DE4005959A1 - LIQUID, FOAMING DETERGENT - Google Patents

Description

The invention relates to an environmentally compatible, liquid cleaning agent. Liquid, foaming cleaning agents are aimed at the manual cleaning of hard surfaces especially in the household, such as e.g. B. ceramics, porcelain, glass, metal and plastic. The most important Areas of application are manual detergents for cleaning of dishes.

Modern products here consist of neutral aqueous solutions Formulations based on highly foaming surfactants. Main ingredients are sulfonates, such as. B. alkylbenzenesulfonates or sec-alkanesulfonates, both combined with fatty alcohol ether sulfates or also fatty alcohol sulfates (EP-A 01 12 047). In small amounts fatty acid alkanolamides and, more rarely, oxyethylates are added. Other common ingredients are solubilizers, color and Fragrances, preservatives, etc.

The rinsing process usually takes place at a slightly elevated temperature (30 up to 50 ° C) in dilute solutions. Really important, due to the long skin contact of the user, the skin tolerance the detergent. When assessing the cleaning power the foaming power of the solution plays a role through the consumer significant role, for example in the sense of the longer the cleaning solution during the rinsing process foams the greater their cleaning power.

Generally recognized methods for determining the cleaning effect are

• a) the plate test with foaming detergents, its end point is determined by the foam disintegration, and
• b) the fat titration as a measure of the cleaning power,

both of which have very similar results (see G. Jakobi in H. Stache, Tensid Taschenbuch, 2nd edition, Munich 1981, pp. 252 ff.).

This parallelism probably has a qualitative foam existence and cleaning ability the manufacturers of conventional detergents  seduced to attach the greatest importance to the foam volume. The result of this is that the items to be washed are more customary Dosage of the detergent in the foam disappears, which is known also reduces the actual cleaning and also in terms of of the skin feeling can be uncomfortable.

Another disadvantage of the known detergents is their low level Skin friendliness, because its essential components - namely the anionic surfactants of the sulfonate or sulfate type - to a high degree are irritating to the skin.

And also disadvantageous with regard to the shortage of raw material reserves is the predominantly petrochemical basis of the above anionic surfactants combined with an incomplete biological Degradability.

The object of the invention was therefore a very skin-friendly cleaning agent with excellent cleaning effect with moderate To provide foaming power, its cleaning surfactant is largely biodegradable.

This problem was solved with a liquid detergent, which contains only alkyl polyglycoside as a cleaning surfactant.

The invention therefore relates to a liquid foaming cleaning agent, consisting of

3 to 40 percent by weight alkyl polyglycoside,
0 to 30 weight percent solubilizer,
0 to 10 percent by weight electrolyte,
0 to 3 weight percent additives and
Water ad 100 weight percent.

The use of alkyl polyglycosides in detergents and cleaning agents is known in combination with other surfactants. So describes the AT-PS 1 35 333 already the effect of lauryl glycoside combined with the sodium salt of ricin oil sulfuric acid ester as Wool detergent. In US-PS 37 21 633 alkyl polyglycosides  in combination with builder substances such as nitrilotriacetic acid or Sodium tripolyphosphate, described as a detergent. The combination of alkyl polyglycosides with fatty alcohol oxyethylates as liquid Detergent claims EP-A 01 05 556. Manual detergent using alkyl polyglycosides are described in the publications EP-A 00 70 074, EP-A 00 70 075 and EP-A 00 70 076, where among others anionic surfactants used as cosurfactant will. DE-OS 35 34 082 also has analogous content, with fatty alkyl glycosides with 1 to 1.4 glycoside units per fatty alkyl residue to be named. Alkyl sulfate or alkyl ether sulfates are used as cosurfactants each in combination with fatty acid alkanolamides. Finally, EP-A 01 99 765 describes a liquid detergent or Detergent with a similar claim. The use of a commercial Alkylpolyglycoside (Triton CG 110) in manual detergents in Combination with other surfactants is also in Rohm & Haas, Techn. Bulletin, Triton CG 110, May 1975.

All of these documents are the combination of alkyl polyglycosides together with other, mostly anionic surfactants. So it was assume that the interaction of the alkyl polyglycosides with others Surfactants is crucial for the cleaning effect.

