DE4315810A1 - Aqueous detergent mixtures - Google Patents

Description

Field of the invention

The invention relates to aqueous detergent mixtures, containing alkyl and / or alkenyl oligoglycoside isethionates and other surfactants, surfactants containing these Mixtures contain as well as the use of the mixtures for Preparation of Surfactants.

State of the art

Alkyl oligoglycosides and in particular alkyl oligoglucosides represent nonionic surfactants that because of their native Raw material base - fatty alcohol and sugar - increasing in importance and, for example, in manual dishwashing detergents or cosmetic products [cf. Tens. Surf.Det. 28, 413 (1991)]. With regard to the exquisite application properties of the glycosides however, also a need for anionic surfactants more related Structure that is beneficial along with other classics surfactants in surfactants and their performance that of the individual substances in syner gist way.  

The object of the invention was thus to provide synergistic Detergent mixtures based on anionically modified Alkyl and / or alkenyl oligoglycosides with further improvement develop properties.

Description of the invention

The invention relates to aqueous detergent mixtures ent cautious

• a) alkyl and / or Alkenyloligoglykosidisethionate and
• b) other anionic, nonionic, cationic and / or ampholytic or zwitterionic surfactants.

Surprisingly, it has been found that the inventive Detergent mixtures over a wash, rinse, foam and Reini fitness and a skin-cosmetic compatibility ver add that of the individual substances in the sense of a synergisti outstrip gain. As a result of a strong pronounced foaming power even in hard water as well as their exceptions proper skin-cosmetic compatibility are the Mixtures, in particular for use in the cosmetics sector. When Particularly compatible with the skin are mixtures of alkyl oligoglucosidisethionates and the corresponding alkyl oligoglucosiden as well as fatty acid N-methylglucamiden and vegetable protein hydrolysates or fatty acid condensates (based on soy protein, for example).  

Alkyl and / or alkenyl oligoglycoside isethionates

Alkyl and / or alkenyl oligoglycoside isethionates provide anio nische surfactants and follow the formula (I),

R¹O (R²O) [G] _p (I)

in the R¹ for an alkyl and / or alkenyl radical having 4 to 22 Carbon atoms, R² is an XO₃S-CH₂CH₂ radical, X is a Alkali or alkaline earth metal, ammonium, alkylammonium or Alkanolammonium, G for a 5 or 6 carbon sugar residue atoms and p stands for numbers from 1 to 10.

For their preparation is usually of alkyl and / or Alkenyl oligoglycosides of the formula (II),

R¹O- [G] _p (II)

in which R¹, G and p have the meanings given above, in the presence of basic compounds at elevated Temperature can be reacted with salts of vinylsulfonic acid.

Particular preference is given to alkyl oligoglucoside isethionates of Formula (I) wherein R¹ is an alkyl radical containing 12 to 18 Koh X atoms for sodium or magnesium, G for one Glucose residue and p for numbers from 1 to 3, in particular 1.1 to 1.9 stands.  

surfactants

Typical examples of anionic surfactants are alkylbenzene sulfonates, alkanesulfonates, olefinsulfonates, alkylethersul fonates, glycerol ether sulfonates, α-methyl ester sulfonates, Sul fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glyce Rinethersulfate, Hydroxymischethersulfate, Monoglyceridsul fate, fatty acid amide (ether) sulfate, sulfosuccinate, sulfosuc cinamate, sulfotriglycerides, amide soaps, ether carboxylic acids, Fatty acid isethionates, sarcosinates, taurides, alkyloligogluco sidsulfates, alkyl (ether) phosphates and vegetable or tie proteinic hydrolysates or their condensation products with fatty acids. Unless the anionic surfactants polyglycol contain ether chains, they can be a conventional, before However, preferably a narrow homolog distribution aufwei sen.

Typical examples of nonionic surfactants are fatty alcohol holpolyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycolic, fatty acid amide polyglycol ethers, fatty amine polyols Glycol ethers, alkoxylated triglycerides, alk (en) yloligoglyco side, fatty acid glucamides, polyol fatty acid esters, sugar esters, Sorbitan esters and polysorbates. Unless the nonionic Surfactants contain polyglycol ether chains, they can be one conventional, but preferably a narrow homolo have gene distribution.

