DE4003098A1 - WAESSFUL LIQUID CLEANING AGENT - Google Patents

Abstract

Aqueous liquid cleaning agent, especially for dishwashing by hand, with an active substance content of 10 to 60, preferably 15 to 40 % wt., consisting of alkyl sulphates, alkyl ether sulphates, betains and alkyl glucosides containing more than 45 % alkyl sulphates and alkyl ether sulphates in the active substance, whereby their content is more than 1.5 times the betain content and at least double the alkyl glucoside content.

Description

Liquid detergents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and usual additives. They are especially for cleaning Hard surfaces, for example of glass, ceramic Materia lien, plastics, painted and polished surfaces ver applies. An important application for liquid cleaning Medium is the manual rinsing of eating and cooking utensils. The Dishwashing is usually done at slightly elevated temperature temperatures of about 35 to 45 ° C in heavily diluted liquors carried out. This is the consumer of the cleaning power Generally speaking, the better and the better the assessment of an agent the longer the cleaning liquor foams. Because of the contact of the Hands with the cleaning liquor for a long period of time with manual rinsing of dishes also the skin friendliness of the agent of particular importance. Already for these reasons the expert in the selection of components and the Composition of a means for the manual cleaning of Dishes other considerations than with liquid cleaning for other hard surfaces. But they are also increasing ecological aspects in the field of interest ge disengaged. Thus, agents are preferred which are free of such In general, conventional amounts of anionic surfactants on  petrochemical base such. B. Alkylbenzenesulfonates and Al sulfonates.

From the literature (eg Landesgewerbeanstalt, Bavaria, number 5 (1987), K. Gossler and R. Miess: Behavior of Linear Alkyl Benzenesulfonates from household detergents in Abwasserbe Action - literature study) is known that the above Anionic surfactants under aerobic conditions - as in the animated level of wastewater treatment plants are biodegradable, but under anaerobic conditions of sludge digestion no or show only partial degradation. However, if you choose the one before here ferred alkyl sulfates and alkyl ether sulfates as surfactants, so be these not only in the aerobic activated sludge stage of sewage treatment plants, but also under anaerobic conditions of sludge digestion very good end-degraded (eg J. Steber, P. Code, W. Cuhl: Fat. Sci. Technol. 90 (1), 32 (1988)).

It is also well known that so-called alkyl ether sulfates, that is, salts of sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols having about 10 to 18, preferably Wise 12 to 16 carbon atoms in the aliphatic radical is a good Foaming and cleaning power as well as skin-friendly properties have. The standard, manually applicable dishes Therefore, detergents (aka dishwashing detergents) are generally used aqueous solutions of such alkyl ether sulfates in conjunction with other surfactants, especially alkylbenzenesulfonates and alkane sulfonates, as well as solubilizers, dyes and fragrances.

From the Swiss Patent 3 54 195 are liquid Detergents for manual dishwashing known a combination of alkyl sulfate containing alkyl ether sulfate and a nonionic surfactant of the fatty acid type alkanolamides of mono- or dialkanolamides with not more than 3 Carbon atoms in each alkanol radical of saturated fatty acids  with 10 to 14 carbon atoms together with water, solutions mediators, dyes and fragrances included and among others have a low freezing point.

From the US Patent 32 19 656 is already known that nonionic alkyl monoglucosides not only self-stable foam but as foam stabilizers for other anioni and nonionic surfactants act.

From the European patent application 70 074 are foaming liquid detergents containing anionic surfactants, in particular alkylbenzenesulfonates, alkylglucosides and amine oxides or fatty acid alkanolamides known, wherein it the alkylglucosides are alkyloligoglucosides, which are the Glucose unit (CE) about 1.5 to 10 times. This Value is an average and also takes into account the presence of Alkyl monoglucosides in a corresponding proportion. As special suitable are alkylglucosides with an oligomerization degree of higher than 2. Mixtures of such Alkyl glucosides and alkyl ether sulfates in the ratio 3: 2 described as only slightly foam-improving.

In the German patent DE 35 34 082 and in the inter national patent applications WO 86/02 943 and WO 89/02 912 wer the liquid detergent for the manual cleaning of Ge containing synthetic anionic surfactants of the sulfo type natural and / or sulphate surfactants, fatty alkylglucosides and optionally Fatty acid alkanolamides containing fatty alkylglucosides average less than 2 GE per fatty alkyl radical, esp from 1 to 1.4 GE.

From the German patent application 37 06 015 it is known that by addition of anionic surfactants, preferably Alkylethersul fats or alkyl sulfates and betaines for liquid cleaning  from sulphosuccinates and alkylglucosides Leistungsstei in the flushing capacity and improvements in storage stability can achieve.

