 1 bis 10;
und wobei der nicht aus dem Einsatzaldehyd oder der Einsatzcarbonsäure bzw. dem Einsatzester stammende aliphatische Teil der Verbindungen der Formel I, II oder III mindestens 3 Kohlenstoffatome aufweisen muss.Also preferred are the compounds of the formulas I, II and III in which one or more of the symbols X, Y and n and one or more of the substituents R ¹ to R ^{8 have} the following meaning:
R ¹ is a linear or branched C ₅ -C ₁₇ alkyl group, preferably a linear or branched C ₆ -C ₁₆ alkyl group or a linear or branched C ₅ -C ₁₇ alkenyl group, preferably a linear or branched C ₆ -C ₁₆ alkenyl group;
R ² is -H;
R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; -NR ¹⁶ R ¹⁷ ; -OR ²² ; and

can have;
R ⁷ and R ⁸ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; NR ¹⁶ R ¹⁷ ; or 1 substituent from the group consisting of

can have;
R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group;
R ²² is selected from the group consisting of C ₁ -C ₄ alkyl groups, acyl groups -C (O) R ²³ and the group consisting of ethylene oxy groups - (CH ₂ -CH ₂ O-) _q , propylene oxy groups - (CH (CH ₃ ) -CH ₂ O-) _r and butylene oxy groups - (CH ₂ CH (C ₂ H ₅ -O-) _s - as well as mixed alkylene oxy groups;
R ²³ is a C ₁ -C ₁₈ alkyl group;
X in formula I, II and III is O or NR ²⁴ ,
Y in formula I and II is N; and Y in Formula III is NR ²⁴ ;
R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which, at one or two positions (depending on the number of carbon atoms in the alkyl group), contains further substituents from the group consisting of -OH, NH ₂ , -OR ²² and NR ¹⁶ R ¹⁷ may contain;
n is 0 or 1;
q is an integer from 1 to 10;
r is an integer from 1 to 10;
s is an integer from 1 to 10;
and wherein the aliphatic part of the compounds of the formula I, II or III not originating from the starting aldehyde or the starting carboxylic acid or the starting ester must have at least 3 carbon atoms.

It is preferred if all of the substituents R ¹ to R ⁸ and the symbols X and Y and n have the meaning given above.

Even more preferred are the compounds of the formulas I, II and III, in which one or more of the symbols X, Y and n and one or more of the substituents R ¹ to R ^{8 have} the following meaning:
R ¹ is a linear or branched C ₅ -C ₁₇ alkyl group, preferably a linear or branched C ₆ -C ₁₆ alkyl group or a linear or branched C ₅ -C ₁₇ alkenyl group, preferably a linear or branched C ₆ -C ₁₆ alkenyl group;
R ² is -H;
R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; -NR ¹⁶ R ¹⁷ ; -OR ²² ;
R ⁷ and R ⁸ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; NR ¹⁶ R ¹⁷ ;
R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group;
R ²² is selected from the group consisting of C ₁ -C ₄ alkyl groups and ethylene oxy groups - (CH ₂ -CH ₂ O-) _q ;
X in formulas I, II and III is O, S, or NR ²⁴ ,
Y in formula I and II is N; and Y in Formula III is NR ²⁴ ;
R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which, at one or two positions (depending on the number of carbon atoms in the alkyl group), contains further substituents from the group consisting of -OH, -NH ₂ , -OR ²² and - May contain NR ¹⁶ R ¹⁷ ;
n is 0 or 1;
q is an integer from 3 to 8;
and the one not originating from the starting aldehyde or the starting carboxylic acid or the starting ester aliphatic part of the compounds of formula I, II or III must have at least 3 carbon atoms.

It is preferred if all of the substituents R ¹ to R ⁸ and the symbols X and Y and n have the meaning given above.

Compounds of the formulas I, II and III in which the radical R ^{1 is} a branched or unbranched C ₇ H ₁₅ alkyl radical or a mixture of branched and unbranched C ₇ H ₁₅ alkyl radicals are very particularly preferred. The C ₇ H ₁₅ alkyl radical is very particularly preferably a C ₄ H ₉ CH (C ₂ H ₅ ) CH ₂ radical, it being possible for the C ₄ H ₉ alkyl radical in turn to be branched or unbranched. The C ₄ H ₉ CH (C ₂ H ₅ ) CH ₂ radical is very particularly preferably in the form of a mixture of at least two isomeric forms, 70 to 99% by weight of compounds in which C ₄ H _{9 is} nC ₄ H ₉ and contains 1 to 30% by weight of compounds in which C ₄ H _{9 is} C ₂ H ₅ CH (CH ₃ ) and / or CH ₃ CH (CH ₃ ) CH ₂ . Furthermore, compounds of the formulas I, II and III are preferred in which R ^{1 is} a branched or unbranched C ₁₂ H ₂₅ or C ₁₄ H ₂₉ alkyl radical or a mixture of these two radicals or with the C ₇ H ₁₅ alkyl radical mentioned above ,

Also the subject of the most preferred embodiment of the present invention are the adducts of the compounds according to the invention with 3 to 10 ethylene oxide units as well as mixtures thereof. The term "mixtures" are used in connection with the present Invention understood both mixtures of adducts of a compound according to the invention with different amounts of added ethylene oxide units as well as mixtures of ethylene oxide adducts of various compounds according to the invention. Such compounds are very particularly preferred.

2-(1-Ethyl-pentyl)-4-methyl-4-hydroxymethyl-4,5-dihydro-oxazol

2-(1-Ethyl-pentyl)-4-ethyl-4-hydroxymethyl-4,5-dihydro-oxazol

2-(1-Ethyl-pentyl)-4-di(hydroxymethyl)-4,5-dihydro-oxazol

(1a) n = 3
(1b) n = 6
(1c) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(2a) n = 3
(2b) n = 6
(2c) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(3a) n + m = 3
(3b) n + m = 6
(3c) m + n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(4a) n = 0
(4b) n = 3
(4c) n = 6
(4d) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(5a) n = 0
(5b) n = 3
(5c) n = 6
(5d) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(6a) n = 0
(6b) n = 3
(6c) n = 6
(6d) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(7a) n = 0
(7b) n = 3
(7c) n = 6
(7d) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(8a) n = 0
(8b) n = 3
(8c) n = 6
(8d) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(9a) n = 0
(9b) n = 3
(9c) n = 6
(9d) n = 10
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)

(10) 2-(1-Ethyl-pentyl)-1-(2-hydroxyethyl)-4,5-dihydro-imidazol

(10a) n = 1
(10b) n = 4
(10c) n = 7
(10d) n = 11
(jeweils zu verstehen als Mittelwert – bezogen auf Moläquivalente – einer Molekulargewichtsverteilung)The following compounds, which can be present individually or in a mixture with one another, are particularly preferred and are selected from the group consisting of:

2- (1-ethyl-pentyl) -4-methyl-4-hydroxymethyl-4,5-dihydro-oxazole

2- (1-ethyl-pentyl) -4-ethyl-4-hydroxymethyl-4,5-dihydro-oxazole

2- (1-ethyl-pentyl) -4-di (hydroxymethyl) -4,5-dihydro-oxazol

(1a) n = 3
(1b) n = 6
(1c) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(2a) n = 3
(2b) n = 6
(2c) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(3a) n + m = 3
(3b) n + m = 6
(3c) m + n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(4a) n = 0
(4b) n = 3
(4c) n = 6
(4d) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(5a) n = 0
(5b) n = 3
(5c) n = 6
(5d) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(6a) n = 0
(6b) n = 3
(6c) n = 6
(6d) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(7a) n = 0
(7b) n = 3
(7c) n = 6
(7d) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(8a) n = 0
(8b) n = 3
(8c) n = 6
(8d) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(9a) n = 0
(9b) n = 3
(9c) n = 6
(9d) n = 10
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(10) 2- (1-ethylpentyl) -1- (2-hydroxyethyl) -4,5-dihydro-imidazole

(10a) n = 1
(10b) n = 4
(10c) n = 7
(10d) n = 11
(to be understood as an average - based on molar equivalents - of a molecular weight distribution)

Mixtures of (6) and (7), mixtures from (8) and (9) and mixtures of (6), (7), (8) and (9). There are mixtures from (6), (7), (8) and (9) are particularly preferred.

Another object of the invention is the use of the compounds of general formulas I, II and III and the derived preferred compounds such as specified above as co-surfactant. The compounds of the invention are particularly characterized by the fact that the skin irritation is very is low, i.e. they are particularly preferred when skin contact can occur.