In addition, comparative studies (see Table 2) have shown that e.g. B. Triton CG 110 alone has no rinsing effect.

Completely surprisingly, it has now been observed that detergents used as Cleaning surfactant containing only alkyl polyglycosides, excellent Achieve cleaning effects when these alkyl polyglycosides satisfy Formula I, d. H. a sufficiently hydrophobic structure exhibit. This can be achieved by using fatty alcohols relatively long hydrocarbon chains in the synthesis, the Quantity ratios of fatty alcohol to monosaccharide units so too choose that the average degree of glycosidation (glycoside units per fatty alkyl residue) is not too high.  

Alkyl polyglycosides

Alkyl polyglycosides used according to the invention satisfy formula I.

RON _n (I)

in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Z _{n represents} a polyglycosyl radical with n = 1.0 to 3 hexose or pentose units or mixtures thereof.

Alkyl polyglycosides with fatty alkyl radicals having 12 to 16 carbon atoms and a polyglycosyl group from n = 1.1 to 2. Alkyl polyglucosides are particularly preferred.

The alkyl polyglycosides used according to the invention can be: known processes based on renewable raw materials will. For example, dextrose is in the presence of an acid catalyst reacted with n-butanol to give butyl polyglycoside mixtures, which with long-chain alcohols also in the presence of an acid Umglycosidiert catalyst to the desired alkyl polyglycoside mixtures will.

The structure of the products can be varied within certain limits. The alkyl radical R is selected by the choice of the long-chain alcohol fixed. On an industrial scale, they are cheap for economic reasons accessible surfactant alcohols with 10 to 18 carbon atoms, in particular native fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives. Ziegler alcohols can also be used Oxo alcohols.

The polyglycosyl radical Z _n is determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization n. B. according to DE-OS 19 43 689. In principle, it is known that polysaccharides, e.g. B. starch, maltodextrins, dextrose, galactose, mannose, xylose, etc. can be used. The commercially available carbohydrates starch, maltodextrins and especially dextrose are preferred. Since the economically interesting alkyl polyglycoside syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with α- and β-glycosidic bonds in pyranose and furanose form. The links between two saccharide residues are also different.

Alkyl polyglycosides used according to the invention can also be used by mixing alkyl polyglycosides with alkyl monoglycosides produce. The latter can e.g. B. according to EP-A 00 92 355 by means of win polar solvents, such as acetone, from alkyl polyglycosides or enrich.

The degree of glycosidation is advantageously determined by means of 1 H-NMR certainly.

The cleaning agents according to the invention preferably contain 3 to 40% 5 to 30% alkyl polyglycoside in aqueous solution.

Compared to all others used in detergents The alkyl polyglycosides are considered to be extremely environmentally compatible. This is the case using a sewage treatment plant simulation model / DOC analysis certain degree of biodegradation for the alkyl polyglycosides according to the invention at 96 ± 3%. This number is against the background to see that with this test procedure (total degradation) a Degradation <70% indicated the substance to be readily degradable.

Acute oral toxicity LD 50 (rat) as well as aquatic Toxicity LC 50 (gold orfe) and EC 50 (daphnia) and values of <10,000 mg / kg, 12 or 30 mg / l are cheaper by a factor of 3 to 5 than the corresponding values of today's most important surfactants. The same applies to the skin and skin that are particularly important in detergents Tolerance to mucous membranes.

The alkyl polyglycosides according to the invention fall as synthesis-related about 50% aqueous amber solution. The solubility in  Water is not too much due to the hydrophobic structure setting high.

Solution broker

By adding solvents such as low-molecular, mono- and polyvalent Alcohols and glycol ethers are particularly soluble increase significantly even at low temperatures. Especially suitable solvents are ethanol, isopropanol, propylene glycol-1.2, etc. The ratio of alkyl polyglycoside / solvent can be 1: 1 to 8: 1.

Electrolytes

In combination with the solubilizer with electrolytes Solubility considerably, especially at low temperatures increase. Alkali and alkaline earth halides have been found to be suitable electrolytes proven. The solvent / electrolyte ratio can be 1: 1 to 8: 1.

