EP0474915B1 - Detergent - Google Patents

Abstract

A low-foam, liquid or powdered machine detergent containing 3 to 30% of alkyl polyglycoside 3 to 30% of fatty alcohol ethoxylate 5 to 30% of soap and 0 to 5% of other surfactants characterised in that the alkyl polyglycoside is a mixture of at least 2 components of the formulae I and II <IMAGE> in which R is a linear or branched, saturated or unsaturated alkyl radical with 8 to 11 carbon atoms or mixtures thereof, Zn is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof, R' is a linear or branched, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms or mixtures thereof, Z'm is a polyglycosyl radical with m = 1 to 3 hexose or pentose units or mixtures thereof.

Description

The present invention relates to liquid or powdery preparations for washing textiles, the surfactants of which are largely produced from renewable raw materials.

Liquid detergents today mainly consist of anionic surfactants, especially alkylbenzenesulfonate, fatty alcohol oxyethylate and soap, whereas washing powders contain not only the surfactants alkylbenzenesulfonate and fatty alcohol oxyethylate, but also builder substances, bleaching agents and other electrolytes as essential active ingredients. Common to liquid and powder detergent formulations is that surfactants, in particular those based on petrochemicals, are used.

In view of the future raw material situation (oil shortage), this petrochemical basis is a considerable disadvantage. Another disadvantage is that the biodegradability and ecotoxicity of these surfactants often do not reach the corresponding level of surfactants on a native basis.

The object of the invention was therefore to find a surfactant combination for low-foaming detergents which are largely made from renewable raw materials and which, in addition to very good washing results, are outstandingly biodegradable.

This object was achieved by a surfactant combination consisting essentially of alkyl polyglycosides, fatty alcohol oxyethylates and soap.

• 3 bis 30 % Alkylpolyglykosid
• 3 bis 30 % Fettalkoholoxethylat
• 5 bis 30 % Seife und
• 0 bis 5 % andere Tenside,
  welches dadurch gekennzeichnet ist, daß das Alkylpolyglycosid eine Mischung aus 2 Komponenten der Formeln I bzw. 11
  
  
  enthält, in denen R einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 11 Kohlenstoffatomen oder Gemische davon, Z_n ein Polyglycosylradikal mit n = 1 bis 3 Hexose- oder Pentoseeinheiten oder Mischungen davon, R' einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen oder Gemische davon und Z'_m ein Polyglycosylradikal mit m = 1 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon bedeuten.

The invention therefore relates to a low-foaming, liquid or powdered machine detergent

• 3 to 30% alkyl polyglycoside
• 3 to 30% fatty alcohol oxyethylate
• 5 to 30% soap and
• 0 to 5% other surfactants,
  which is characterized in that the alkyl polyglycoside is a mixture of two components of the formulas I and 11
  
  
  contains, in which R is a linear or branched, saturated or unsaturated alkyl radical having 8 to 11 carbon atoms or mixtures thereof, Z _{n is} a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof, R 'is a linear or branched, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms or mixtures thereof and Z ' _{m is} a polyglycosyl radical with m = 1 to 3 hexose or pentose units or mixtures thereof.

The use of an alkyl polyglycoside in combination with fatty alcohol oxyethylates and also with anionic surfactants is known per se. DE-OS 593 422 already mentions the washing effect-enhancing effect of alkylglycoside in soaps. Later documents such as EP-A 0 075 994, 075 995, 075 996, 094 118 and 317 614 describe the use of alkyl polyglycoside in combination with anionic and / or nonionic surfactants in detergents.

Surprisingly, it has now been found that the formulation according to the invention with 2 different alkyl polyglycosides delivers excellent washing results.

The alkyl polyglycoside used is a mixture of at least 2 components which, on the one hand, differ greatly in terms of the chain length of their alkyl groups and, on the other hand, are used in different concentrations. The main components are alkyl polyglycosides, the alkyl groups of which contain 12 to 18 carbon atoms; Secondary components are those whose alkyl group contains 7 to 11 carbon atoms. According to the invention in the above. The surfactant content is a short-chain alkyl polyglycoside content of 1 to 10% and a long-chain content of 2 to 20%.

Other constituents of the detergent according to the invention, depending on the state of aggregation, are fatty alcohol oxyethylates and other surfactants in small amounts, complexing agents, bleaching agents, optical brighteners, graying inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizers, etc.