The inventive to be used as co-surfactants Substances of the formulas I, II and III are suitable for use in industrial, institutional or household detergents and cleaners as well as in the so-called body care sector, i.e. body cleaning and care products.

• – Feuchthaltemittel, insbesondere für die Druckindustrie.
• – Kosmetische, pharmazeutische und Pflanzenschutzformulierungen. Geeignete kosmetische Formulierungen sind beispielsweise in der deutschen Anmeldung mit dem Aktenzeichen 103 01 704.6 mit dem Titel „Alkylglycolalkoxylate oder Dialkylglycolalkoxylate enthaltende kosmetische Zusammensetzungen" beschrieben, worin die erfindungsgemäßen Verbindungen als Tenside gemeinsam mit den darin genannten Co-Teniden oder anstelle der darin genannten Co-Tenide eingesetzt werden können. Geeignete Pflanzenschutzformulierungen sind beispielsweise in der EP-A-0 050 228 beschrieben. Es können für Pflanzenschutzmittel übliche weitere Inhaltsstoffe vorliegen.
• – Lacke, Beschichtungsmittel, Farben, Pigmentpräparationen sowie Klebstoffe in der Lack- und Folienindustrie.
• – Lederentfettungsmittel.
• – Formulierungen für die Textilindustrie wie Egalisiermittel oder Formulierungen zur Garnreinigung.
• – Faserverarbeitung und Hilfsmittel für die Papier- und Zellstoffindustrie.
• – Metallverarbeitung wie Metallveredelung und Galvanobereich.
• – Lebensmittelindustrie.
• – Wasserbehandlung und Trinkwassergewinnung.
• – Fermentation.
• – Mineralverarbeitung und Staubkontrolle.
• – Bauhilfsmittel.
• – Emulsionspolymerisation und Herstellung von Dispersionen.
• – Kühl- und Schmiermittel.

Other applications are:

• - Humectants, especially for the printing industry.
• - Cosmetic, pharmaceutical and crop protection formulations. Suitable cosmetic formulations are described, for example, in the German application with the file number 103 01 704.6 with the title “Cosmetic Compositions Containing Alkyl Glycol Alkoxylates or Dialkyl Glycol Alkoxylates”, in which the compounds according to the invention are used as surfactants together with the co-tenids mentioned therein or instead of the co-tenides mentioned therein Suitable crop protection formulations are, for example, in the EP-A-0 050 228 described. There may be other common ingredients for pesticides.
• - Lacquers, coating agents, paints, pigment preparations and adhesives in lacquers and foils industry.
• - Leather degreaser.
• - Formulations for the textile industry such as leveling agents or formulations for yarn cleaning.
• - Fiber processing and tools for the paper and pulp industry.
• - Metal processing such as metal finishing and electroplating.
• - Food industry.
• - Water treatment and drinking water production.
• - fermentation.
• - Mineral processing and dust control.
• - Building aids.
• - emulsion polymerization and dispersion production.
• - coolants and lubricants.

The detergents are more solid, liquid, gel or more pasty Form before. Solid materials include powders and compactates, for example granules and moldings such as tablets.

The detergents contain 0.1 to 40% by weight, in particular 0.5 to 30% by weight, very particularly 1 to 20 % By weight, based on the total amount of the formulation, at least a substance of the formulas I, II and / or III. Other components are listed below.

Detergent formulations usually contain ingredients such as surfactants, builders, fragrances and dyes, complexing agents, polymers and other ingredients. Typical formulations are described, for example, in WO 01/32820. Other ingredients suitable for different applications are in EP-A-0 620 270 , WO 95/27034, EP-A-0 681 865 . EP-A-0 616 026 . EP-A-0 616 028 . DE-A-42 37 178 and US 5,340,495 described as an example.

Detergent in the sense of this invention are usually used to wash more or less flexible Materials, preferably those that are natural, synthetic or semi-synthetic Contain or consist of fiber materials and consequently usually at least partially have a textile character. The fiber-containing or fiber-based materials can in principle in any occurring use or manufacture and processing Form. For example Fibers disordered in the form of flakes or piles, arranged in Form of threads, Yarns, twists, or in the form of fabrics such as fleeces, loden fabrics or felt, fabrics, knitted fabrics in all conceivable types of weave.

It can be raw fibers or around Fibers act at any stage of processing and it can be natural protein or Cellulose fibers such as wool, silk, cotton, sisal, hemp, coconut fibers or synthetic fibers such as polyester, polyamide or Be polyacrylonitrile fibers.

Detergents containing the co-surfactants according to the invention can also for cleaning fibrous materials, such as. B. back coated Use carpets with cut or cut pile.

The compositions of the detergents are preferably adapted to different purposes as is is known to the person skilled in the art from the prior art. For this, the Detergents all appropriate from the prior art known auxiliaries and additives are added.

• – Builder und Cobuilder, wie Polyphosphate, Zeolithe, Polycarboxylate, Phosphonate oder Komplexbildner
• – ionische Tenside, wie Alkoholsulfate/-ethersulfate, Alkylbenzolsulfonate, α-Olefinsulfonate und andere Alkoholsulfate/-ethersulfate
• – nichtionische Tenside, Alkoholalkoxylate wie Alkylaminalkoxylate, Alkylpolyglucoside
• – optische Aufheller
• – Farbübertragungsinhibitoren, wie Polyvinylpyrrolidon der Molmassen 8.000 bis 70.000, Vmylimidazol/Vinylpyrrolidon-Copolymere mit einem Molverhältnis der Monomeren von 1:10 bis 2:1 und Molmassen von 8.000 bis 70.000 sowie Poly-4-vinylpyridin-N-oxide mit Molmassen von 8.000 bis 70.000.
• – Stellmittel, wie Natriumsulfat oder Magnesiumsulfat
• – -Soil Release-Mittel
• – Inkrustationsinhibitoren
• – Bleichsysteme, enthaltend Bleichmittel, wie Perborat, Percarbonat und Bleichaktivatoren, wie Tetraacetylethylendiamin sowie Bleichstabilisatoren
• – Parfum/-öle
• – Schaumdämpfer, wie Silikonöle
• – Enzyme, wie Amylasen, Lipasen, Cellulasen, Proteasen
• – Alkalispender, wie lösliche Alkalisilikate, z. B. Pentanatriummethasilikat, Nariumcarbonat.

In addition to the co-surfactants according to the invention, detergents can contain, for example:

• - Builders and cobuilders, such as polyphosphates, zeolites, polycarboxylates, phosphonates or complexing agents
• - Ionic surfactants, such as alcohol sulfates / ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates and other alcohol sulfates / ether sulfates
• - Nonionic surfactants, alcohol alkoxylates such as alkylamine alkoxylates, alkyl polyglucosides
• - optical brighteners
• - Color transfer inhibitors, such as polyvinylpyrrolidone with a molecular weight of 8,000 to 70,000, vinylimidazole / vinylpyrrolidone copolymers with a molar ratio of the monomers from 1:10 to 2: 1 and molecular weights from 8,000 to 70,000 and poly-4-vinylpyridine-N-oxides with a molecular weight of 8,000 to 70,000.
• - adjusting agents, such as sodium sulfate or magnesium sulfate
• - Soil release funds
• - incrustation inhibitors
• - Bleaching systems containing bleaching agents such as perborate, percarbonate and bleach activators such as tetraacetylethylene diamine and bleach stabilizers
• - perfume / oils
• - foam absorbers, such as silicone oils
• - Enzymes, such as amylases, lipases, cellulases, proteases
• - Alkaline dispensers, such as soluble alkali silicates, e.g. B. pentasodium methasilicate, sodium carbonate.

In liquid detergents, for example additionally Solvent, such as ethanol, isopropanol, 1,2-propylene glycol, butyl glycol, etc. used become.

In tablet detergents, tableting aids, such as polyethylene glycols with molecular weights of more than 1000 g / mol, polymer dispersions and tablet disintegrants, such as cellulose derivatives, crosslinked polyvinylpyrrolidone, cross-linked polyacrylates or combinations of acids such as citric acid and Sodium bicarbonate can be used. A more detailed performance possible Ingredients are given below.

In some cases it may be useful those used according to the invention Co-surfactants with other co-surfactants or with amphoteric surfactants, such as B. alkylamine oxides, or betaines to combine.

