WO1993020171A1

WO1993020171A1 - Low foaming aqueous detergent mixtures

Info

Publication number: WO1993020171A1
Application number: PCT/EP1993/000724
Authority: WO
Inventors: Wolfgang Poly; Christian Nitsch
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-04-02
Filing date: 1993-03-25
Publication date: 1993-10-14
Also published as: DE4210912A1

Abstract

Low foaming aqueous detergent mixtures contain: (a) alkyl- and/or alkenyloligoglycoside ethers having the formula (I): (R1-0-[G]¿p)(R?2)n, in which R1 stands for a linear or branched aliphatic hydrocarbon residue with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds; R2 stands for a linear or branched alkyl residue with 1 to 8 carbon atoms or a benzyl residue, [G] stands for a sugar residue with 5 to 6 carbon atoms, p stands for numbers from 1 to 10 and n for numbers from 0.1 p to 2 p; and (b) anionic, non-ionic and/or amphoteric or zwitterionic surface-active agents.

Description

Low-foaming aqueous petroleum mixture

Field of the Invention

The invention relates to low-foaming aqueous detergent mixtures comprising alkyl and / or alkenyl oligoglycoside ethers and anionic, nonionic and / or amphoteric or zwitterionic surfactants, and to the use of alkyl and / or alkylene oligoglycoside ethers as defoamers for producing low-foam aqueous detergent mixtures and the products containing them.

State of the art

The effective and uniform control of the amount of foam that is formed during washing, rinsing and cleaning is a traditional and well-known aspect of the product formulation, the additional improvement of which is desired. Excessive foaming can adversely affect the overall benefits of modern detergent mixtures, for example when washing is performed in a drum type washing machine. Excessive foaming in the washing machine is undesirable because it not only reduces the effect of the washing liquor on the textiles, but also less Foam in the washing machine can be transferred to the rinse cycle. This not only amounts of foam at the ^"Rinse and thereby associated difficulties are the Unter¬ suppression same increases, but it is also the added during the rinsing agents, for example Weich¬ maker, adversely affecting [SFW, 117. 177 (1991)] .

In the past there has been no lack of attempts to solve the problem of excessive foam development, in particular anionic surfactants, by adding suitable foam regulating agents, which are also often referred to as "foam brakes". The most important include the salts of long-chain fatty acids [DE-PS-10 56 316, DE-PS-10 80 250, Procter & Gamble Co.] as well as end-capped fatty alcohol polyglycol ethers, so-called "mixed ethers" [DE-Al- 33 45 349, EP-B1-0 303 928, Henkel KGaA].

Disadvantages when using the foam regulating agents mentioned are due to the fact that

o they cannot be applied to all anionic surfactant systems, o have a reduced regulating activity at temperatures in the range from 60 to 90 ° C, o have a reduced activity in soft water, o show uneven regulation over the practical application range and o zu can have a negative influence on the application properties of the foam-regulated products. The object of the invention was therefore to schaumregu¬ profiled detergent mixtures based on anionic, nonionic to provide ^"shear and / or amphoteric or zwitterionic surfactants are available which are free from the share Nach¬.

Description of the invention

The invention relates to low-foam aqueous detergent mixtures containing

a) alkyl and / or alkenyl oligoglycoside ethers of the formula (I)

(Rl-0- [G] _p ) (R2) _n (I)

in the

Rl is a linear or branched aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

R2 represents a linear or branched alkyl radical having 1 to 8 carbon atoms or a benzyl radical,

[G] for a sugar residue with 5 or 6 carbon atoms, p for numbers from 1 to 10 and n for numbers from 0.1 p to 2 p

stands, and b) anionic, nonionic and / or amphoteric or zwitterionic surfactants.

Surprisingly, it has been found that the addition of alkyl and / or alkenyl oligoglycoside ethers reduces the foaming power of a large number of anionic surfactants in a synergistic manner. The detergent mixtures according to the invention have low foaming and a constantly high performance over a wide temperature range. Alkyl oligoglucoside benzyl ethers have proven to be particularly effective foam brakes.

Alkyl and / or alkenyl oligoglycoside ethers are known low-foaming substances which are known, for example, from DE-Al-38 35 199 (BASF AG). For their preparation, one can start from alkyl and / or alkenyl oligoglycosides which are etherified with alkyl or alkyl aryl halides in the presence of alkali metal hydroxides.

