DE4036663A1 - LIQUID, LUBRICANT CLEANING AGENT WITH INCREASED VISCOSITY - Google Patents

Abstract

Conventional liquid dishwashing agents are predominantly produced on a petrochemical basis and have the disadvantage of incomplete biodegradability. A liquid, foaming detergent which has all the beneficial properties of conventional dishwashing agents while, at the same time, being well tolerated by skin and very environmentally compatible is now proposed. The surfactant ingredients are 5 - 40 % alkyl polyglycoside and 0.1 - 2.9 % anionic surfactant and 0 - 3 % other surfactants.

Description

The invention relates to an environmentally friendly, foaming, liquid Cleaning supplies.

Liquid, foaming detergents aim at manual cleaning tion hard surfaces, especially in the home, such. Ceramic, Porcelain, glass, metal and plastic. The most important application There are manual dishwashing detergents for cleaning dishes.

Modern products here consist of neutral aqueous For emulsions based on strongly foaming surfactants. Main components are sulfonates, such as. B. alkylbenzenesulfonates or sec-alkanesulfo nate, both combined with fatty alcohol ether sulfates or fat alcohol sulfates (EP-A-01 12 047). In small quantities become part Fatty acid alkanolamides and more rarely added oxethylates. Further over Liche components are solubilizers, dyes and fragrances, Konser vierungsmittel etc.

The rinsing process usually takes place at a slightly elevated temperature (30 to 50 ° C) in dilute solutions. Really important, because of the long skin contact of the user, the skin is tolerated speed of the detergent. When assessing the cleaning power by the consumer, the foaming power of the solution plays a significant Role, roughly in the sense, the longer the cleaning solution during the Flushing foams, the greater their cleaning power.

Another important consumer property of the cleaning fluid is the flow behavior. Too high and too low viscosities he heavy manual dosing of the cleaning concentrate. Very low viscosity also leads to the impression of low drug content. Ideal for household products are average viscosities between 150 and 300 mPa · s at shear rates of about 10 sec ^-1 . Another important feature is the compatibility of the active ingredients with drinking water, and clear solutions are desirable.

The currently common cleaning agents usually show sufficient Cleaning effect and a strong foaming power, suitable flow Ver and sufficient compatibility with the hardness of the Water. In contrast, these mixtures but have a low skin friend because its essential components - namely the ionic surfactants of the sulfonate or sulfate type - highly skin are irritating.

Another serious disadvantage with regard to the shortage of Raw material reserves is the predominantly petrochemical base of ge called anionic surfactants associated with an incomplete bio logical degradability.

The object of the invention was therefore to provide a cleaning agent to put, which implies all desired characteristics, at the same time early high skin compatibility and excellent environmental compatibility friendliness.

The problem has been solved by a liquid cleaning agent, as Surfactant largely contains only alkylpolyglycoside.

The invention therefore provides a liquid, foaming cleaning agent with increased viscosity, consisting of
From 5 to 40% by weight of alkylpolyglycoside,
0.1 to 2.9% by weight of anionic surfactant,
From 0 to 3% by weight of other surfactants,
as well as conventional non-surfactant additives and water ad 100 wt .-%.

The use of alkyl polyglycosides in detergents and cleaners is known in combination with other surfactants. That's how it describes AT-PS 1 35 333 already combines the effect of lauryl glycoside with the sodium salt of Ricinolschwefelsäureesters as wool detergent. In US Pat. No. 3,721,633 discloses alkylpolyglycosides in combination with Buil substances such as nitrilotriacetic acid or sodium tripolyphosphate, described as a detergent. The combination of alkyl polyglycosides  claimed with Fettalkoholoxethylaten as a liquid detergent EP-A-01 05 556. Manual rinsing agents using alkylpoly glycosides are described in the publications EP-A-00 70 074, EP-A-00 70 075 and EP-A-00 70 076, wherein u. a. anionic surfactants as Cotenside miteingesetzt be. Analogous content also has the DE-OS 35 34 082, wherein fatty alkyl glycosides having 1 to 1.4 glycoside units be mentioned per fatty alkyl radical. The cosurfactants used here are alkyl sulphate or alkyl ether sulphates, in each case in combination with fatty acid alkanolamides. Finally, EP-A-01 99 765 describes a liquid detergents or dishwashing detergents with similar claims.