Another class of non-ionic Surfactants are alkyl polyglucosides with 6 to 22, preferably 10 to 18 Carbon atoms in the alkyl chain. Contain these connections usually 1 to 20, preferably 1.1 to 5 glucoside units.

wobei B¹ ein C₆- bis C₂₂-Alkyl, B² Wasserstoff oder C₁- bis C₄-Alkyl und D ein Polyhydroxyalkyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise steht B¹ für C₁₀- bis C₁₈-Alkyl, B² für CH₃ und D für einen C₅- oder C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀- bis C₁₈-Carbonsäuren.Another class of nonionic surfactants are N-alkyl glucamides of the general structures

where B ^{1 is} a C ₆ to C ₂₂ alkyl, B ^{2 is} hydrogen or C ₁ to C ₄ alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. B ¹ is preferably C ₁₀ to C ₁₈ alkyl, B ^{2 is} CH ₃ and D is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

Other suitable nonionic surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225 R ¹ -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ² in the
R ¹ denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,
R ^{2 represents} a C ₁ to C ₄ alkyl group,
A ^{1 represents} C ₂ to C ₄ alkylene,
y denotes the number 2 or 3 and
x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula HN ₂ - (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyltetraglycolamine of the formula HN ₂ - (CH ₂ -CH ₂ - O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

(- BASF and Tetronic ^® brands of Pluronic ^®), polyhydroxy or Polyalkoxyfettsäurederivate as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxyfatty, Fettsäureamidethoxylate, in particular end-capped, are also suitable as nonionic surfactants are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, as well as fatty acid alkanolamide alkoxylates.

The additional non-ionic surfactants ("Nonionic surfactants") are in the detergents containing the invention Co-surfactants used preferably in an amount of 0.01 to 30% by weight, in particular 0.1 to 25% by weight, especially 0.5 to 20 % By weight.

It is also possible to use individual nonionic surfactants or a combination of different nonionic surfactants. Nonionic surfactants from only one class can be used, in particular only alkoxylated C ₈ to C ₂₂ alcohols, but surfactant mixtures from different classes can also be used.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, C ₁₂ -C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by firstly using a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation, 1 to 50, preferably 1 to 20, mol of ethylene oxide being used per mol of alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are alkoxylated C ₈ to C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide. The alkoxylated C ₈ to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are alkane sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates, and soaps such as the Na and K salts of saturated and / or unsaturated ten C ₈ to C ₂₄ carboxylic acids.

Further suitable anionic surfactants are linear C ₈ to C ₂₀ alkylbenzenesulfonates (“LAS”), preferably linear C ₉ to C ₁₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Also suitable as anionic surfactants are C ₈ to C ₂₄ olefin sulfonates and disulfonates, which can also be mixtures of alkene and hydroxyalkane sulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyate, paraffin glycolsulfonate with parolinesulfonate, paraffin 20 up to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acyl sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are the Detergent preferably added in the form of salts. suitable Cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as e.g. B. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

The anionic surfactants are present in the detergents containing the cosurfactants according to the invention preferably in an amount of up to 30% by weight, for example from 0.1 to 30% by weight, especially 1 to 25% by weight, in particular 3 up to 10% by weight. If C ₉ to C ₂₀ linear alkyl-benzenesulfonates (LAS) are also used, they are usually used in an amount of up to 15% by weight, in particular up to 10% by weight.

One can use single anionic surfactants or use a combination of different anionic surfactants. It can anionic surfactants from only one class are used, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but you can also use surfactant mixtures from different classes, e.g. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.

Furthermore, surfactant mixtures containing the co-surfactants to be used according to the invention with cationic surfactants, usually in an amount of up to 25% by weight, preferably 1 to 15% by weight, for example C ₈ to C ₁₆ dialkyldimethylammonium salts, dialkoxydimethylammonium salts or imidazolinium salts long chain alkyl group; and / or with amphoteric surfactants, usually in an amount up to 15 wt .-%, preferably 1 to 10 wt .-%, for example derivatives of secondary or tertiary amines such as. B. C ₆ -C ₁₈ alkyl betaines or C ₆ -C ₁₅ alkyl sulfobetaines or alkyl amido betaines or amine oxides such as alkyldimethylamine oxides can be combined.

Cationic surfactants can also be used as described in WO 99/19435.

Mixtures are usually included the according to the invention Co-surfactants to be used with builders (sequestrants) such. B. polyphosphates, Polycarboxylates, phosphonates, complexing agents, e.g. B. methylglycinediacetic acid and their salts, nitrilotriacetic acid and their salts, ethylenediaminetetraacetic acid and their salts and optionally combined with co-builders.

Individual builder substances which are highly suitable for combination with mixtures comprising the co-surfactants to be used according to the invention are listed below:
Suitable inorganic builders are, above all, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as, in particular, zeolites. Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in US Pat US-A-4604224 ,

Suitable crystalline silicates as builders are, for example, disilicates or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates. Amorphous silicates such as sodium metasilicate, which has a polymeric structure, or amorphous disilicate can also be used.

Suitable inorganic builder substances carbonates and carbonates are based on carbonate. These can be in Form used their alkali metal, alkaline earth metal or ammonium salts become. Na, Li and Mg carbonates or bicarbonates, especially sodium carbonate and / or sodium bicarbonate used.

usual, Phosphates used as inorganic builders are alkali orthophosphates, and / or polyphosphates such. B. pentasodium triphosphate.

The Builder components mentioned can used individually or in mixtures with one another.

Furthermore, it is expedient in many cases to add co-builders to the detergents containing the co-surfactants to be used according to the invention. Examples of suitable substances are listed below:
In a preferred embodiment, the detergents containing the cosurfactants to be used according to the invention contain, in addition to the inorganic builders, 0.05 to 20% by weight, in particular 1 to 10% by weight, organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids special polycarboxylic acids, or phosphonic acids or their salts, in particular sodium or potassium salts.

Examples of suitable low-molecular carboxylic acids or phosphonic acids as organic cobuilders are:
Phosphonic acids such as B. 1-hydroxyethane-1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), ethylenediamine-tetra (methylenephosphonic acid), hexamethylenediamine-tetra (methylenephosphonic acid) and diethylenetriamine-penta (methylenephosphonic acid);
C ₄ - to C ₂₀ di, tri and tetracarboxylic acids such as. B. succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ - to C ₁₆ -alkyl or -alkenyl radicals;
C ₄ - to C ₂₀ hydroxycarboxylic acids such. B. malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
Aminopolycarboxylic acids such as. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, alkylethylenediamine triacetates, N, N-bis (carboxymethyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl- and ethylenediacetic acid, methyl- and ethylacetic acid.

Examples of suitable oligomeric or polymeric carboxylic acids as organic cobuilders are:
Oligomaleic acids, as for example in EP-A 451508 and EP-A 396303 are described;
Copolymers and terpolymers of unsaturated C ₄ to C ₈ dicarboxylic acids, the comonomers being monoethylenically unsaturated monomers from group (i) given below in amounts of up to 95% by weight and from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight.

Examples of suitable unsaturated C ₄ to C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) comprises monoethylenically unsaturated C ₂ to C ₂₂ olefins, vinyl alkyl ethers with C ₁ to C ₈ alkyl groups, styrene, vinyl esters of C ₁ to C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ -olefins, vinyl alkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate.

If the polymers of group (ii) contain vinyl esters in copolymerized form, these can also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are, for example, from US-A 3887806 such as DE-A 4313909 known.

Group (iii) comprises (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ to C ₈ amines, N-vinylformamide and N-vinylimidazole.

Also suitable as organic cobuilders are homopolymers of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids such as. B. acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, especially acrylic acid and methacrylic acid,
Copolymers of dicarboxylic acids, such as. B. copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molar masses of 1000 to 150,000;
Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid for vinyl ester can vary in the range from 30:70 to 70:30;
Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446 . DE-A 4415623 and DE-A 4313909 , are also suitable as organic cobuilders.

Suitable unsaturated carboxylic acids are here, for example, maleic acid, fumaric acid, itaconic, citraconic, Acrylic acid, methacrylic acid, crotonic and vinyl acetic acid as well as mixtures of acrylic acid and maleic acid, those in amounts of 40 to 95 wt .-%, based on the to be grafted Component to be grafted on.

For modification you can add up to 30% by weight, based on the component to be grafted, further monoethylenically unsaturated Monomers are present in copolymerized form.