In the European patent application 3 41 071 liquid Detergent for manual dishwashing with a Active substance content of 5 to 60 wt .-% described that to 30 to 60 wt .-% of an alkyl glucoside with preferably 1 to 1.4 GE in the molecule, to 12 to 30 wt .-% of a betaine and to 1.5-fold amount, based on the betaine, of alkyl sulfates and / or alkyl ether sulfates may exist. This surfactant mixture should be characterized by good foam stability and good Reini performance.

Of aqueous detergents, especially for the manual Cleaning of dishes are designed, the consumer expects but not only a high cleaning power and a good foam formation and foam stability in case of fat load as well as ecological Compatibility, but also a visually appealing appearance ance. Many products for manual cleaning of dishes are often in transparent and / or translucent bottles offered. In trade, the products should, even if they are over for a long time in usually non-tempered camps stood have, therefore optically perfect, d. H. transparent. Be considered as particularly favorable such products, the egg have a clear point of less than about 15 ° C.

It has now surprisingly been found that quaternary Combinations of alkyl sulfate, alkyl ether sulfate, betaine and Alkylglucoside with a certain quantitative composition to a better cold behavior, characterized by the clear point, lead as known binary, ternary or quaternary Combinations of these surfactants. The lower the clear point The better the cleaning agents are.  

The invention thus relates to aqueous liquid detergents, especially for manual dishwashing, with one active substance content of 10 to 60, preferably 15 to 40 wt percent, consisting of alkyl sulfates, alkyl ether sulfates, beta and alkylglucosides, which are characterized in that they contain more than 45% of the active substance in alkyl sulfates and Al contain kylethersulfaten, the content of which is greater than that Is 1.5 times the betaine content and that at least double the Alkylglucosidgehalts makes.

The content of alkyl sulfates and alkyl ether sulfates can be maximum about 50 times the betaine content and / or the alkylglucoside make up for salary.

The alkyl sulfates or alkyl ether sulfates preferably used are commercially available, they have a straight-chain, aliphatic C _12-18 , preferably C _12-14 - alkyl radical. The associated cation is preferably an alkali metal or ammonium ion. In the case of alkyl ether sulfates, the degree of ethoxylation is 1 to 5, preferably 2 to 4. Further preferred is the use of an alkyl ether sulfate mixture consisting of 50% by weight of a C ₁₂ -alkyl ether sulfate and 50% by weight of a C ₁₄ -alkyl ether sulfate with 1 to 5, preferably 2 to 4 ethylene oxide groups instead of or together with the usually used Al kylethersulfatgemisch (es) containing the same components in Ge weight ratio 70: 30. Small amounts of shorter or longer alkyl chains in alkyl sulfates and / or alkyl ether sulfates change the results only insignificantly. The well-te alkyl sulfate in technically produced alkyl ether sulfates is attributed to this. The claimed alkyl sulfate content is added separately. The quantitative ratio of alkyl sulfate to alkyl ether sulfate is preferably 4: 1 to 1: 5.

Betaine can be "simple betaine" of the type:

and / or "amidobetaines" of the type:

be used; where:

R₁ or R₄ = C _8-18 linear or branched,
R₂ or R₃ = CH₃, C₂H₅, C₃H₇.

The alkylglucosides are of the fatty alcohol glucoside type. you here means connections with less on average as 2 GE per fatty alkyl radical, especially those with 1.0 to 1.4 GE. The fatty alkyl radical has 10 to 18, in particular 12 to 14 Carbon atoms on. By "fatty alkyl" are the radicals of Fat produced by hydrogenation of natural fatty acids alcohols which are completely or predominantly saturated, understood.

Furthermore, the agents according to the invention may also be preferred nor solubilizers, solvents, dyes and fragrances ent hold.  

As a solubilizer, for example for low dye and perfume Oil additives, for example, alkanolamines, polyols, such as ethylene glycol, propylene glycol-1,2 or clycerol. Your commitment amounts are generally between 1 and 15 percent by weight, based on the total mean.

In addition, most solvents, such as low molecular weight Alka noles having 1 to 4 carbon atoms in the molecule, preferably etha nol and isopropyl alcohol used. Their amounts used amount up to 15% by weight, based on the total agent. Also Viscosity regulators such as urea, sodium chloride, ammonium chloride, magnesium chloride and salts of mono-, di- and tricar Bonsäuren and mixtures thereof can be used individually or in combination be used in required quantities. Other usual Optional additives are corrosion inhibitors and preservatives insurance agent.

A still about to total 100 percent by weight to be calculated Remainder for the total agent consists of water.

The liquid detergent according to the invention according to the fol The following examples were obtained by combining the individual Ingredients and leaving the mixture to bubble free received.  

