EP1323819B1 - Aqueous detergent composition with reduced oxidation power - Google Patents

Abstract

Aqueous surfactant preparations with reduced oxidizing power contain: <??>(A) amphoteric and/or zwitterionic surfactants; and <??>(B) thio-salts containing at least one sulfur-sulfur bond. <??>Independent claims are also included for: <??>(1) a method for reducing the oxidizing power of (A), involving addition of 0.01-1 wt.% (B) to (A); and <??>(2) the use of (B) for reducing the oxidizing power of (A).

Description

Field of the invention

The invention is in the field of surfactants and relates to novel preparations with betaines or amphoacetates and stabilizers and dyes, a method for reducing the oxidizing power of these surfactants, compositions containing these surfactants and the use of stabilizers to reduce the oxidizing power amphoteric or zwitterionic surfactants.

State of the art

Amphoteric or zwitterionic surfactants, especially substances known as "betaines", are important constituents of detergents, dishwashing detergents and cleaners, especially of manual dishwashing detergents, because of their high cleaning performance and excellent skin compatibility. In recent years Two trends are emerging in this sector: on the one hand, betaines which are still easily flowable despite the high paste concentration, which makes it easier to incorporate larger amounts of these surfactants in the final formulation, and, on the other hand, the consumer's desire for means that can be used have a tropical finish and smell, for example, mango, peach or lime. For the production of such products, however, not only special flavoring, but also dyes are needed, after all, you can not turn a dishwashing liquid that smells of pineapple green. However, the combination of the two mentioned developments leads to a hitherto unobserved problem: if the known betaines are used in high concentrations together with new dyes and fragrances, especially those which have -SS bonds as structural elements, oxidation processes occur the consequence of which the dyes decompose completely or partially. So it may happen that a green-colored rinse will turn blue within a few days or a yellow product is colorless at once. It is immediately clear that there is a desire to avoid these undesirable effects.

The object of the present invention has therefore been to provide novel aqueous surface-active preparations based on amphoteric or zwitterionic compounds, which are free from the disadvantages described, i. Even in high concentrations can be easily used with oxidation-sensitive dyes and fragrances.

Description of the invention

• (a) amphotere und/oder zwitterionische Tenside,
• (b) Alkali- und/oder Erdalkalithiosulfate und
• (c) Farbstoffe, die mindestens eine S-S-Bindung als Strukturelement aufweisen.

The invention relates to novel aqueous surface-active preparations with reduced oxidizing power, containing

• (a) amphoteric and / or zwitterionic surfactants,
• (b) alkali and / or alkaline earth metal thiosulfates and
• (C) dyes having at least one SS bond as a structural element.

Surprisingly, it has been found that the addition of thiosulfates reduces the oxidizing power of amphoteric or zwitterionic surfactants to such an extent that they can now be used without difficulty even in high concentrations with dyes which have S-S bonds, without resulting in undesired oxidation reactions.

Amphoteric or zwitterionic surfactants

in der R¹ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische.Examples of suitable amphoteric or zwitterionic surfactants which form component (a) are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (I) ,

in the R ^{1 is} alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R ^{2 is} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{3 is} alkyl radicals having 1 to 4 carbon atoms, q1 is a number from 1 to 6 and Z is a Alkali and / or alkaline earth metal or Ammonium stands. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C _12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C _16/18 tallowalkyldimethylamine, and technical mixtures thereof.

in der R⁴CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R⁵ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R⁶ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q2 für Zahlen von 1 bis 6, q3 für Zahlen von 1 bis 3 und Z wieder für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethyl-aminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat.Also suitable as component (a) are carboxyalkylation products of amidoamines which follow the formula (II) ,

in the R ⁴ CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ^{5 is} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{6 is} alkyl radicals having 1 to 4 carbon atoms, q 2 is from 1 to 4 6, q3 represents numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethyl-aminopropylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

Also suitable as component (a) are imidazolinium betaines. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

The amphoteric or zwitterionic surfactants may be present in the form of aqueous pastes with solids or water contents in the range of 45 to 55 wt .-%, wherein the active substance content is usually 35 to 40 wt .-% and the pH is both may be in the alkaline as well as acidic range. Corresponding products are commercially available, for example, under the name Dehyton® PK from Cognis Deutschland GmbH or Tegobetain® from Th.Goldschmidt AG.

antioxidants

The invention includes the recognition that only selected reducing agents are suitable for reducing the oxidizing power of the amphoteric or zwitterionic compounds; For example, sulfites or borohydrides are almost ineffective. For the purposes of the invention are as component (b) alkali and / or alkaline earth metal and especially sodium thiosulfate in question. The formulations may contain components (a) and (b) in a weight ratio of 99: 1 to 99.99: 0.01.

method

Another object of the invention relates to a method for reducing the oxidizing power of amphoteric and / or zwitterionic surfactants, which is characterized in that they 0.01 to 1, preferably 0.1 to 0.5 wt .-% of at least one alkali and / or alkaline earth thiosulfate and in particular sodium thiosulfate added.