Suitable modifying monomers are the above-mentioned monomers of groups (ü) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolyzates and reduced (hydrogenated or hydrated aminated) degraded polysaccharides such as. B. mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as polyalkylene glycols with molecular weights with up to M _W = 5000 such. B. polyethylene glycols, ethylene oxide / propylene oxide or ethyl lenoxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C ₁ to C ₂₂ alcohols (cf. US-A-5756456 )

Polyglyoxylic acids suitable as organic cobuilders are described, for example, in EP-B-001004 . US-A-5399286 . DE-A-4106355 and EP-A-656 914 , The end groups of the polyglyoxylic acids can have different structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids suitable as organic cobuilders are known, for example, from EP-A-454126 . EP-B-511037 , WO-A-94/01486 and EP-A-581 452 ,

Organic cobuilders used include, in particular, polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ to C ₂₅ mono- or dicarboxylic acids and / or C ₄ to C ₂₅ mono- or diamines. Particularly preferred are prepared in phosphorus-containing acids, with C ₆ - to C ₂₂ used modified mono- or diamines, polyaspartic acids - to C ₂₂ -mono- or -dicarboxylic acids or with C. ₆

Are suitable as organic cobuilders continue iminodisuccinic acid, oxydisuccinic, Aminopolycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylenephosphonates, Polyglutamates, hydrophobically modified citric acid such as B. agaricic acid, poly-α-hydroxyacrylic acid, N-acylethylene diamine triacetate such as lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid such as EDTA-tallow amide.

Oxidized starches can also be used as organic cobuilders can be used.

Other suitable (co) builders are described in WO 99/19435.

In a further preferred embodiment contain the detergents containing those to be used according to the invention Additional co-surfactants, especially additional to the inorganic builders, the anionic surfactants and / or the nonionic surfactants, 0.5 to 20 wt .-%, in particular 1 to 10% by weight, glycine-N, N-diacetic acid derivatives, as described in WO 97/19159.

Frequently it is also appropriate to Detergents containing the co-surfactants to be used according to the invention Bleaching systems consisting of bleaching agents, such as. B. perborate, Percarbonate and optionally bleach activators, such as. B. tetraacetylethylenediamine, + Bleach stabilizers and optionally bleach catalysts add.

In these cases, the detergents contain containing the invention Co-surfactants to be used additionally 0.5 to 30 wt .-%, in particular 5 to 27 wt .-%, especially 10 to 23% by weight bleach in the form of percarboxylic acids, e.g. B. diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic or - terephthalic acid, adducts of hydrogen peroxide to inorganic salts, e.g. B. sodium perborate monohydrate, Sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, Adducts of hydrogen peroxide with organic compounds, e.g. B. Urea perhydrate, or of inorganic peroxo salts, e.g. B. Alkali metal persulfates, or -peroxodisulfates, optionally in Combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8 wt .-%, bleach activators.

• – polyacylierte Zucker, z. B. Pentaacetylglucose;
• – Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkaiimetallsalze, z. B. Natrium-p-nonanoyloxybenzolsulfonat oder Natrium-p-benzoyloxybenzolsulfonat;
• – N,N-diacylierte und N,N,N',N'-tetraacylierte Amine, z. B. N,N,N',N'-Tetraacetylmethylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• – N-Alkyl-N-sulfonylcarbonamide, z. B. N-Methyl-N-mesylacetamid oder N-Methyl-N-mesylbenzamid;
• – N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetylmaleinsäurehydrazid;
• – O,N,N-trisubstituierte Hydroxylamine, z. B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinylhydroxylamin oder O,N,N-Triacetylhydroxylamin;
• – N,N'-Diacylsulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyisulfurylamid;
• – acylierte Lactame wie beispielsweise Acetylcaprolactam, Octanoylcaprolactam, Benzoylcaprolactam oder Carbonylbiscaprolactam;
• – Anthranilderivate wie z. B. 2-Methylanthranil oder 2-Phenylanthranil;
• – Triacylcyanurate, z. B. Triacetylcyanurat oder Tribenzoylcyanurat;
• – Oximester und Bisoximester wie z. B. O-Acetylacetonoxim oder Bisisopropyliminocarbonat;
• – Carbonsäureanhydride, z. B. Essigsäureanhydrid, Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• – Enolester wie z. B. Isopropenylacetat;
• – 1,3-Diacyl-4,5-diacyloxy-imidazoline, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• – Tetraacetylglycoluril und Tetrapropionylglycoluril; diacylierte 2,5-Diketopiperazine, z. B. 1,4-Diacetyl-2,5-diketopiperazin;
• – ammoniumsubstituierte Nitrile wie z. B. N-Methylmorpholiniumacetonitrihnethylsulfat;
• – Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff z. B. Tetraacetylpropylendiharnstoff;
• – α-Acyloxypolyacylmalonamide, z. B. α-Acetoxy-N,N'-diacetylmalonamid;
• – Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin;
• – Benz-(4H)1,3-oxazin-4-one mit Alkylresten, z. B. Methyl, oder aromatischen Resten z. B. Phenyl, in der 2-Position;
• – kationische Nitrile, wie in DE-A-101 48 577 beschrieben.

Suitable bleach activators are:

• - polyacylated sugars, e.g. B. Pentaacetylglucose;
• - Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. B. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate;
• - N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B. N, N, N ', N'-tetraacetylmethylene diamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5 , 5-dimethylhydantoin;
• - N-alkyl-N-sulfonylcarbonamides, e.g. B. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
• - N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;
• - O, N, N-trisubstituted hydroxylamines, e.g. B. O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetylhydroxylamine;
• - N, N'-diacylsulfurylamides, e.g. B. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionyisulfurylamide;
• Acylated lactams such as acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonyl biscaprolactam;
• - Anthranil derivatives such as B. 2-methylanthranil or 2-phenylanthranil;
• - Triacylcyanurate, e.g. B. triacetyl cyanurate or tribenzoyl cyanurate;
• - Oxime esters and bisoxime esters such as. B. O-acetylacetone oxime or bisisopropyliminocarbonate;
• - Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• - enol esters such as B. isopropenyl acetate;
• - 1,3-diacyl-4,5-diacyloxy-imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• - tetraacetylglycoluril and tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, e.g. B. 1,4-diacetyl-2,5-diketopiperazine;
• - Ammonium substituted nitriles such as. B. N-methylmorpholinium acetonitrile methyl sulfate;
• - Acylation products of propylene diurea and 2,2-dimethylpropylene diurea e.g. B. tetraacetylpropylene diurea;
• - α-Acyloxypolyacylmalonamide, e.g. B. α-acetoxy-N, N'-diacetylmalonamide;
• - Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• - Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, e.g. B. methyl, or aromatic radicals such. B. phenyl, in the 2-position;
• - cationic nitriles, as in DE-A-101 48 577 described.

The described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US-A 5 360 569 and EP-A 453 003 , Manganese complexes, which are described, for example, in WO-A 94/21777, are particularly effective bleaching catalysts. When used in detergents, such compounds are used in amounts of up to 1.5% by weight, in particular up to 0.5% by weight, and in the case of very active manganese complexes in amounts of up to 0.1% by weight. , incorporated. Further suitable bleaching catalysts are described in WO 99/19435.

Other bleaching systems based on arylimidoperalkanoic acids that can be used are in EP-A-0 325 288 and EP-A-0 490 409 described.

bleach stabilizer

These are additives can absorb, bind or complex the traces of heavy metals. Examples for usable according to the invention additions with a bleach-stabilizing effect are polyanionic compounds such as polyphosphates, polycarboxylates, polyhydroxypolycarboxylates, soluble Silicates as complete or partially neutralized alkali or alkaline earth salts, in particular as neutral Na or Mg salts, which are relatively weak bleach stabilizers. Strong usable according to the invention Bleach stabilizers are, for example, complexing agents such as ethylenediaminetetraacetate (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), β-alaninediacetic acid (ADA), Ethylenediamine-N, N'-diesuccinat (EDDS) and phosphonates such as ethylenediaminetetramethylenephosphonate, Diethylene triamine pentamethylene phosphonate or hydroxyethylidene-1,1-diphosphonic acid in the form of acids or as partial or complete neutralized alkali metal salts. The complexing agents are preferred used in the form of their Na salts.

In addition to the described bleaching system consisting of bleaching agents, bleach activators and, if appropriate, bleaching catalysts, detergents containing the co-surfactants to be used according to the invention can also be used with systems with enzymatic peroxide release or with photoactivated bleaching systems. B. US 4,033,718 ,

For a number of use cases it is useful if the detergents containing the co-surfactants to be used according to the invention Contain enzymes. Enzymes preferably used in detergents are proteases, amylases, lipases and cellulases. From the enzymes quantities of 0.1 to 1.5 wt .-%, in particular preferably 0.2 to 1.0% by weight of the compounded enzyme is added. Suitable proteases are e.g. B. Savinase and Esperase. A suitable one Lipase is e.g. B. Lipolase. A suitable cellulase is e.g. B. Celluzym. The use of peroxidases to activate the bleaching system is possible. One can use single enzymes or a combination of different ones Use enzymes. The detergent may optionally contain the according to the invention Co-surfactants to be used still enzyme stabilizers, e.g. B. calcium propionate, Sodium formate or boric acids or their salts, and / or contain antioxidants.