Alkyl polyglycosides

in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 7 bis 11 Kohlenstoffatomen oder Gemische davon und Z_n für einen Polyglycosylrest mit n = 1,0 bis 3 Hexose-oder Pentoseeinheiten oder Gemische davon stehen.Short-chain alkyl polyglycosides used according to the invention satisfy the formula I.

in which R represents a linear or branched, saturated or unsaturated aliphatic alkyl radical having 7 to 11 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 alkyl radicals having 8 to 11 carbon atoms and a polyglycosyl radical from n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.

in der R' für einen linearen oder verzweigten, gesättigten oder ungesättigten aliphatischen Alkylrest mit 12 bis 18 Kohlenstoffatomen oder Gemische davon und Z'_m für einen Polyglycosylrest mit n = 1,0 bis 3 Hexose- oder Pentoseeinheiten oder Gemische davon stehen.Longer-chain alkyl polyglycosides used according to the invention satisfy formula II

in which R 'is a linear or branched, saturated or unsaturated aliphatic alkyl radical having 12 to 18 carbon atoms or mixtures thereof and Z' _{m is} 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 radical from n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.

The alkyl polyglycosides used according to the invention can be produced by known processes based on renewable raw materials.

For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols, likewise in the presence of an acidic catalyst, to give the desired alkylpolyglycoside mixtures. Or dextrose is immediately reacted with the desired long-chain alcohol.

The structure of the products can be varied within certain limits. The alkyl radical R or R 'is determined by the choice of the long-chain alcohol. Favorable for economic reasons are the industrially accessible alcohols with 7 to 18 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives. Ziegler alcohols or oxo alcohols can also be used.

The polyglycosyl radicals Z _n and Z ' _m are determined on the one hand by the selection of the carbohydrate and on the other hand by setting the average degree of polymerization n or m. 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 industrially 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 are present side by side with a- and ß-glycosidic bonds in pyranose and furanose form. The junctions between two Saccachrid residues are also different.

Alkyl polyglycosides used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can e.g. B. according to EP-A 0 092 355 using polar solvents, such as acetone, from alkyl polyglycosides. The degree of glycosidation is expediently determined by means of ¹ H-NMR.

The detergents according to the invention contain 1 to 10% short-chain alkyl polyglycoside, preferably 2 - 8%, and 2 - 20% long-chain alkyl polyglycoside, preferably 3 - 15%, the ratio of short-chain to long-chain fraction 1:10 to 2: 1, preferably 2: Is 10 to 1: 1.

Compared to almost all other surfactants used in detergents, the alkyl polyglycosides are considered to be extremely environmentally compatible. The degree of biodegradation for the alkyl polyglycosides according to the invention, determined by means of a sewage plant simulation model / DOC analysis, is 96 ± 3%. This number can be seen against the background that with this test method (total degradation) a degree of degradation 70% already indicates that the substance is readily degradable.

The acute oral toxicity LD 50 (rat) with> 10,000 mg / kg as well as the aquatic toxicity LC 50 (gold orfe) with approx. 12 mg / I and EC 50 (daphnia) with 30 mg / I are by a factor of 3 to 5 cheaper than the corresponding values of today's most important surfactants. The same applies to skin and mucous membrane compatibility.

Fatty alcohol oxyethylates

in der R" einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 22, vorzugsweise 10 - 20 Kohlenstoffatomen und x = 2 bis 20, vorzugsweise 3 bis 15 bedeuten.Fatty alcohol oxyethylates are compounds of the formula III

in the R "a linear or branched, saturated or unsaturated alkyl radical with 8 to 22, preferably example, 10 to 20 carbon atoms and x = 2 to 20, preferably 3 to 15.

The compounds are generally prepared by addition of ethylene oxide onto longer-chain alcohols in the presence of basic or acidic catalysts. For economic reasons, commercially available alcohols with 8 to 22 carbon atoms from the hydrogenation of carboxylic acids or carboxylic acid derivatives are favorable. Ziegler alcohols or oxo alcohols can also be used.

The alcohol oxyethylates are known to be readily biodegradable; Their data regarding aquatoxicity, skin and mucous membrane compatibility are also favorable.

The detergents according to the invention contain 3 to 30% fatty alcohol oxyethylates, which can also be mixtures. A content of 5 to 20% is preferred.

Soap

in der R'" einen gesättigten oder ungesättigten Alkylrest mit 8 bis 22 C-Atomen und P Wasserstoff, Alkali, Ammonium oder Alkanolammonium bedeuten.Fatty acid salts or their acids according to the invention correspond to formula IV

in which R '"is a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P being hydrogen, alkali, ammonium or alkanolammonium.

The detergents according to the invention contain 5 to 30%, preferably 7 to 20% soap, which will usually be a mixture of different components.