Washing, rinsing and cleaning agents

Another object of the invention relates to detergents, dishwashing detergents and cleaners, especially manual dishwashing detergents containing surface-active compounds, dyes and perfume oils, which are characterized in that they contain amphoteric and / or zwitterionic surfactants whose oxidizing power by adding thiosalts with at least one SS binding has been reduced. Preferably, these agents contain the amphoteric and / or zwitterionic surfactants in amounts of 5 to 20, preferably 10 to 15 wt .-%, wherein the amounts refer to the amount of surfactant active substance in the amphoteric or zwitterionic surfactant. Preferably, these agents also contain those dyes having at least one SS bond as a structural element in amounts of 0.001 to 0.005 wt .-% - based on the means.

The washing, rinsing and cleaning agents may also contain other typical auxiliaries and ingredients. In the first place, these will be further anionic, nonionic or cationic surfactants.

Typical examples of anionic cosurfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates , Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat based vegetable products) and alkyl (ether ) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using alkyl sulfates, alkyl ether sulfates, alkanesulfonates, olefinsulfonates, soaps and mixtures thereof.

Typical examples of nonionic cosurfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters , Sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.

Typical examples of cationic cosurfactants are finally tetraalkylammonium compounds or esterquats. The cosurfactants may be present individually or in total in the final formulations in amounts of from 1 to 50, preferably from 10 to 40, and in particular from 15 to 30,% by weight.

Industrial Applicability

The addition of the thiosulfates means that the amphoteric or zwitterionic surfactants are compatible even in high concentrations with oxidation-sensitive dyes and fragrances. A final object of the invention therefore relates to the use of alkali metal and / or alkaline earth thiosulfates as agents for reducing the oxidizing power of amphoteric or zwitterionic surfactants. The amount used can, as already explained 0.01 to 1, preferably 0.05 to 0.5 wt .-% - based on the surfactants - amount.

Examples Examples 1 and 2, Comparative Examples C1 to V4

To check the reductive properties, 20% strength by weight aqueous solutions of various betaines were prepared and, if appropriate, 0.5% by weight, based on the betaine content, of two reductants was added. The formulations were further 0.0025 wt .-% dye (Basacid Yellow 099 liquid, BASF) was added, which led to an intense yellow color. Subsequently, the various mixtures were placed in a light chamber in which they were exposed to the white light of a mercury-vapor lamp over a period of 72 hours at 20 ° C. Subsequently, the color quality was assessed subjectively. The results are summarized in Table 1. Examples 1 and 2 are according to the invention, examples V1 to V4 are for comparison. <b><u> Table 1 </ u> Color Quality </ b> Ex. betaine reduktor colour V1 cocamidopropylbetaine without colorless V2 cocamidopropylbetaine sodium borohydride colorless 1 cocamidopropylbetaine sodium thiosulfate intense yellow V3 Cocoyldimethylaminobetain without colorless V4 Cocoyldimethylaminobetain sodium borohydride colorless 2 Cocoyldimethylaminobetain sodium thiosulfate intense yellow

It can be seen that the use of sodium borohydride leads to no improvement over the blank test, while the addition of sodium thiosulfate effectively prevents the yellow dye from being oxidized and thus destroyed.

Claims (9)

1. Water-based surface-active preparations with reduced oxidizing power containing

   (a) amphoteric and/or zwitterionic surfactants,

   (b) alkali metal and/or alkaline earth metal thiosulfates and

   (c) dyes having at least one S-S bond as a structural element.
2. Preparations as claimed in claim 1, characterized in that they contain as component (a) alkylbetaines corresponding to formula (I):

   

   in which R¹ represents alkyl and/or alkenyl groups containing 6 to 22 carbon atoms, R² represents hydrogen or alkyl groups containing 1 to 4 carbon atoms, R³ represents alkyl groups containing 1 to 4 carbon atoms, q1 is a number of 1 to 6 and Z is an alkali metal and/or alkaline-earth metal or ammonium.
3. Preparations as claimed in claims 1 and/or 2, characterized in that they contain as component (a) carboxyalkylation products of amidoamines corresponding to formula (II):

   

   in which R⁴CO represents an aliphatic acyl group containing 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R⁵ represents hydrogen or alkyl groups containing 1 to 4 carbon atoms, R⁶ represents alkyl groups containing 1 to 4 carbon atoms, q2 is a number of 1 to 6, q3 is a number of 1 to 3 and Z is again an alkali metal and/or alkaline-earth metal or ammonium.
4. Preparations as claimed in at least one of claims 1 to 3, characterized in that they contain imidazolinium betaines as component (a).
5. Preparations as claimed in at least one of claims 1 to 4, characterized in that they contain components (a) and (b) in a ratio by weight of 99:1 to 99.99:0.01.
6. Preparations as claimed in at least one of claims 1 to 5, characterized in that they have a water content of 45 to 55% by weight.
7. A process for reducing the oxidizing power of amphoteric and/or zwitterionic surfactants, characterized in that 0.01 to 1% by weight of at least one alkali metal and/or alkaline-earth metal thiosulfate is added to them.
8. The use of alkali metal and/or alkaline-earth metal thiosulfates as agents for reducing the oxidizing power of amphoteric or zwitterionic surfactants.
9. The use claimed in claim 8, characterized in that the thiosulfates are used in quantities of 0.01 to 1% by weight, based on the surfactants.