The ingredients of detergents are known in principle to the person skilled in the art. The above and the ones below The following lists of suitable components are only an example Section of the known suitable components again.

The detergents containing the co-surfactants to be used according to the invention can contain the following further customary additives in the usual amounts in addition to the main components mentioned above:
Known dispersants, such as naphthalenesulfonic acid condensates or polycarboxylates, soil release agents, soil release agents, such as polyether esters, incrustation inhibitors, pH-regulating compounds, such as alkalis or alkali donors (NaOH, KOH, pentasodium metasilicate, sodium carbonate) or acids (hydrochloric acid, phosphoric acid, amidosulfonic acid, amidosulfonic acid) such as acetate or phosphate buffer, ion exchangers, perfume, dyes, graying inhibitors, optical (fluorescent) brighteners, color transfer inhibitors such as. B. polyvinylpyrrolidone, biocides such as isothiazolinones or 2-bromo-2-nitro-1,3-propanediol, hydrotropic compounds as solubilizers or solubilizers, such as cumene sulfonates, toluenesulfonates, short-chain fatty acids, urea, alcohols or phosphoric acid alkyl / aryl esters, foam regulators Stabilization or damping of the foam, e.g. As silicone oils, skin and anti-corrosion agents, disinfectant compounds or systems such. B. those that release chlorine or hypochlorous acid such as dichloroisocyanurate or which contain iodine, thickeners and adjusting and confectioning agents.

graying and soil release polymers

Suitable soil release polymers and / or graying inhibitors for detergents are, for example:
Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
Polyester made of polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3,557,039 . GB-A 1 154 730 . EP-A-185 427 . EP-A-241 984 . EP-A-241 985 . EP-A-272 033 and US-A 5,142,020 ,

Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US-A 4,746,456 . US-A 4,846,995 . DE-A-37 11 299 . US-A 4,904,408 . US-A 4,846,994 and US-A 4,849,126 ) or modified celluloses such. B. methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Color transfer inhibitors

Color transfer inhibitors used are, for example, homopolymers and copolymers of vinylpyrrolidone, vinylimidazole, vinyloxazolidone and 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000 and crosslinked, finely divided polymers based on these monomers. The use of such polymers mentioned here is known, cf. DE-B-22 32 353 . DE-A-28 14 287 . DE-A-28 14 329 and DE-A-43 16 023 ,

Suitable polyvinyl pyridine betaines are z. B. in Tai, Formulating Detergents and Personal Care Products, AOCS Press, 2000, page 113.

In addition to use in washing and Detergents for the textile laundry The detergent compositions which can be used according to the invention are in the household also in the field of commercial textile washing and cleaning used. As a rule, peracetic acid is used in this area Bleaching agents used, which are added to the wash liquor as an aqueous solution becomes.

use in textile detergents

• – 0,5 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-%, mindestens eines anionischen und/oder nichtionischen Tensids, einschließlich der erfindungsgemässen Co-Tenside,
• – 0,5 bis 60 Gew.-%, vorzugsweise 15 bis 40 Gew.-%, mindestens eines anorganischen Builders,
• – 0 bis 20 Gew.-%, vorzugsweise 0,5 bis 8 Gew.-%, mindestens eines organischen Cobuilders,
• – 2 bis 35 Gew.-%, vorzugsweise 5 bis 30 Gew.-%, eines anorganischen Bleichmittels,
• – 0,1 bis 20 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, eines Bleichaktivators, gegebenenfalls in Abmischung mit weiteren Bleichaktivatoren,
• – 0 bis 1 Gew.-%, vorzugsweise bis höchstens 0,5 Gew.-%, eines Bleichkatalysators,
• – 0 bis 5 Gew.-%, vorzugsweise 0 bis 2,5%, eines polymeren Farbübertragungsinhibitors,
• – 0 bis 1,5 Gew.-%, vorzugsweise 0,1 bis 1,0 Gew.-%, Protease,
• – 0 bis 1,5 Gew.-%, vorzugsweise 0,1 bis 1,0 Gew.-%, Lipase,
• – 0 bis 1,5 Gew.-%, vorzugsweise 0,2 bis 1,0% Gew.-% eines Soil-Release-Polymers,

ad 100% übliche Hilfs- und Begleitstoffe und Wasser.A typical powder or granular heavy-duty detergent to be used according to the invention can have, for example, the following composition:

• 0.5 to 50% by weight, preferably 5 to 30% by weight, of at least one anionic and / or nonionic surfactant, including the co-surfactants according to the invention,
• 0.5 to 60% by weight, preferably 15 to 40% by weight, of at least one inorganic builder,
• 0 to 20% by weight, preferably 0.5 to 8% by weight, of at least one organic cobuilder,
• 2 to 35% by weight, preferably 5 to 30% by weight, of an inorganic bleaching agent,
• 0.1 to 20% by weight, preferably 0.5 to 10% by weight, of a bleach activator, optionally in a mixture with other bleach activators,
• 0 to 1% by weight, preferably up to at most 0.5% by weight, of a bleaching catalyst,
• 0 to 5% by weight, preferably 0 to 2.5%, of a polymeric color transfer inhibitor,
• 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, protease,
• 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, lipase,
• 0 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of a soil release polymer,

ad 100% usual auxiliary and accompanying substances and water.

Preferably used in detergents inorganic builders are sodium carbonate, sodium hydrogen carbonate, Zeolite A and P as well as amorphous and crystalline Na silicates as well Phyllosilicates.

Preferably used in detergents organic cobuilders are acrylic acid / maleic acid copolymers, Acrylic acid / maleic acid / Vinylester terpolymers and citric acid.

Preferably used in detergents inorganic bleaching agents are sodium perborate and sodium carbonate perhydrate.

Preferably used in detergents Anionic surfactants are linear and slightly branched alkylbenzenesulfonates (LAS), fatty alcohol sulfates / ether sulfates and soaps.

Enzymes preferably used in detergents are protease, lipase, amylase and cellulase. Of the commercially available enzymes, amounts of 0.05 to 2.0% by weight, preferably 0.2 to 1.5% by weight, of the finished enzyme are generally added to the detergent. Suitable proteases are, for example, Sa vinase, desazyme and esperase. A suitable lipase is e.g. B. Lipolase. A suitable cellulase is e.g. B. Celluzym.

Graying inhibitors and soil release polymers preferably used in detergents are graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2,500-8,000 in a weight ratio of 1.2: 1 to 3.0: 1, polyethylene terephthalate / oxyethylene terephthalate of molecular weight 3,000 to 25,000 made of polyethylene oxides of molecular weight 750 to 5,000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate of 8: 1 to 1: 1 and block polycondensates according to DE-A-44 03 866 ,

Preferably used in detergents Color transfer inhibitors are soluble NVP homopolymers and / or vinylpyrrolidone and vinylimidazole copolymers with molecular weights above 5,000.

The detergents are often in firmer, more powdery Form before, and then usually contain additional usual adjusting means that them good flow, Dosage and solubility lend and prevent caking and dusting, like Sodium sulfate or magnesium sulfate.

Powder or granular detergent containing the invention Co-surfactants to be used contain up to 60% by weight of inorganic fillers. Preferably but these detergents are low in agents and only contain up to 20% by weight, particularly preferably only up to 8% by weight, of adjusting agents.

Detergents containing those to be used according to the invention Co-surfactants can different bulk densities in the range from 300 to 1,200, in particular 500 to 950g / l. Modern compact laundry detergents generally have high bulk densities and show a granulate structure. Compact or ultra-compact detergent and extrudates have a bulk density> 600 g / 1. This are becoming more and more important.

If they are used in liquid form should, can them as watery Microemulsions, emulsions or solutions are present. In liquid detergents can additionally solvent such as ethanol, i-propanol, 1,2-propylene glycol, or butyl glycol used become.

With gel detergents, thickeners such as. B. polysaccharides and / or weakly crosslinked polycarboxylates (for example Carbopol ^® from Goodrich) can be used.