Other surfactant components

According to the invention, up to 5% of other anionic, nonionic, zwitterionic and ampholytic surfactants are to be used. In particular, these are alkanesulfonates, olefinsulfonates, alkylbenzenesulfonates, a-sulfofatty acid esters, fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic esters, fatty acid alkanolamides, amine oxides, betaines, sulfobetaines, etc.

Other non-surfactant components

Builders are primarily to be mentioned as non-surfactant components. According to the invention, water-soluble builders such as different polyphosphates, phosphonates, carbonates, polycarboxylates, citrates, polyacetates such as NTA and EDTA, etc. or mixtures thereof are used. These compounds are usually used as alkali salts, preferably as sodium salts. Although not complexing, sodium sulfate should also be mentioned here. The use of water-insoluble builders, such as aluminosilicates of suitable particle size, is also according to the invention (cf. EP-A 0 075 994). The concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50%.

Bleaching agents such as sodium perborate, optionally combined with bleach activators such as tetraacetylethylene diamine etc. or percarbonate, are also used according to the invention; Other bleaching agents are of course also possible (cf. K. Engel, Tenside Surfactants 25, p. 21 (1988). The concentration of the bleaching agents is 0 to 40%, preferably 0 to 30%.

Adjusting agents such as low molecular weight monohydric or dihydric alcohols, alkyl ethers of polyhydric alcohols, hydrotropics such as alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical, alkanolamines or urea, enzymes such as in particular proteases and enzyme stabilizers, corrosion inhibitors such as alkali silicates, optical are optionally used according to the invention Brighteners based in particular on stilbene and pyrazoline, foam regulators, graying inhibitors such as, for. B. carboxymethyicellulose, perfume oils, dyes and other ingredients customary for liquid or powder detergents.

The total use concentration in the machine detergents according to the invention is 0.3-20 g / l for the surfactant fraction. 0.5-10 g / l are preferred.

Examples

The invention is illustrated by the following examples. The liquid detergent formulations listed in Table 1 each contain 6% triethanolamine, 12% ethanol, 6% 1,2-propylene glycol and water ad 100% in addition to the surfactant components mentioned according to the invention.

The powders listed in Tab. 2 contain, in addition to the surfactant constituents mentioned according to the invention, each 10% sodium perborate, 4.5% Na, Mg silicate, 14% Na ₂ SO ₄ , 24% Wessalith P, 3% Sokalan CP 5, 8 % Na ₂ CO ₃ , 3.5% TAED and 0.4% phosphonate.

The foaming power was determined in accordance with DIN 53 902, Part 1. The concentration of detergent substance was 1 g / I in each case, the foam volume was registered after 5 minutes. The washability was measured both in the Linitest laboratory washing machine (i.e. with moderate mechanical stress) and in a normal household washing machine, and the foam development was also checked, which corresponded approximately to the DIN values.

11 x 18 cm rags made of WFK test fabric with skin fat pigment soiling served as model fabric: polyester (PE), mixed fabric (MG) and cotton (BW), and drinking water (13 _° dH) as water. Polyester was washed at 30 ° C, blended fabrics and cotton at 60 _° C. In the Linitest laboratory washing machine, the active ingredient concentration was 1 g / I, in the household washing machine 5 g / I, the pH in each case about 7, the liquor ratio in about 1: 60 and 1: 4, the washing times in both cases were about 30 minutes .

In the Linitest machine, the washing process was repeated twice after each rinse. The washing values after drying the fabrics were - as usual - measured spectrophotometrically relative to a white standard (Datacolor, 560 nm).

Liquid formulations

Tab. 1 shows the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and with a liquid brand detergent, in which one can presuppose a formulation optimization. The clear point and viscosity correspond approximately to the standard customary for liquid detergents. The foaming power of the formulations according to the invention shows favorable values without further regulating additives. This applies in particular to the washing ability.

In comparison with the branded detergent (Example 13 (V) and even with the alkylpolyglycoside-containing formulations (Examples 1 (V) to 5 (V), the detergents according to the invention behave far superior in their washing activity.

Powder formulations:

Tab. 2 shows the comparison of the properties of powdery detergent formulations according to the invention with those of a known combination or with a branded detergent. Bulk density and foaming power were determined according to DIN methods.

The solubility can be estimated by plotting the electrical conductivity over time, 80% of an average final conductivity being taken as the measured value when 3 g powder is dissolved in 800 ml drinking water (13 _° dH). The measured values contain an error of ± 5%.

Apart from a somewhat higher bulk density, typical of agglomerated washing powders compared to the spray-dried branded product (example 23), the powders according to the invention behave very similarly and have a much better washing value.