Typical examples of cationic surfactants are quaternary amines monium compounds and quaternized difatty acid trialkanol aminester.  

Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, Aminoglycinates, imidazolinium betaines and sulfobetaines.

The surfactants mentioned are exclusively known compounds. Regarding structure and production these substances are included in relevant reviews For example J.Falbe (ed.), "Surfactants in Consumer Pro ducts ", Springer Verlag, Berlin, 1967, 5.54-124 or J. Falbe (ed.), "Catalysts, Teusides and Mineral Oil Additives", Thiele Verlag, Stuttgart, 1978, 5.123-217.

Detergent mixtures

The aqueous detergent mixtures according to the invention can the Alkyl and / or alkenyl oligoglycoside isethionates in amounts of 1 to 99, preferably 30 to 75 wt .-% - based on the Solids content of the mixtures - included.

The preparation of the aqueous detergent mixtures can by simple mechanical mixing of the aqueous solutions of Components, optionally at elevated temperatures of 30 up to 50 ° C; a chemical reaction takes place here not happening.

Surfactants

In the following, further items are described on the the invention also extends:

• - Powdered universal detergents containing 10 to 30 Wt .-% - based on the mean - a mixture of Alkyl and / or alkenyl oligoglycoside isethionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and given if necessary further auxiliaries and additives.
• Liquid universal detergents containing 10 to 70 Wt .-% - based on the mean - a mixture of Alkyl and / or alkenyl oligoglycoside isethionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and given if necessary further auxiliaries and additives.
• Liquid mild detergents containing 10 to 50% by weight based on the agent - a mixture of alkyl and / or Alkenyl oligoglycoside isethionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and optionally further Auxiliaries and additives.
• - Liquid detergents and disinfectants, containing 10 to 30 wt .-% - based on the mean - a Mi tion of alkyl and / or Alkenyloligoglykosidise thionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and optionally further auxiliaries and additives.
• - Hair shampoos, containing 10 to 30 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic,  nonionic, cationic and / or amphoteric or zwitterionic surfactants and optionally further Auxiliaries and additives.
• - Hair rinses, containing 10 to 30 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic cationic and / or amphoteric or zwitterio nischen surfactants and optionally further auxiliary and Additives.
• - Foam baths containing 10 to 30 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic rule, cationic and / or amphoteric or zwitter ionic surfactants and optionally further auxiliary and Additives.
• - Syndetseifen containing 10 to 50 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic cationic and / or amphoteric or zwitterio nischen surfactants and optionally further auxiliary and Additives.
• Flotation aid containing 10 to 95% by weight based on the means - a mixture of alkyl and / or Alkenyl oligoglycoside isethionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and optionally further Auxiliaries and additives.

Detergents and cleaning agents based on the invention Detergent mixtures can be added as auxiliaries and additives For example, builders, salts, bleaches, bleach activators, optical brighteners, grayness inhibitors, solubilizers ler, defoamers and enzymes.

Common builders are sodium aluminum silicates (zeolites), Phosphates, phosphonates, ethylenediaminetetraacetic acid, Ni tri-tri-acetate, citric acid and / or polycarboxylates. When Salts or adjusting agents are, for example, sodium sulfate, Sodium carbonate or sodium silicate (water glass) into consideration. As typical individual examples of other additives are Sodium Borate, Starch, Sucrose, Polydextrose, TAED, Style benverbindungen, methyl cellulose, toluenesulfonate, cumolsul fonat, long-chain soaps, silicones, mixed ethers, lipases and To name proteases.

Hair shampoos, hair lotions or foam baths based on Detergent mixtures according to the invention can be used as auxiliary and Additives such as emulsifiers, oil components, fats and waxes, thickeners, superfatting agents, biogenic Active ingredients, film formers, fragrances, dyes, pearlescent medium, preservatives and pH regulators.