In the case of tablet detergents additionally Tableting aids such as B. polyethylene glycols with molecular weights> 1000 g / mol, polymer dispersions, and tablet disintegrants such as cellulose derivatives, crosslinked polyvinylpyrrolidone, cross-linked polyacrylates or combinations of acids, e.g. B. citric acid + sodium bicarbonate, to name just a few.

Another subject of the present Invention is the use of the mixtures in the manufacture of Detergents.

• – ionische Tenside, wie z. B. Alkoholsulfat/-ethersulfaten, Alkylbenzolsulfonate, α-Olefinsulfonate, Sulfosuccinate, wie oben unter "Waschmittel" beschrieben.
• – nichtionische Tenside, wie z. B. Alkoholalkoxilate, Alkylaminalkoxilate, Alkylamidethoxilate, Alkylpolyglucoside, wie oben unter "Waschmittel" beschrieben.
• – amphotere Tenside, wie z. B. Alkylaminoxide, Betaine, wie oben unter "Waschmittel" beschrieben.
• – Builder wie z. B. Polyphosphate, Polycarboxilate, Phosphonate, Komplexbildner, z. B. Methylglycindiessigsäure und deren Salze, Nitrilotriessigsäure und deren Salze, Ethylendiamintetraessigsäure und deren Salze, wie oben unter "Waschmittel" beschrieben.
• – Dispergiermittel, wie z. B. Naphthalinsulfonsäurekondensate, Polycarboxilate, wie oben unter "Waschmittel" beschrieben.
• – pH-regulierende Verbindungen wie z. B. Alkalien (NaOH, KOH, Pentanatriummetasilikat) oder Säuren (Salzsäure, Phosphorsäure, Amidoschwefelsäure, Citronensäure)
• – Enzyme, wie z. B. Lipasen, Amylasen, Proteasen
• – Parfüm
• – Farbstoffe
• – Biozide, wie z. B. Isothiazolinone, 2-Bromo-2-nitro-1,3-propandiol, wie oben unter "Waschmittel" beschrieben.
• – Bleichsysteme, bestehend aus Bleichmitteln, wie z. B. Perborat, Percarbonat etc., plus Bleichaktivatoren, wie z. B. Tetraacetylethylendiamin, plus Bleichstabilisatoren, wie oben unter "Waschmittel" beschrieben.
• – Solubilisatoren, wie z. B. Cumolsulfonate, Toluolsulfonate, kurzkettige Fettsäuren, Phosphorsäurealkyl/-arylester
• – Lösemittel, wie z. B. kurzkettige Alkyloligoglykole wie Butylglykol, Butyldiglykol, Propylenglykolmonomethylether, Alkohole wie Ethanol, i-Propanol, aromatische Lösemittel wie Toluol, Xylol, N-Alkylpyrrolidone, Alkylencarbonate

In connection with the present invention, the term “household cleaner” or “cleaner” is generally understood to mean formulations which are used to clean hard surfaces. They are liquid, as a gel, paste or solid. Solid materials include powders and compacts, such as granules and moldings, such as tablets. Examples include hand dishwashing detergents, machine dishwashers, metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, pressure washers, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, upholstery, plastic and bathroom cleaners. They contain 0.01 to 40% by weight, preferably 0.1 to 25% by weight, based on the total formulation of at least one substance of the formulas I, II and / or III. Other components are listed below.

• - Ionic surfactants, such as. B. alcohol sulfate / ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates, sulfosuccinates, as described above under "detergent".
• - Nonionic surfactants, such as. B. alcohol alkoxylates, alkylamine alkoxylates, alkylamide ethoxylates, alkyl polyglucosides, as described above under "detergent".
• - amphoteric surfactants, such as. B. alkylamine oxides, betaines, as described above under "detergent".
• - Builders such as B. polyphosphates, polycarboxylates, phosphonates, complexing agents, for. B. methylglycinediacetic acid and its salts, nitrilotriacetic acid and its salts, ethylenediaminetetraacetic acid and its salts, as described above under "detergent".
• - Dispersants, such as. B. naphthalenesulfonic acid condensates, polycarboxylates, as described above under "detergent".
• - pH-regulating compounds such. B. alkalis (NaOH, KOH, pentasodium metasilicate) or acids (hydrochloric acid, phosphoric acid, amidosulfuric acid, citric acid)
• - Enzymes such as B. lipases, amylases, proteases
• - Perfume
• - dyes
• - biocides such as B. isothiazolinones, 2-bromo-2-nitro-1,3-propanediol, as described above under "detergent".
• - Bleaching systems consisting of bleaching agents, such as. As perborate, percarbonate, etc., plus bleach activators, such as. B. tetraacetylethylenediamine, plus bleach stabilizers, as described above under "detergent".
• - Solubilizers, such as. B. cumene sulfonates, toluenesulfonates, short-chain fatty acids, phosphoric acid alkyl / aryl esters
• - Solvents, such as. B. short-chain alkyl oligoglycols such as butyl glycol, butyl diglycol, propylene glycol monomethyl ether, alcohols such as ethanol, i-propanol, aromatic solvents such as toluene, xylene, N-alkylpyrrolidones, alkylene carbonates

The components of cleaners for hard surfaces are known in principle to the person skilled in the art. The list above only represents an exemplary section of the components.

The cleaners for hard surfaces are usually, but not exclusively, aqueous and are in the form of microemulsions, emulsions or solutions.

Should they be in solid, powdered form can exist additionally Adjustment means such as B. sodium sulfate, magnesium sulfate, etc. used become.

In the case of tablet-shaped cleaners, tabletting aids are also used such as B. polyethylene glycols with molecular weights> 1000 g / mol, polymer dispersions etc., and tablet disintegrants such. B. cellulose derivatives, crosslinked Polyvinyl pyrrolidone, cross-linked polyacrylates or combinations of acids, z. B. citric acid plus Sodium bicarbonate, to name a few, is needed.

In a particularly preferred embodiment In the present application, the cleaners are concerned Hand dishwashing detergents. Another subject of the present application is therefore a hand dishwashing liquid containing at least one compound of the general formulas I, II or III as co-surfactant, and the use of the compounds of the general formulas I, II or III as co-surfactants in hand dishwashing detergents.

Products from the body care sector include shampoos, shower and bath gels, shower and bath lotions, Lipsticks and cosmetic formulations with care and / or conditioning properties like styling products. Examples are hair foams, hair gels, hair sprays or Post-treatment agents such as hair lotions, lotions, course rinses, Spa packs, top fluids, hair repair products, "hot oil treatments", shampoos, liquid soaps, Care creams, hair fixatives, hair dyes and permanent waving agents. When used in body care products, the substances show the Formulas I, II and III have the advantage of being physiological irritant the surfactant mixtures are softened and the mucous membranes are protected.

The invention will now be described in the following Examples explained.

Examples

example 1

576 g (4 mol) of 2-ethylhexanoic acid were submitted together with 420 g (4 mol) of 2-amino-2-methylpropanediol and over from this mixture 1 h at 170 ° C and then water for eight hours at a reaction temperature of 200 ° C distilled off (123 g). The resulting residue contained the desired product. Analysis by GC / MS.

Example 2

576 g (4 mol) of 2-ethylhexanoic acid were submitted together with 476 g (4 mol) of 2-amino-2-ethylpropanediol and over from this mixture 1 h at 170 ° C and then water for eight hours at a reaction temperature of 200 ° C distilled off (120 g). The resulting residue contained the desired product. Analysis by GC / MS.

Example 3a

196.1 g (1.5 mol) 2-ethylhexanal were made under a nitrogen atmosphere together with 183.5 g (1.5 mol) Tris (hydroxymethyl) aminomethane and 1.5 g Amberlyst 15 (acidic form) submitted in 300 ml of toluene. Up to none was heated under reflux at the water separator more water was separated off (approx. 4 h). Then allowed to cool and filtered the ion exchanger. The product was left without further notice Cleaning in the next Stage used. Analysis by GC / MS.

Example 3b

Product: N = 3, aldehyde = ethyl hexanal.

295 g (1.5 mol) of the acetal, 200 ml of water and 27 g of 50% KOH solution were dewatered on a rotary evaporator at 90 ° C. and 20 mbar for 3 h. The resulting mixture was placed in a pressure autoclave. The The reactor was made inert twice with nitrogen and then heated to 120 ° C. At 120 ° C was ethylene oxide (198 g, 4.5 mol) in portions up to a maximum Total pressure of 6 bar added. After adding all of the ethylene oxide stir up to constant pressure (approx. 3 h). The attempt was subsequently made filled in the autoclave and at 80 ° C and degassed 30 mbar at the rotary evaporator. Weight: 502 g, the the wished Contain product in addition to double bond isomers. Analysis by GC / MS.