It is surprising that, when alkyl polyglycoside is used, particularly in the case of mixed fabrics, the nibbling ability, which is significantly increased, is further improved by the formulation according to the invention.

• Triton^R BG 10 - Alkylpolyglycosid von Rohm und Haas
• Triton^R CG 110 - Alkylpolyglycosid von Rohm und Haas
• C₁₂C₁₄ [G 1.2] - C_12/14-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.2
• C₁₂C₁₃ [G 1.1] - C_12/13-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.1
• C₁₂C₁₃ [G 1.7] - C_12/13-Alkylpolyglycosid mit einem Glycosidierungsgrad von 1.7
• MARLIPAL^R 24/60 - C_12/14-Fettalkoholoxethylat mit 6 mol EO/mol
• MARLIPAL^R 24/80 - C_12/14-Fettalkoholoxethylat mit 8 mol EO/mol
• Seife 1 - Kokosfettsäure neutralisiert mit Triethanolamin
• Seife 2 - 90 Teile Rindertalg, 10 Teile Kokosfettsäure mit NaOH verseift
• PE - Polyester
• MG - Mischgewebe
• BW - Baumwolle
  
  
  
  

The following abbreviations were used in the tables:

• Triton ^R BG 10 - alkyl polyglycoside from Rohm and Haas
• Triton ^R CG 110 - alkyl polyglycoside from Rohm and Haas
• C ₁₂ C ₁₄ [G 1.2] - C _12/14 alkyl polyglycoside with a degree of glycosidation of 1.2
• C ₁₂ C ₁₃ [G 1.1] - C _12/13 alkyl polyglycoside with a degree of glycosidation of 1.1
• C ₁₂ C ₁₃ [G 1.7] - C _12/13 alkyl polyglycoside with a degree of glycosidation of 1.7
• MARLIPAL ^R 24/60 - C _12/14 fatty alcohol oxyethylate with 6 mol EO / mol
• MARLIPAL ^R 24/80 - C _12/14 fatty alcohol oxyethylate with 8 mol EO / mol
• Soap 1 - coconut fatty acid neutralized with triethanolamine
• Soap 2 - 90 parts beef tallow, 10 parts coconut fatty acid saponified with NaOH
• PE - polyester
• MG - blended fabric
• BW - cotton
  
  
  
  

Claims (8)

1. A low-foam, liquid or powder machine detergent containing

3 to 30% of alkyl polyglycoside

3 to 30% of fatty alcohol oxyethylate

5 to 30% of soap and

0 to 5% of other surfactants,
characterized in that the alkyl polyglycoside contains a mixture of at least 2 components of the formulae I and/or II

in which R is a linear or branched, saturated or unsaturated alkyl radical with 8 to 11 carbon atoms or mixtures thereof, Z_n is a polyglycosyl radical with n = 1 to 3 hexose or pentose units or mixtures thereof, R' is a linear or branched, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms or mixtures thereof and Z'_m is a polyglycosyl radical with m = 1 to 3 hexose or pentose units or mixtures thereof.

2. A low-foam, liquid or powder detergent according to claim 1, characterized in that the alkyl poly- glycoside components according to formulae I and II are employed in the ratio 1:10 to 2:1.

3. A low-foam, liquid or powder detergent according to either of claims 1 and 2, characterized in that the alkyl polyglycosides are fatty alcohol glucosides with n = 1.1 to 2 and m = 1.1 to 2.

4. A low-foam, liquid or powder detergent according to any of claims 1 to 3, characterized in that the fatty alcohol oxyethylate corresponds to the formula III

in which R" is a linear or branched, saturated or unsaturated alkyl radical with 8 to 22 carbon atoms and x is 2 to 20.

5. A low-foam, liquid or powder detergent according to claim 4, characterized in that R" in formula III is an alkyl radical with 10 to 20 carbon atoms and x is 3 to 15.

6. A low-foam, liquid or powder detergent according to any of claims 1 to 5, characterized in that the soap corresponds to the formula IV

in which R'" is a saturated or unsaturated alkyl radical with 8 to 22 carbon atoms and P is hydrogen, alkali metal, ammonium or alkanolammonium.

7. A low-foam, liquid or powder detergent according to any of claims 1 to 6, characterized in that builders, bleaches, fillers, enzymes, stabilizers, antiredeposition agents, corrosion inhibitors, optical brighteners, dyes, perfume oils and, where appropriate, further additives are present as non-surfactant ingredients.

8. A low-foam, liquid or powder detergent according to any of claims 1 to 7, characterized in that the concentration of the surfactant constituent is 0.3 to 20 g/I.