Common oil components are substances such as paraffin oil, Pflan zenoyl, fatty acid esters, squalane and 2-octyldodecanol while as fats and waxes, for example, spermaceti, beeswax, mon tan wax, paraffin and cetylstearyl alcohol find use. As Überfettungsmittel substances such as polyethoxylated lanolin derivatives, lecithin derivatives and fat acid alkanolamides are used, the latter  simultaneously serve as foam stabilizers. Suitable Ver Thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar, alginates and tyloses, Carboxymethylcellulose and hydroxyethylcellulose, further hermolecular polyethylene glycol mono- and diesters of fat acids, polyacrylates, polyvinyl alcohol and polyvinylpyrroli don and electrolytes such as table salt and ammonium chloride. Under biogenic agents are, for example, plant extracts, Protein hydrolysates and vitamin complexes to understand. Gebräuch Liche film formers are for example polyvinylpyrrolidone Vinylpyrrolidone-vinyl acetate copolymers, polymers of Acrylic acid series, quaternary cellulose derivatives and the like Links. Suitable preservatives are, for example example formaldehyde solution, p-hydroxybenzoate or sorbic acid. For example, glycol distearate can be used as pearlescing agent acid esters such as ethylene glycol distearate, but also fatty acid monoglycol ester. As dyes, the for cosmetic purposes suitable and approved substances used, as for example in the publication "Cosmetic Dyes" of the Dye Commission of German Research Foundation, published by the publisher Chemistry, Weinheim, 1984, are compiled. This color Substances are usually added in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture used.  

Industrial Applicability

The detergent mixtures according to the invention are characterized by excellent washing, rinsing, foam and cleaning performance as well as an advantageous skin-cosmetic and ecotoxicological Compatibility.

Another object of the invention therefore relates to their Use for the production, washing, rinsing, cleaning and cleaning Flotation auxiliaries, hair and body care products, in which they are in quantities of 1 to 99, preferably 10 to 30 Wt .-% - based on the means - may be included.

The following examples are intended to form the subject of the invention explain it in more detail without restricting it to it.  

Examples I. Surfactants used Production Example A1

In a 500 ml three-necked flask with stirrer, internal thermometer and dropping funnels were 250 g (1 mol) of lauryloligoglucoside (Hydroxyl number: 656, average degree of oligomerization 1.3, Fa.Kenkel KGaA, Dusseldorf, FRG) and 2.8 g (0.02 mol) Submitted potassium carbonate and heated to 160 ° C. Subsequently The mixture was portionwise over a period of 1 h with 30 g (0.23 mol) of vinylsulfonic acid sodium salt, wherein the reaction temperature gradually increased to 190 ° C has been. After a further 3 h, the reaction was stopped, the crushed solid reaction product and dispersed in water.

Production Example A2

In a 500 ml three-necked flask equipped with stirrer, internal thermometer and dropping funnel, 170 g (0.67 mol) of C _12/14 co-gligo glucoside (Plantaren® APG 600 CSUP, average degree of oligomerization 1.3, Fa Henkel KGaA, Dusseldorf / FRG) and 4.5 g (0.03 mol) of potassium carbonate and dissolved at a tem perature of 90 ° C in about 50 ml of water. Over a period of 1 h, the reaction mixture was added in portions with 26 g (0.2 mol) of vinyl sulfonic acid sodium salt in the form of a 30 wt .-% aqueous solution and stirred for a further 8 h.

B1) Dodecylbenzenesulfonate Na salt
(Maranail® A 55, Fa.Kenkel KGaA, Dusseldorf / FRG)
B2) C _16/18 tallow fatty acid sulfate Na salt
(Sulfopon® T 50, Fa.Kenkel KGaA, Dusseldorf / FRG)
B3) C _12/14 coconut fatty alcohol-3,6 EO sulfate Na salt with a narrow homolog distribution, catalysis with calcined hydrotalcite
(Texapon® K14S-NRE, Fa.Kenkel KGaA, Dusseldorf / FRG)
B4) alpha-sulfo C _16/18 tallow fatty acid methyl ester Na salt
(Texin® ES 68, Fa.Kenkel KGaA, Dusseldorf / FRG)
C1) C _12/14 coconut fatty alcohol-2.5 EO adduct with narrow homolog distribution ex catalysis with calcined hydro talcit
(Arlypon® F-NRE, Fa.Kenkel KGaA, Dusseldorf / FRG)
C2) C _12/14 cocoalkyl oligoglucoside
(Plantaren® APG 600 CS UP, Fa.Kenkel KGaA, Dusseldorf / FRG)
C3) lauric acid N-methylglucamide

