EP0513138A1

EP0513138A1 - Aqueous liquid cleaning agent.

Info

Publication number: EP0513138A1
Application number: EP91903675A
Authority: EP
Inventors: Ortburg Guirr; Birgit Dr Middelhauve
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1990-02-02
Filing date: 1991-01-24
Publication date: 1992-11-19
Anticipated expiration: 2011-01-24
Also published as: DE59102570D1; EP0513138B2; EP0513138B1; ES2059120T3; ES2059120T5; DE4003098A1; WO1991011506A1; ATE110106T1

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

"Aqueous liquid detergent"

Liquid cleaning agents usually consist of aqueous solutions of synthetic anionic and / or nonionic surfactants and conventional additives. They are used in particular for cleaning hard surfaces, for example glass, ceramic materials, plastics, painted and polished surfaces. An important area of application for liquid cleaning agents is the manual washing of eating and cooking utensils. The cleaning of the dishes is usually carried out at slightly elevated temperatures of about 35 to 45 ° C. in very dilute liquors. The cleaning power of an agent is generally assessed by the consumer the better and the longer the cleaning liquor foams. Because of the contact of the hands with the cleaning liquid over a long period of time, the skin-friendliness of the product is of particular importance when washing dishes manually. For these reasons alone, the expert makes different considerations when selecting the components and the composition of an agent for the manual cleaning of dishes than with liquid detergents for other hard surfaces. However, ecological aspects are also increasingly becoming the focus of interest. Thus, agents are preferred which are free from the proportions of anionic surfactants which are generally customary for such agents petrochemical basis such as B. Alkylbenzenesulfonates and alkanesulfonates.

From the literature (e.g. Landesgewerbeanstalt, Bayern, Issue 5 (1987), K. Goßler and R. Miess: Behavior of linear alkyl benzenesulfonates from household detergents during wastewater treatment - literature study) it is known that the anionic surfactants mentioned above are biodegradable under aerobic conditions - as they exist in the activated stage of sewage treatment plants - but show no or only partial degradation under anaerobic conditions of sludge digestion. However, if one chooses the preferred alkyl sulfates and alkyl ether sulfates as surfactants, these are not only very well finally degraded not only in the aerobic activation stage of the sewage treatment plants, but also under anaerobic conditions of sludge digestion (e.g. J. Steber, P. Gode, W Guhl: Fat. Sci. Technol. 90 (1), 32 (1988)).

It is also generally known that so-called alkyl ether sulfates, that is to say salts of sulfated adducts of about 2 to 5 moles of ethylene oxide with fatty alcohols having about 10 to 18, preferably 12 to 16, carbon atoms in the aliphatic radical have good foaming and cleaning power and skin-friendly properties own. The commercially available manual dishwashing agents (also known as dishwashing detergents) therefore generally represent aqueous solutions of such alkyl ether sulfates in conjunction with other surfactants, in particular alkylbenzenesulfonates and alkane sulfonates, and solubilizers, colorants and fragrances.

Swiss patent 354 195 discloses liquid detergents for manual dishwashing, which are a combination of an alkyl ether sulfate containing alkyl sulfate and a nonionic surfactant of the fatty acid alkanolamide type from mono- or dialkanolamides with no more than 3 carbon atoms in each alkanol residue saturated fat containing 10 to 14 carbon atoms, together with water, solubilizers, colorants and fragrances and, inter alia, have a low solidification point.

It is already known from US Pat. No. 3,219,656 that nonionic alkyl monoglucosides not only develop stable foam themselves, but also act as foam stabilizers for other anionic and nonionic surfactants.

European patent application 70 074 discloses foaming liquid detergents containing anionic surfactants, in particular alkylbenzenesulfonates, alkylglucosides and amine oxides or fatty acid alkanolamides, the alkylglucosides being alkyloligoglucosides which the glucose unit (GE) about 1.5 to 10 times included, acts. This value is an average value and also takes into account the presence of alkyl monoglucosides in a corresponding proportion. Alkyl glucosides with a degree of oligomerization of higher than 2 are found to be particularly suitable. Mixtures of such alkyl glucosides and alkyl ether sulfates in a ratio of 3: 2 are described as only slightly foaming.

In the German patent specification DE 35 34 082 and in the international patent applications WO 86/02943 and WO 89/02912, liquid cleaning agents for the manual cleaning of dishes, containing synthetic anionic surfactants of the sulfonate and / or or sulfate surfactants, fatty alkyl glucosides and optionally fatty acid alkanolamides which contain fatty alkyl glucosides with an average of less than 2 units per fatty alkyl radical, in particular 1 to 1.4 units.