Alkyl and / or Alkenyloligoglykosidether, which can be used in the context of the invention preferably provide Um¬ reduction products of Cg-C22 ~ ^A lkyl- and / or Alkenyloligogly¬ kosiden with Ci-Cg-alkyl halides or benzyl halides. Typical examples are reaction products of Ci2 / 14 ~ cocoalkyl oligoglucoside, Cg i _Q -Ko ^ os- ^ lkyloligoglucosid or Ci6 / ιg-tallow alkyl oligoglucoside with methyl chloride, butyl chloride, octyl chloride or benzyl chloride.

Preferred alkyl and / or alkenyl oligoglycoside ethers are the alkyl and / or alkenyl oligoglycoside ethers of the formula (I) in which R! for an alkyl radical with 12 to 18 carbon atoms. R2 fo _r ^* a benzyl radical, p is a number from 1 to 3 and n is a number from 0.7 to 1.3.

Suitable anionic surfactants which can make up the mixture component b) are soaps, alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, alkyl ether sulfonates, alpha sulfo fatty acids, internal sulfo fatty acids, alpha ester sulfonates, glycerol ether sulfonates, alkyl sulfates, alkyl ether sulfates with conventional narrow homolog distribution, glycerol ether sulfates, monoglyceride (ether) sulfates, hydroxy mixed ether sulfates, alkyl oligoglucoside sulfates, isethionates,

Taurides, sarcosinates, ether carboxylic acids, sulfosuccinates, sulfotriglycerides, protein fatty acid condensates and / or alkyl (ether) phosphates. Detergent mixtures in the sense of the invention. Processes are preferred because of their particularly effective foam regulation and contain, as component b), alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates and / or alpha-ester sulfonates.

Suitable nonionic surfactants which can constitute mixture component b) are alkyl and / or alkenyl oligoglycosides, sugar esters, sorbitan esters and polysorbates. Detergent mixtures which are preferred in the sense of the process according to the invention because of their particularly effective foam regulation contain as component b) alkyl oligoglucosides.

Finally, alkyl betaines, alkylaminopropionates, imidazolinium betaines and sulfobetaines are suitable as amphoteric or zwitterionic surfactants, which can also be used as mixture component b). The low-foam aqueous detergent mixtures according to the invention can the alkyl and / or alkenyl oligoglycoside ethers and the anionic, nonionic and / or amphoteric or zwitterionic surfactants in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5 and in particular 1: 1 to 1: 4 included.

To prepare the detergent mixtures according to the invention, it is sufficient to combine the individual components, if appropriate at an elevated temperature of 40 to 50 ° C., with stirring. The mixing takes place in a purely mechanical way - there is no chemical reaction.

Industrial applicability

The detergent mixtures according to the invention are low-foaming and are distinguished by excellent surface-active properties. They are therefore suitable for the production of detergents, dishwashing detergents and cleaning products and products for hair and body care, in which they can be present in concentrations of 1 to 50, preferably 5 to 25% by weight, based on the composition.

Another object of the invention further relates to the use of alkyl and / or alkenyl oligoglycoside ethers as defoamers for the preparation of low-foam aqueous detergent mixtures and agents containing them.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it. Examples

I. Preparation of C- _\ 7/14-Kokosalkyloligoglucosidbenzylether

In a 1-1 three-necked flask equipped with a stirrer and internal thermometer

434 g (1 mol) Ci2 / 14 ^-K ° kosalkylglucoside,

Average degree of oligomerization: 1.4 hydroxyl number: 635.5 and

126 g (1 mole) of benzyl chloride

submitted and stirred over a period of 1 h at a temperature of 90 ° C. Then 44 g (1 mol) of sodium hydroxide were added and the reaction mixture was stirred at 80 ° C. for 8 h. After cooling, the crude benzyl ether was diluted with water and neutralized with 50% by weight sulfuric acid. The organic phase was separated off using a separating funnel and then freed from any traces of water in a water jet vacuum at 200 ° C. Finally, the product was filtered in the presence of a filter aid (Celite ^(R )). The anhydrous alkyl glucoside benzyl ether was obtained as a clear, yellow colored liquid. The product showed the following key figures:

Hydroxyl number: 437

Middle. Degree of etherification: 1 II. Examples of application technology

The application tests of the foaming power were carried out in accordance with DIM 53 902.2 under the following conditions:

Concentration: 0.5 g / 1 (based on active substance) Water hardness: 16 ° d Temperature: 40 ° C.