Additives

Further components of the cleaning agents according to the invention are minor Quantities (0.1 to 3 percent by weight) are common dyes and perfume oils and alkanolamines or hydrotropics, such as non- surfactant alkylbenzenesulfonates with 1 to 3 carbon atoms in Alkyl residue - usually as sodium salts - as well as urea.

To set suitable viscosity, water-soluble ones may be used Polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, Xanthans, polyethylene oxide, polyacrylate, etc. can be added.

Citric acid, EDTA, NTA have also been found to be suitable additives and other complexing agents.

Examples

The following examples are intended to illustrate the invention.

The mini-plate test (cf. R.M. Anstett u. E.J. Schuck JAOCS 43, 576 (1966).

Here watch glasses are loaded with fat at elevated temperature manually cleaned with a brush in the surfactant solution. The test conditions (Preparations, geometries, amounts and concentrations of substances, Temperatures, temperature gradients, times) are accurate Are defined. The test is carried out by several people and provides reproducible results. Disappearing foam shows the number of cleaned plates (watch glasses). As soiling Pork lard served at 50.0 ° C on the glasses was applied, then a defined cooling process to 23 ° C (room temperature). The rinse start temperature is also 50 ° C.

Table 1 compares the cleaning effect of individual surfactants with alkyl polyglycosides strongly with increasing molecular hydrophobicity increases.

Table 2 demonstrates that there is also a sharp increase in surfactant concentration only gives unsatisfactory cleaning effects if the alkyl polyglycoside is too hydrophilic, as in the case of Triton CG 110.

Table 3a compares the cleaning effect of the invention Alkyl polyglycosides with those of optimized branded products depending the detergent concentration for a medium water hardness; Table 3b gives the analogous ratios for soft Water.  

Table 1

Mini plate test, concentration of detergent: 0.075 g / l, drinking water: 13 ° dH

Table 2

Mini plate test with Triton CG 110 *) (Rohm & Haas) depending on the water hardness and the surfactant concentration

Table 3a

Mini plate test with hydrophobic alkyl polyglycosides compared to branded detergents, water: 13 ° dH, pH 6-7

Table 3b

Mini-plate test with hydrophobic alkyl polyglycosides compared to branded detergents, water: 2 ° dH, pH 6-7

The excellent cleaning effect is shown in Tables 3a and 3b the alkyl polyglycosides according to the invention, which are very environmentally compatible individual surfactants in detergents an excellent Achieve cleaning effect.  

Table 4

Data and cleaning effect of preparations according to the invention

Table 4 shows the physical data of some of the invention Prepared preparations. The cleaning values also listed (Mini plate test) demonstrate the high effectiveness of the new cleaning systems.

Claims (8)

1. Liquid, foaming cleaning agent, consisting of 3 to 40 percent by weight alkyl polyglycoside,
0 to 30 weight percent solubilizer,
0 to 10 percent by weight electrolyte,
0 to 3 weight percent additives and
Water ad 100 weight percent. 2. Liquid, foaming cleaning agent according to claim 1, characterized in that the alkyl polyglycoside corresponds to the formula I RON _n (I), where R is a saturated or unsaturated, branched or unbranched alkyl radical having 10 to 18 carbon atoms, Z _{n is} a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof. 3. Liquid, foaming cleaning agent according to claim 1, characterized in that the alkyl polyglycoside corresponds to the formula I RON _n (I), where R is a saturated or unsaturated fatty alcohol having 10 to 18 carbon atoms and Z _{n is} a polyglucosyl radical with n = 1.1 to 2 mean glycoside units. 4. Liquid, foaming cleaning agent according to the claims 1 to 3, characterized, that as a solvent ethanol, i-propanol or propylene glycol-1,2 or mixtures thereof can be used.   5. Liquid, foaming cleaning agent according to the claims 1 to 4, characterized, that the ratio alkyl polyglycoside / solvent 1: 1 to 8: 1 is. 6. Liquid, foaming cleaning agent according to the claims 1 to 5, characterized, that the solvent / electrolyte ratio is 1: 1 to 8: 1. 7. Liquid, foaming cleaning agent according to the claims 1 to 6, characterized, that used as electrolyte, alkali and / or alkaline earth chloride becomes. 8. Use of the liquid, foaming cleaning agent according to Claims 1 to 7 as a manual detergent.