All these combinations imply more or more in comparative terms less good cleaning effect the disadvantage of relatively high content not purely native or based on petrochemical Coten siden and thus usually the limited environmental compatibility speed and skin friendliness.

So z. For example, EP-A-00 70 074 indicates a minimum coside content Alkylbenzenesulfonate of 50% or sulfates of 60% based on Total surfactant.

And EP-01 99 765 describes cleaning liquids with a Minimum content of anionic cosurfactant of 3%.

An ideal problem solution would be in use of alkylpolyglycoside as the only surfactant component of the cleaning fluid be stand. In fact, pure alkylpolyglycoside solutions are also prominent excellent cleaning effects, provided they are sufficiently hydro phob set. The latter succeeds by a longer-chain hydro phoben alkyl radical or by a less pronounced hydrophilic Moiety.

It has now surprisingly been found that the addition of extremely ge Quenching amounts of anionic surfactant to alkylpolyglycosides good foaming assets and high rinsing effect with good skin compatibility in the to be observed according to the invention liquid detergent, wherein an increase in viscosity compared to the pure alkyl polyglycol Sidkonzentrat by a factor of 15 to 20 is observed.  

alkylpolyglycosides

Alkylpolyglycosides used according to the invention satisfy the formula I.

RON _n (I)

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

Preference is given to alkylpolyglycosides having fatty alkyl radicals having 12 to 16 Carbon atoms and a polyglycosyl radical of n = 1.1 to 2. Be alkylpolyglycosides with n = 1.1 to 1.5 are particularly preferred.

The alklypolyglycosides used in accordance with the invention can be prepared according to knew processes based on renewable raw materials produced who the. For example, dextrose in the presence of an acidic cata tors reacted with n-butanol to Butylpolyglycosidgemischen, which with long-chain alcohols also in the presence of an acidic catalyst fors to the desired Alkylpolyglycosidgemischen umglycosidiert who the.

The structure of the products can be varied within certain limits. The Alkyl radical R is determined by the choice of long-chain alcohol sets. Favorably for economic reasons are the industrially too surfactant alcohols having 10 to 18 carbon atoms, in particular native Fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives It is also possible to use Ziegleralkohole or Oxoalkohole.

The polyglycosyl Z _n is on the one hand by the choice of Kohlenhy drats and on the other hand by the setting of the average degree of polymerization n z. B. according to DE-OS 19 43 689. In principle, polysaccharides, z. As starch, maltodextrins, dextrose, galactose, mannose, xylose, etc. are used. Preferably, the carbohydrates available on a large scale are starch, maltodextrins and especially dextrose. Since the economically interesting Alkylpolygylco sidsynthesen do not run regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They are adjacent to each other with α- and β-glycosidic bonds in pyranose and furanose form. Also, the sites of linkage between two saccharide residues are different.

Alkylpolyglycosides used according to the invention can also be obtained by Mixing of alkyl polyglycosides with alkyl monoglycosides produce. The latter can be z. B. according to EP-A-00 92 355 by means of polar Lösemit tel, such as acetone, from alkyl polyglycosides win or accumulate.

The degree of glycosidation is suitably determined by means of ¹ H-NMR be.

The cleaning agents according to the invention contain 5 to 40%, preferably Wise 10 to 30%, alkylpolyglycoside in aqueous solution.

Compared to all other Ten used in detergents siden the alkyl polyglycosides are considered to be environmentally friendly. So is determined by the treatment plant simulation model / DOC analysis biodegradation degree for the alkylpolyglycosides according to the invention 96 ± 3%. This number should be seen against the background that this Test method (total degradation) already a degree of degradation <70% the substance indicated as readily degradable.