Examples example 1

The following substances were used:

FAS: C _12-14 alkyl sulfate, Na salt FES-1: C _12-14 alkyl ether sulfate, 2 EO, Na salt Betaine 1: C _8-18 dimethylacylamidobetaine APG: C _12-14 alkyl glucoside 1.4 GE EtOH: ethanol

The listed, neutral combinations were with common salt and / or ethanol at viscosities between 300 and 400 mPas (according to Höppler, 20 ° C). The samples were 24 hours stored at -15 ° C. As a clear point, the temperature was true, at which the products became optically clear again.

The following results (Table 1) show that the quaternary Combinations of alkyl sulfate, alkyl ether sulfate, betaine and Alkylpolyglucoside over a wide mixing range have excellent cold behavior.  

Table 1

Example 2

The following results (Table 2) show that the quaternary Combinations of alkyl sulfate, alkyl ether sulfate, betaine and Alkylpolyglucoside over a wide mixing range - also in Presence of larger amounts of alcohol - an excellent Have cold behavior. The viscosities were as in Example 1 set and the clear point accordingly certainly.

Table 2

Example 3

The following results show that the quaternary combinati of alkyl sulfate, alkyl ether sulfate, betaine and alkyl polygluco not only have advantages in terms of their cold behavior, but also to excellent rinsing results to lead. The cleaning performance was determined using the plate test determined as described below:

(A): beef tallow pollution

The saucers are mixed with 2 g of molten beef tallow (Test soil A) coated. Then 8 l of tap water water (16 ° d) at 50 ° C in a bowl. For cleaning the plate soiled with (A) was 4 g, d. H. 0.5 g / l, of Detergent added and washed the plates. Until the Disappearance of the foam of the initially strong foaming Solution could clean the dishes listed in Table 3 be rinsed.

(B): mixed soiling

The saucers are mixed with 2 g of mixed soil (test soiled B). This soiling is obtained by mixing in water a mixture of protein, fat and Carbohydrates (Mi No 1 from Henkel). Then 8 l line water (16 ° d) of 45 ° C in a bowl. For cleaning the plate soiled with (B) was 3.2 g, d. H. 0.4 g / l, of the detergent produced and the plates washed. The clean until the disappearance of the foam rinsed plates are listed in Table 3.  

Table 3

Example 4

The following results (Table 4) show that not only amidobetaines (betaine-1) but also simple betaines (betaine-2) can be used. As alkyl ether sulfates not only products with a mean EO degree of about 2 and normal coconut chain distribution (C ₁₂ : C ₁₄ = 70:30) can be used, but also products with a mean EO degree of about 3.6 and a chain distribution C ₁₂ : C ₁₄ = 50:50.

The following substances were used:

FES-2: C _12-14 alkyl ether sulfate, 3.6 EO, Na salt. Betaine 2: C _12-18 dimethylalkyl acetobetaine

Table 4

Example 5

The following results show that not only the binary Surfactant combinations of alkyl sulfate and alkyl ether sulfate to Lead products with good cold behavior, but that the ternary surfactant combinations of alkyl sulfate and various Alkyl ether sulfates meet these requirements.

Table 5

Example 6

The following results show that the active ingredient content of formulations of the invention over a wide range can vary and certainly advantages over the corresponding combinations according to the EP application 3 41 071 (Formulas A and B) are obtained.

Table 6

Claims (7)

1. Aqueous liquid detergent, in particular for manual dishwashing, having an active ingredient content of 10 to 60, preferably 15 to 40 percent by weight, consisting of alkyl sulfates, alkyl ether sulfates, betaines and alkyl glucosiden, characterized in that they contain more than 45% of the active substance in alkyl sulfates and Alkylethersulfaten keep ent, wherein the content of which is greater than 1.5 times the Be taingehaltes and at least twice the Alkylglu cosidgehalts makes. 2. Composition according to claim 1, characterized in that the Content of alkyl sulfates and alkyl ether sulfates at most about which is 50 times the betaine content. 3. Composition according to claims 1 and 2, characterized that the content of alkyl sulfates and alkyl ether sulfates maximum is about 50 times the alkylglucoside content. 4. Composition according to claims 1 to 3, characterized in that the alkyl sulfates contain straight-chain, aliphatic C _12-18 , preferably C _12-14 , alkyl radicals. 5. Composition according to claims 1 to 4, characterized in that the alkyl ether sulfates _contain straight-chain, aliphatic C _12-18- preferably C _12-14 - alkyl radicals and 1 to 5, preferably 2 to 4 ethylene oxide groups. 6. Composition according to claims 1 to 5, characterized that the weight ratio of alkyl sulfate to alkyl ether sulfate 4: 1 to 1: 5.   7. Composition according to claims 1 to 6, characterized that they additionally compounds from the group of solutions mediators, solvents, dyes, fragrances and preserves contained.