The following products were manufactured according to analog regulations:
N = 3, aldehyde = ethyl hexanal
N = 6, aldehyde = ethyl hexanal
N = 10, aldehyde = ethyl hexanal
N = 3, aldehyde = C _13/15 aldehyde
N = 6, aldehyde = C _13/15 aldehyde
N = 10, aldehyde = C _13/15 aldehyde.

Claims (22)

Unsaturated cyclic compounds of the general formulas

in which the symbols X, Y and R ¹ to R ^{8 have} the following meaning: R ¹ is a linear or branched, substituted or unsubstituted C ₃ -C ₂₉ alkyl group or a linear or branched, substituted or unsubstituted C ₃ -C ₂₉ alkenyl group, it being possible for one or more carbon atoms in the alkyl or alkenyl chain to be replaced by -O-, -NR ¹⁴ -, -C (O) NR ¹⁵ - or -S- and - OO and SS are excluded; R ² is hydrogen or -CH ₃ ; R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group of substituents consisting of: H; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents;

and C ₁ -C ₅ alkyl groups which have 1 to 4 substituents from the group -OH; SH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 to 2 substituents from the group consisting of -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have; or R ⁷ and R ⁸ are independently selected from the group of substituents consisting of: H; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents;

and C ₁ -C ₅ alkyl groups which have 1 to 4 substituents from the group -OH; SH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 to 2 substituents from the group consisting of -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ^3– ; -SO ^3– ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have; or R ¹⁴ is a linear or branched C ₁ -C ₄ alkyl group; R ¹⁵ is hydrogen or a linear or branched C ₁ -C ₄ alkyl group; R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group; R ¹⁸ is selected from the group consisting of C ₁ -C ₆ alkyl groups and ethylene oxy groups - (CH ₂ -CH ₂ O-) _p ; R ¹⁹ , R ²⁰ independently have the same meaning as R ¹⁶ , R ¹⁷ ; R ²¹ is a C ₁ -C ₄ alkyl group or -C ₆ H ₅ ; R ²² is selected from the group consisting of C ₁ -C ₁₀ alkyl groups, acyl groups -C (O) R ²³ and the group consisting of ethylene oxy groups - (CH ₂ -CH ₂ O-) _q , propylene oxy groups - (CH (CH ₃ ) -CH ₂ O-) _r , butyleneoxy groups - (C ₄ H ₉ O-) _s , and alkyleneoxy groups containing at least two of the above-mentioned groups in the form of block or random copolymers and containing a maximum of 15 alkyleneoxy units in total; R ²³ is a C ₁ -C ₁₈ alkyl group; X for formula I, II and III is 0, S, or NR ²⁴ , Y for formula I and II is N; and Y in Formula III is NR ²⁴ ; R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which may contain further substituents from the group OH, NH ₂ , OR ²² and NR ¹⁶ R ¹⁷ at 1 to 3 positions; n is 0 or 1; p is an integer from 1 to 15; q is an integer from 1 to 15; r is an integer from 1 to 15; s is an integer from 1 to 15; and wherein the aliphatic part of the compounds of the formula I, II or III which does not originate from the starting aldehyde or the starting carboxylic acid or its derivative must have at least 3 carbon atoms. A compound according to claim 1, in which one, more or all of the symbols X and Y, one, more or all of the substituents R ¹ to R ⁸ and n have the following meaning: R ¹ is a linear or branched C ₅ -C ₁₇ - Alkyl group or a linear or branched C ₃ -C ₁₇ alkenyl group, where one or more carbon atoms in the alkyl chain can be replaced by O or NR ¹⁴ and -OO- is excluded; R ² is -H; R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of: -H; -C (O) OH; -C (O) OR ¹⁸ ;

and C ₁ -C ₅ alkyl groups which have 1 or 2 substituents from the group -OH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 substituent from the group consisting of -C (O) OH; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have; or R ⁷ and R ⁸ are independently selected from the group consisting of: -H; -C (O) OH; -C (O) OR ¹⁸ ;

and C ₁ -C ₅ alkyl groups which have 1 or 2 substituents from the group -OH; -CN; NR ¹⁶ R ¹⁷ ; -OR ²² ; or 1 substituent from the group consisting of -C (O) OH; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

can have; or R ¹⁴ is a linear or branched C ₁ -C ₄ alkyl group; R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group; R ¹⁸ is selected from the group consisting of C ₁ -C ₆ alkyl groups and ethylene oxy groups - (CH ₂ -CH ₂ O-) _p ; R ²² is selected from the group consisting of C ₁ -C ₄ alkyl groups, acyl groups -C (O) R ²³ and the group consisting of ethylene oxy groups - (CH ₂ -CH ₂ O-) _q , propylene oxy groups - (CH (CH ₃ ) -CH ₂ O-) _r and butylene oxy groups - (C ₄ H ₉ O-) _s and mixed alkylene oxy groups; R ²³ is a C ₁ -C ₁₈ alkyl group; X in formula I, II and III is 0 or NR ²⁴ , Y in formula I and II is N; and Y in Formula III is NR ²⁴ ; R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which may contain further substituents from the group OH, NH ₂ , OR ²² and NR ¹⁶ R ¹⁷ at 1 to 2 positions; n is 0 or 1; p is an integer from 1 to 15; q is an integer from 1 to 10; r is an integer from 1 to 10; s is an integer from 1 to 10; and wherein the aliphatic part of the compounds of the formula I, II or III which does not originate from the starting aldehyde or the starting carboxylic acid or its derivative must have at least 3 carbon atoms. A compound according to claim 1 or 2, in which one, more or all of the symbols X, Y and 1, m, and n and one, more or all of the substituents R ¹ to R ^{8 have} the following meaning: R ¹ is a linear or branched C ₅ -C ₁₇ alkyl group, preferably a linear or branched C ₆ -C ₁₆ alkyl group or a linear or branched C ₅ -C ₁₇ alkenyl group, preferably a linear or branched C ₆ -C ₁₆ alkenyl group; R ² is -H; R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; -NR ¹⁶ R ^{1 7} ; -OR ²² and

can have; R ⁷ and R ⁸ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; NR ¹⁶ R ¹⁷ ; or 1 substituent from the group consisting of and

can have; R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group; R ²² is selected from the group consisting of C ₁ -C ₄ alkyl groups, acyl groups -C (O) R ²³ and the group consisting of ethylene oxy groups - (CH ₂ -CH ₂ O-) _q , propylene oxy groups - (CH (CH ₃ ) -CH ₂ O-) _r and butylene oxy groups - (CH ₂ CH (C ₂ H ₅ -O-) _s - as well as mixed alkylene oxy groups; R ²³ is a C ₁ -C ₁₈ alkyl group; X in formulas I, II and III is O or NR ²⁴ , Y in formula I and II is N; and Y in formula III is NR ²⁴ ; R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which has further substituents from the group OH at 1 to 2 positions , NH ₂ , OR ²² and NR ¹⁶ R ^{1 7} ; n is 0 or 1; q is an integer from 1 to 10; r is an integer from 1 to 10; s is an integer from 1 to 10 and where the aliphatic part of the compounds of the formula I, II or III which does not originate from the starting aldehyde or the starting carboxylic acid or its derivative must have at least 3 carbon atoms. A compound according to any one of claims 1 to 3, in which one, more or all of the symbols X, Y and n and one, more or all of the substituents R ¹ to R ^{8 have} the following meaning: R ¹ is a linear or branched C ₅ -C ₁₇ alkyl group, preferably a linear or branched C ₆ -C ₁₆ alkyl group or a linear or branched C ₅ -C ₁₇ alkenyl group, preferably a linear or branched C ₆ -C ₁₆ alkenyl group; R ² is -H; R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; -NR ¹⁶ R ¹⁷ ; -OR ²² ; R ⁷ and R ⁸ are independently selected from the group consisting of: -H; and C ₁ -C ₃ alkyl groups which have 1 or 2 substituents from the group -OH; NR ¹⁶ R ¹⁷ ; R ¹⁶ , R ¹⁷ are independently hydrogen or a linear or branched C ₁ -C ₄ alkyl group; R ²² is selected from the group consisting of C ₁ -C ₄ alkyl groups and ethylene oxy groups - (CH ₂ -CH ₂ O-) _q ; X in formula I, II and III is O, S, or NR ²⁴ , Y in formula I and II is N; and Y in formula III is NR ²⁴ R ²⁴ is hydrogen or a C ₁ -C ₄ alkyl group which may contain further substituents from the group -OH, -NH ₂ , -OR ²² and NR ¹⁶ R ¹⁷ at 1 to 2 positions ; n is 0 or 1; q is an integer from 3 to 8; and wherein the aliphatic part of the compounds of the formula I, II or III which does not originate from the starting aldehyde or the starting carboxylic acid or its derivative must have at least 3 carbon atoms. Compound according to one of Claims 1 to 4, characterized in that the symbol R ^{1 is} a branched or unbranched C ₇ H ₁₅ alkyl radical, C ₁₂ H ₂₅ alkyl radical or C ₁₄ H ₂₅ alkyl radical or a mixture of the branched and unbranched alkyl radicals mentioned is. A compound according to claim 1 or a mixture of the compounds mentioned below selected from the group consisting of:

2- (1-ethyl-pentyl) -4-methyl-4-hydroxymethyl-4,5-dihydro-oxazole

2- (1-ethyl-pentyl) -4-ethyl-4-hydroxymethyl-4,5-dihydro-oxazole

2- (1-ethyl-pentyl) -4-di (hydroxyrnethyl) -4,5-dihydro-oxazol

(1a) n = 3 (1b) n = 6 (1c) n = 10 (to be understood in each case as an average - based on molar equivalents - a molecular weight distribution)

(2a) n = 3 (2b) n = 6 (2c) n = 10 (each to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(3a) n + m = 3 (3b) n + m = 6 (3c) m + n = 10 (each to be understood as an average - based on molar equivalents - a molecular weight distribution)

(4a) n = 0 (4b) n = 3 (4c) n = 6 (4d) n = 10 (each to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(5a) n = 0 (5b) n = 3 (5c) n = 6 (5d) n = 10 (each to be understood as an average - based on molar equivalents - a molecular weight distribution)

(6a) n = 0 (6b) n = 3 (6c) n = 6 (6d) n = 10 (each to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(7a) n = 0 (7b) n = 3 (7c) n = 6 (7d) n = 10 (each to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(8a) n = 0 (8b) n = 3 (8c) n = 6 (8d) n = 10 (each to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(9a) n = 0 (9b) n = 3 (9c) n = 6 (9d) n = 10 (to be understood as an average - based on molar equivalents - of a molecular weight distribution)

(10) 2- (1-ethylpentyl) -1- (2-hydroxyethyl) -4,5-dihydro-imidazole and

(10a) n = 1 (10b) n = 4 (10c) n = 7 (10d) n = 11 (each to be understood as an average - based on molar equivalents - of a molecular weight distribution) Compound according to one of claims 1 to 6, characterized in that the substituent R ^{1 has} an average degree of branching from 0 to 2.5, preferably 0.2 to 1.6. A process for the preparation of compounds of general structure I, II or III according to one of claims 1 to 7, comprising the steps: - step a) - condensation reaction of an aldehyde or an aldehyde mixture with a polyfunctional compound to be reacted therewith containing at least one primary amino function - (in Preparation of compounds of formula I or II) or a primary or secondary amino function if R ^{4 is} hydrogen (when preparing compounds of formula III) and at least one second functional group selected from hydroxyl, diol, carboxyl and primary and secondary amino functions or a mixture of polyfunctional compounds, if appropriate in the presence of a suitable acid, - step b) - heating the reaction product from step a) in the presence of a basic compound, optionally additionally evacuating and / or adding an alkylene oxide. A method according to claim 8, characterized in that in step a) known Lewis or Bronsted acids in liquid or solid form, preferably sulfuric acid, p-toluenesulfonic acid, p-toluenesulfonic acid-pyridinium salt or acidic ion exchanger. A method according to claim 8 or 9, characterized in that the aldehyde is a linear or branched aliphatic C ₄ -C ₃₀ aldehyde, preferably a C ₆ -C ₁₈ aldehyde, with an average degree of branching from 0 to 2.5, preferably 0, 2 to 1.6, is used. Process for the preparation of a compound of formula I according to one of the claims 1 to 7, characterized in that in a known per se Condensation reaction a carboxylic acid or its derivative or a mixture of different carboxylic acids or their derivatives a polyfunctional compound or a mixture of several polyfunctional ones Compounds each containing at least one primary or secondary Amino function, and at least one second functional group selected from Hydroxyl, diol, carboxyl and primary and secondary amino functions. Process according to claim 11, characterized in that the carboxylic acid or its ester is a linear or branched aliphatic C ₄ -C ₃₀ carboxylic acid or its ester, preferably a C ₆ -C ₁₈ carboxylic acid or its ester, with an average degree of branching from 0 to 2.5, preferably 0.2 to 1.6, is used. Method according to one of claims 8 to 12, characterized in that a compound is selected from the following groups as the polyfunctional compound: linear and branched aliphatic C ₃ -C ₆ alkanolamines with at least one primary or secondary amino function and one hydroxyl function, in which at most 4 further hydroxyl or amino functions can be present, preferably exactly one amino function, and further substituents can be present from the group: -SH; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; -OR ²² ; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

linear and branched aliphatic C ₃ -C ₆ diamines with 2 to 6 primary or secondary amino functions; preferably 2 to 4 primary or secondary amino functions, and further substituents can be present from the group: -OH; SH; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; -OR ²² ; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

linear and branched aliphatic C ₃ -C ₆ aminothiols with at least one primary or secondary amino function and one thiol function, preferably the aminothiol used has exactly one primary or secondary amino function and exactly one thiol function and further substituents can be present from the group: -OH; -CN; -C (O) OH; -C (O) OR ¹⁸ ; -C (O) NR ¹⁹ R ²⁰ ; -OSO ₃ ^- ; -SO ₃ ^- ; -OPO ₃ ^2- ; OPO (OR ²¹ ) ₂ ; -OR ²² ; -C ₆ H ₅ , in which one or more hydrogens can be replaced by substituents; and

linear and branched aliphatic C ₃ -C ₆ amino acids with at least one primary or secondary amino function and one carboxyl function, preferably exactly one primary or secondary amino function; wherein the polyfunctional compound has at least one primary amino group in the preparation of compounds of formulas I and II by a process according to any one of claims 8 to 10. Method according to one of claims 8 to 13, characterized in that as alkanolamine trimethylolmethylamine, diethanolamine, propanolamine, dipropanolamine, aminosugar, as diamine propylene diamine, diethylene triamine, triethylene tetramine, N-aminopropylethylene diamine (N ₃ -amine), N, N'-bis (Aminopropyl) ethylenediamine (N ₄ amine), hydroxyethyl ethylenediamine, as aminothiol cysteine, tyrosine, mercaptopropylamine, as amino acid iminodiacetic acid HN (CH ₂ CO ₂ H) 2, ethylenediamine triacetic acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamine, Glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, or N-phosphonomethylglycine is used. Use of a substance according to one of claims 1 to 7 or a mixture thereof as a co-surfactant. Household detergents, household cleaners, personal cleansers or personal care products containing at least one compound according to any one of claims 1 to 7th Detergent according to claim 16 in solid, liquid, gel or more pasty Form, preferably as a powder, compact, granulate, tablet or Gel. Containing detergent according to claim 16 or 17 0.1 to 40% by weight, in particular 0.5 to 30% by weight, very particularly 1 to 20% by weight, based on the total amount of the formulation, at least a connection according to one of claims 1 to 6. Household cleaner according to claim 16 in liquid, gel or solid form, preferably as a liquid, gel, powder or Compact. Household cleaner according to claim 19 in the form of a Hand dishwashing detergent, machine dishwashers, metal degreasers, glass cleaners, Floor cleaner All-purpose cleaner, pressure washer, alkaline cleaner, acidic Cleaners, spray degreasers, dairy cleaners, upholstery, plastic, and bathroom cleaners. Household cleaner according to claim 19 or 20 containing 0.01 to 40 wt .-%, preferably 0.1 to 25 wt .-% based on the Overall formulation, at least one substance according to one of claims 1 to 7th Body wash or personal care products in the form of a shampoo, shower or Bath gel, shower or bath lotion, lipstick, cosmetic formulations with care and / or conditioning properties or a styling product, especially a liquid soap, a care cream, a hair foam, hair gel, hair sprays or Post-treatment agent, a hair tonic, a lotion, course rinse, spa pack, a top fluid, hair repair agent, "hot oil treatments", hair fixative, hair dye or permanent waving agent containing at least one substance one of the claims 1 to 7.