Also the acute oral toxicity LD 50 (rat) as well as the aquatic Toxicity LC 50 (Goldorfe) and EC 50 (Daphnia) and values of <10 000 mg / kg, 12 or 30 mg / l are more favorable by a factor of 3 to 5 than the corresponding values of today's most important surfactants. something similar applies to skin and mucous membranes, which are particularly important for dishwashing detergents compatibility.

The alkylpolyglycosides according to the invention are considered to be synthesis-related about 50% aqueous solution. The solubility in water is due the hydrophobic structural adjustment not too high.  

Anionic surfactant

Suitable anionic surfactants are fatty alcohol ether sulfates, fatty alcohol sulfates, fatty alcohol ether phosphates, carboxymethylated Fettalkoholox ethylate, paraffin, olefin, alkylbenzenesulfonates and mixtures thereof. Particularly suitable are anionic surfactants with alkyl or alkylene radicals of 10 to 20 carbon atoms in the hydrophobic moiety. Preference is given to fatty alcohol ether sulfates having from 1 to 4 mol of ethylene oxide / mol, carboxymethylated fatty alcohol oxethylates having from 2 to 10 mol of ethylene oxide / mol and fatty alcohol sulfates. Preferred cations are Na, K, NH ₄ and Mg or mixtures thereof.

The cleaning concentrates according to the invention contain from 0.1 to 2.9% anionic surfactant in aqueous solution. Preference is given to 0.15 to 2.5%.

Other ingredients

By adding solvents such as low molecular weight, one or more Alcohols and glycol ethers, the solubility is particularly increase significantly even at low temperatures. Particularly suitable Solvents are ethanol, isopropanol, 1,2-propylene glycol, etc. Typical Concentrations in the detergent and 3 to 12% in the aqueous Solution.

In combination of the solvent with electrolyte, the sol especially at low temperatures, eg. T. considerably increase. Suitable electrolytes are alkali metal and alkaline earth metal halides proved. The ratio of solvent / electrolyte can 1: 1 to 8: 1.

Other additives are nonionic, ampholytic and / or zwitter ionic surfactants with total concentrations between 0 and 3% in the aqueous solution.

Finally, the cleaning liquid according to the invention in ge Ranges (0.1 to 3 weight percent) conventional dyes and Perfume oils and alkanolamines or hydrotropics, such as non-tensi dische Alkylbenzolsulfoante having 1 to 3 carbon atoms in the alkyl radical - Usually as sodium salts - and contain urea.  

To adjust suitable viscosity may optionally water-soluble Liche polymers, such as carboxymethylcellulose, hydroxyethylcellulose, Xanthans, polyethylene oxide, polyacrylate, etc. may be added.

Other suitable additives include citric acid, EDTA, NTA and other complexing agents proved.

Examples

The following examples are intended to illustrate the invention.

To test the rinsing agent effect, the Minitellertest (see R. M. Anstett u. J. Schuck JAOCS 43, 576 (1966). Here are loaded with fat watch glasses at elevated temperature with Manually cleaned a brush in the surfactant solution. The experiment conditions (preparations, geometries, quantities and concentrations) tions, temperatures, temperature gradients, times) are exactly defi ned. The test is carried out by several persons and delivers good reproducible results. Vanishing foam indicates the on number of cleaned plates (watch glasses). As a stain served Lard, which was applied to the glasses at 50.0 ° C, the then a defined cooling process to 23 ° C (room temperature) subject. The initial rinse temperature is also 50 ° C.

The foaming power of the cleaning agent was according to DIN 53 902, part 1. The concentration of washing-active substance was 1 g / l each. The foam volume was registered after 5 Minutes.

The viscosity of the cleaning liquid was measured in a rotary viscometer (Haake RV 20) under defined shear rates (D approx. 10 sec ^-1 ).

For clarification, 10 g of detergent were used in a Shukoff cooled to -20 ° C and then heated. The tem is measured temperature of the product in complete clarification.  