For the measurements, 250 ml of the test solutions were first transferred to a 500 ml standing cylinder. The foam was produced with the aid of a perforated disk attached to a stamp, which was immersed in the solutions and was moved up and down there at a high frequency over a short period of time. The foam height was read off immediately, ie after the end of foam generation, and the foam disintegration was monitored over a period of 20 minutes.

Mixed> τ.e substances;

Anionic surfactants: AI) Ci2 / 14 ^coconut alcohol sulfate _r Na salt

Texapon ( ^R ) LS 35, from Henkel KGaA A2) dodecylbenzenesulfonate Na salt

Maranil ( ^R ) A55, Henkel KGaA ^A 3) Cig / ig tallow methyl ester sulfonate Na salt

Texin ( ^R ) ES 68, Henkel KGaA A4) Cis / ig tallow alcohol sulfate Na salt

Sulfopon ( ^R ) T 55, Henkel KGaA

Nonionic surfactants ^B1 ) Ci2 / χ4-Kokosalkyloligoglucosidbenzylether according to I) B2) Ci2 / 14 "K ° kosalkyloligoglucosid

Plantaren ( ^R ) APG 600, Fa. Henkel KGaA

^B3 ) Ci2 / 18 ^{coconut lime 1} ~ ¹⁰ EO-butyl ether Dehypon ( ^R ) LT 104, from Henkel KGaA

The results of the foam measurements are summarized in Tab. 1. Detergent mixtures with B1 are according to the invention, the mixtures with B2 and B3 are used for comparison.

Tab. 1: Foam measurements

Legend: AT = anionic surfactant NT = nonionic surfactant AT: E = weight ratio of anionic / nonionic surfactant

Claims

1. Containing low-foam aqueous detergent mixtures

a) alkyl and / or alkenyl oligoglycoside ethers of the formula (I)

in the

R1 for a linear or branched aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

stands, and

b) anionic, nonionic and / or amphoteric or zwitterionic surfactants.

2. Low-foam aqueous detergent mixtures according to claim 1, characterized in that they contain alkyl and / or alkylene oligoglucoside ethers of the formula (I) in which R ^{1 stands} for an alkyl radical with 12 to 18 carbon atoms, R2 for a benzyl radical, p for numbers from 1 to 3 and n ^" for numbers from 0.7 to 1.3.

3. Low-foam aqueous detergent mixtures according to claim 1, characterized in that they selected anionic surfactants from the group formed by soaps, alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, alkyl ether sulfonates, alpha-sulfofatty acids, internal sulfofatty acids, alpha Ester sulfonates, glycerol ether sulfonates, alkyl sulfates, alkyl ether sulfates with conventional or narrow homolog distribution, glycerol ether sulfates, monoglyceride (ether) sulfates, hydroxymixed ether sulfates, alkyl oligoglucoside sulfates, isethionates, taurides, sarcosinates, sulfosuccinate acid, sulfonate carboxylates Alkyl (ether) phosphates formed.

4. Low-foam aqueous detergent mixtures according to claim 1, characterized in that they contain nonionic surfactants selected from the group consisting of alkyl and / or alkenyl oligoglycosides, sugar esters, sorbitan esters and polysorbates.

5. Low-foam aqueous detergent mixtures according to claim 1, characterized in that they contain amphoteric or zwitter¬ ionic surfactants selected from the group consisting of alkyl betaines, alkylaminopropionates, imidazoliniuπibe- taines and sulfobetaines.

6. Low-foam aqueous detergent mixtures according to claim 1, characterized in that they contain the alkyl and / or Al¬ kenyloligoglycosidether and the anionic, non-ionic and / or amphoteric or zwitterionic Ten¬ side in a weight ratio of 10: 1 to 1:10 .

7. Use of alkyl and / or alkenyl oligoglycoside ethers as defoamers for the preparation of low-foam aqueous detergent mixtures and agents containing them.