From German Offenlegungsschrift 37 06 015 it is known that by adding anionic surfactants, preferably alkyl ether sulfates or alkyl sulfates and betaines, to liquid cleaning agents with sulfosuccinates and alkyl glucosides can increase performance in rinsing and improve storage stability.

European patent application 341 071 describes liquid detergents for manual dishwashing with an active substance content of 5 to 60% by weight, 30 to 60% by weight of an alkyl glucoside with preferably 1 to 1.4 GE in the molecule 12 to 30 wt .-% of a betaine and up to 1.5 times the amount, based on the betaine, of alkyl sulfates and / or alkyl ether sulfates. These surfactant mixtures are said to be distinguished by good foam stability and good cleaning performance.

However, the consumer expects not only a high cleaning power and good foam formation and foam stability when exposed to fat and ecological compatibility, but also an optically appealing appearance from aqueous cleaning agents which are specifically designed for the manual cleaning of dishes. Many products for manual cleaning of dishes are often offered in transparent and / or translucent bottles. In the trade, the products, even if they have been in warehouses that are usually not at a constant temperature, should be optically flawless. H. are transparent. Products which have a clear point below approximately 15 ° C. are considered to be particularly favorable.

It has now surprisingly been found that quaternary combinations of alkyl sulfate, alkyl ether sulfate, betaine and alkyl glucoside with a certain quantitative composition lead to better cold behavior, characterized by the clear point, than known binary, ternary or quaternary combinations of these surfactants. The lower the clear point, the better the cleaning agents are to be rated. The invention thus relates to aqueous, liquid cleaning agents, in particular for manual dishwashing, with an active substance content of 10 to 60, preferably 15 to 40 percent by weight, consisting of alkyl sulfates, alkyl ether sulfates, betaines and alkyl glucosides, which are characterized in that that they contain more than 45% of the active substance of alkyl sulfates and alkyl ether sulfates, their content being greater than 1.5 times the betaine content and being at least twice the alkyl glucoside content.

The content of alkyl sulfates and alkyl ether sulfates can be a maximum of about 50 times the betaine content and / or the alkyl glucoside content.

The preferred alkyl sulfates or alkyl ether sulfates are commercially available, they have a straight-chain, aliphatic C 1-4 _g , preferably C. - alkyl radical. The associated cation is preferably an alkali metal or ammonium ion. Alkyl ether sulfates in the degree of ethoxylation is from 1 to 5, preferably preferably from 2 to 4. Furthermore, the use of a Alkylethersulfatgemisches, consisting of 50 wt.-_ A C _-Alkylethersulfa.es and 50 wt -.% Of a C _{l ü} - Alkyl ether sulfates with 1 to 5, preferably 2 to 4, ethylene oxide groups instead of or together with the alkyl ether sulfate mixture (es) used, which contains the same components in a weight ratio of 70:30. Small amounts of shorter or longer alkyl chains in alkyl sulfates and / or alkyl ether sulfates change the results only insignificantly. The known proportion of alkyl sulfate in industrially produced alkyl ether sulfates is included here. 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. As betaines "simple betaines" of the type can:

^R 2

R. - N - CH-COO ©

R.

and / or "amidobetaines" of the type:

CH.

^R 4 ^{~ C} C \ I ©

N - CH ₂ - CH ₂ - CH ₂ - N - CH ₂ C00 Q

I I

H CH ₃

be used; the following applies to:

R. or R „= C _ß _ _lg linear or branched,

R ₂ or R ₃ = CH ₃ , C ₂ H ₅ , C ₃ H _? ,

The alkyl glucosides are of the fatty alcohol glucoside type. Compounds with an average of less than 2 GE per fatty alkyl radical are understood here, in particular those with 1.0 to 1.4 GE. The fatty alkyl radical has 10 to 18, in particular 12 to 14, carbon atoms. "Fatty alkyl" is understood to mean the residues of the fatty alcohols which are produced by hydrogenation of natural fatty acids and which are wholly or predominantly saturated.

Furthermore, the agents according to the invention can preferably also contain solubilizers, solvents, colorants and fragrances. Alkanolamines, polyols, such as ethylene glycol, propylene glycol-1, 2 or glycerol, for example, can serve as solubilizers, for example for small amounts of dye and perfume oil. The amounts used are generally between 1 and 15 percent by weight, based on the total composition.

In addition, mostly solvents, such as low molecular weight alkanols with 1 to 4 carbon atoms in the molecule, preferably ethanol and isopropyl alcohol, are used. The amounts used are up to 15 percent by weight, based on the total agent. Viscosity regulators such as urea, sodium chloride, ammonium chloride, magnesium chloride and salts of mono-, di- and tricarboxylic acids and mixtures thereof can also be used individually or in combination in the required amounts. Further customary optional additives are corrosion inhibitors and preservatives.

A remainder, to be calculated for a total of 100 percent by weight, for the total composition consists of water.