Tables 1 a and 1 b show the properties of the erfindungsge appropriate preparations. The addition of small amounts of anionic surfactant to solutions of hydrophobically-adjusted alkylpolyglycoside (cf. play I (V)) causes a clarification of the liquid. simultaneously Foaming power and viscosity increase strongly and reach very soon the level of commercially available cleaning agents (Example 7 (V) The effect of this effect is limited by the addition of anionic surfactants the measuring error is not affected and completely corresponds to the market standard.

The following abbreviations were used in the tables:

APG 1 Alkylpolyglycoside with alkyl chain length C _12/14 and G = 1,2 APG 2 Alkylpolyglycoside with alkyl chain length C _12/13 and G = 1,1 Alkylethersulfat Alkyl chain = C _12/14 , 2 mol EO / mol, Na salt Alkyletheracetat Alkyl chain = C _12/14 , 4 mol EO / mol, Na salt alkyl sulfate Alkyl chain = C _12/14 , Na salt PS n-paraffin _sulfonate with alkyl chain = C _13/17 SECTION Alkylbenzenesulfonate with alkyl chain = C _10/13

Table 1a

Properties of the preparations according to the invention

Table 1b

Properties of the preparations according to the invention

The diagram ( FIG. 1) shows the properties of the preparations according to the invention of APG 1 / alkyl ether sulfate as a function of the ether sulfate additive in detail, the content of APG 1 = 15% by weight being used. While the foamability with Ethersulfatzusatz increases very strong, the clearing point changes only relatively small. Completely unexpected is the pronounced viscosity maximum in the range of low anionic surfactant concentrations. This reasoning property of the present invention has also been observed in the addition of other anionic surfactants. With the aid of such a diagram, cleaning agents can also be tailor-made with regard to optimum environmental compatibility.

S = Foam [ml] at 25 ° C after 300 sec = Viscosity [mPa.s] at 25 ° C T = Cleaning effect [plate] K = Clearing point [° C] APG 1 Alkyl polyglycoside with alkyl chain length = C _12/14 and degree of glycosidation = 1.2 Alkylethersulfat Alkyl chain = C _12/14 , 2 mol EO / mol, Na salt.

Claims (10)

1. Liquid, foaming detergent with increased viscosity, consisting of
From 5 to 40% by weight of alkylpolyglycoside,
0.1 to 2.9% by weight of anionic surfactant,
From 0 to 3% by weight of other surfactants,
as well as conventional non-surfactant additives and water ad 100 wt .-%. 2. Liquid, foaming detergent according to claim 1, characterized in that the alkylpolyglycoside of the formula I corresponds to RZ _n (I), wherein 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 Pentoseein units or mixtures thereof. 3. Liquid, foaming detergent according to claim 1, characterized in that the alkylpolyglycoside of the formula I corresponds to RON _n (I), wherein R is a saturated or unsaturated, fatty alcohol having 10 to 18 carbon atoms and Z _{n is} a polyglycosyl radical with n = 1 , 1 to 2 glycoside units. 4. Liquid, foaming detergent according to the claims 1 to 3, characterized, that the anionic surfactant from fatty alcohol ether sulfate, fatty alcohol sulfate, carboxymethylated fatty alcohol oxethylate, olefinsulfonate,  Alkanesulfonate, alkylbenzenesulfonate or mixtures thereof. 5. Liquid, foaming detergent according to the claims 1 to 4, characterized, the anionic surfactant is fatty alcohol ether sulfate. 6. Liquid, foaming detergent according to the claims 1 to 4, characterized, the anionic surfactant is fatty alcohol sulfate. 7. Liquid, foaming detergent according to the claims 1 to 4, characterized, the anionic surfactant is carboxymethylated fatty alcohol oxethylate is. 8. Liquid, foaming detergent according to the claims 1 to 4, characterized, that the anionic surfactant is alkanesulfonate. 9. Liquid, foaming detergent according to the claims 1 to 8, characterized, that as further additives solvents such as mono- and polyvalent Alcohols, electrolytes, complexing agents, hydrotropics, polymers, Dyes, fragrances, etc. are used. 10. Use of the liquid, foaming detergent with Increased viscosity according to claims 1 to 9 as a manual Detergent.