The liquid cleaning agents according to the invention according to the following examples were obtained by stirring the individual constituents together and allowing the mixture to stand until there were no bubbles.

Examples

Example 1 : .

The following substances were used:

FAS: C _{1 2} _ ₁₄ alkyl sulfate, Na salt

FES-1: C _{1 2} _ _{1 4} alkyl ether sulfate, 2 EO, Na salt

Betaine-1: C_, g-dimethylacylamidobetaine

APG: C _{1 2} _ _{1 4} alkyl glucoside 1, 4 GE

EtOH: ethanol

The neutral combinations listed were adjusted with sodium chloride and / or ethanol to viscosities between 300 and 400 mPas (according to Höppler, 20 ° C). The samples were stored at -15 ° C for 24 hours. The temperature at which the products became optically clear was determined as a clear point.

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

Table 1

Example 2:

The following results (Table 2) show that the quaternary combinations of alkyl sulfate, alkyl ether sulfate, betaine and alkyl polyglucoside have an excellent low-temperature behavior over a wide mixing range - even in the presence of large amounts of alcohol. The viscosities were set as described in Example 1 and the clear point was determined accordingly.

Example 3

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

(A): Beef tallow soiling

The saucers are each covered with 2 g of melted beef tallow (test soil A). Then 8 l of tap water (16 ° d) at 50 ° C. are placed in a bowl. To clean the plates soiled with (A), 4 g, i.e. 0.5 g / l, of the cleaning agent added and the plates washed. The plates listed in Table 3 could be rinsed clean until the foam of the initially foaming solution disappeared.

(B): mixed soiling

The saucers are each covered with 2 g of mixed soiling (test soiling B). This soiling is obtained by mixing water, fat and carbohydrates (Mi No 1 from Henkel) with water. Then 8 l tap water (16 ° d) at 45 ° C are placed in a bowl. To clean the plates soiled with (B), 3, 2 g, i.e. 0.4 g / l, of the detergent produced are added and the plates are washed. The plates that were rinsed clean until the foam disappeared are listed in Table 3. Table 3

(A): Number of cleanly washed plates: use of grease (B): Number of cleanly washed plates: use of grease Example 4:

The following results (Table 4) show that not only amido betaines (betaine-1) but also simple betaines (betaine-2) can be used. Not only products with an average EO degree of approx. 2 and normal coconut chain distribution (C: C_. = 70: 30) can be used as alkyl ether sulfates, but also products with an average EO degree of approx. 3.6 and a chain distribution C _.-: C_. = 50: 50. The following substances were used:

FES-2: C 1-4 alkyl ether sulfate, 3.6 EO, Na salt

Betain-2: C_- _1Q -dimethylalkylacetobetaine

1 - 1 o

Example 5:

The following results show that not only the binary surfactant combinations of alkyl sulfate and alkyl ether sulfate lead to products with good cold behavior, but also 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 substance content of the formulations according to the invention can vary over a wide range and in any case advantages over the corresponding combinations according to EP application 341 071 (formulas A and B) are obtained.

Table 6

Formula No.

Water (rest) R R

Clear point (° C) 13 16 17

Plate (A) 12 18 17 16 18 18

Plate (B) 26 4.0 45 45 39 36

Claims

Patent claims

1. Aqueous liquid cleaning agents, in particular for manual dishwashing, with an active substance content of 10 to 60, preferably 15 to 40 percent by weight, consisting of alkyl sulfates, alkyl ether sulfates, betaines and alkyl glucosides, characterized in that they contain more than 45% of the active ingredient contain alkyl sulfates and alkyl ether sulfates, the content of which is greater than 1.5 times the betaine content and is at least twice the alkyl glucoside content.

2. Composition according to claim 1, characterized in that the content of alkyl sulfates and alkyl ether sulfates makes up a maximum of about 50 times the betaine content.

3. Composition according to claims 1 and 2, characterized in that the content of alkyl sulfates and alkyl ether sulfates makes up a maximum of about 50 times the alkyl glucoside content.

4. Composition according to claims 1 to 3, characterized in that the alkyl sulfates contain straight-chain, aliphatic C _._ _ _._-, preferably C. «_ -" - alkyl radicals.

5. Composition according to claims 1 to 4, characterized in that the alkyl ether sulfates straight-chain, aliphatic C.- _. _g -, preferably C-- _. "- contain alkyl radicals and 1 to 5, preferably 2 to 4 ethylene oxide groups.

6. Composition according to claims 1 to 5, characterized in that the weight ratio of alkyl sulfate to alkyl ether sulfate is 4: 1 to 1: 5.

7. Composition according to claims 1 to 6, characterized in that they additionally contain compounds from the group of solvents, solvents, dyes, fragrances and preservatives.