II. Performance studies:

A) Evaluation of foaming power (Sv). The assessment the foamability was in accordance with DIN 53 902, Part 1, after performed by the Götte-Schlagschaum method. There were 1 % by weight surfactant solutions in water of 160 hardness puts; the temperature was 20 ° C. The results of Foaming experiments are summarized in Tab.1; stated is the base foam volume in ml.

B) Assessment of Network Assets (IV). The assessment of the Netzvermögens was according to DIN 53 901 after the diving network method carried out. There were 1 wt .-% Tensidlö solutions used in water of 160 hardness; the tempera ture was 20 ° C. The results of the grid trials are in Tab.1 summarized; the net time is given in s.

C) Assessment of dishwashing power (TSV). The Ermitt The dishwashing power was calculated with the help of Tel ler-Testes [Fats, soaps, paints., 74, 163 (1972)]. For this dishes were with a Diameter of 14 cm with 2 ml of beef tallow (acid number 9-10) and stored at room temperature for 24 h. Subsequently, the plates were at 50 ° C with 5 l lei water of hardness 16 ° d. The test mixture was added at a dosage of 0.15 g of active substance / l used. The rinse attempt was canceled as soon as the foam on the surface had completely disappeared. The results of the rinsing tests are summarized in Tab.1 combined; the number of purged plates is indicated.  

D) Assessment of the detergency (WV). The investigation of laundering was in a launderometer at a Dust-skin-fat-soiling on polyester-cotton (ver noble tissue) at 40 ° C. The assessment of Brightening of the washed fabric was done by pho tometric remission measurement with an Elrepho RFC 3/24 device against a barium sulfate standard, the remission was set at 1.00%. The indication takes place in% remission (% -R).

Liquor | 250 ml fleet load 1 part by weight of fabric / 30 parts by weight of water dosage 10 g / l water hardness 16 ° d determination Means of 3 determinations

The results of the washing experiments are summarized in Tab.1 quantity handled.  

Table 1

Application engineering investigations

Claims (17)

1. Aqueous detergent mixtures containing

• a) alkyl and / or Alkenyloligoglykosidisethionate and
• b) other anionic, nonionic, cationic and / or ampholytic or zwitterionic surfactants.

2. Aqueous detergent mixtures according to claim 1, characterized in that they contain alkyl and / or Alkenyloligogly kosidisethionate of the formula (I), R¹O (R²O) [G] _p (I) in the R¹ for an alkyl and / or alkenyl radical with 4 to 22 carbon atoms, R² is an XO₃S-CH₂CH₂ radical, X is an alkali or alkaline earth metal, ammonium, alkyl ammonium or alkanolammonium, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. 3. Aqueous detergent mixtures according to claims 1 and 2, characterized in that they entan anionic surfactants hold, which are selected from the group of Alkylbenzenesulfonates, alkanesulfonates, Olefinsulfona alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, Fatty alcohol ether sulfates, glycerol ether sulfates, Hy hydroxymethylene ether sulfates, monoglyceride (ether) sulfates, Fatty acid amide (ether) sulfates, sulfosuccinates, sulfo  succinamates, sulfotriglycerides, amide soaps, ethers carboxylic acids, fatty acid isethionates, sarcosinates, tau riden, Alkyloligoglucosidsulfaten, alkyl (ether) phos phaten and vegetable or animal protein hydroly and their condensation products with fatty acids is formed. 4. Aqueous detergent mixtures according to claims 1 and 2, characterized in that they are nonionic surfactants included, which are selected from the group of Fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide poly glycol ethers, fatty amine polyglycol ethers, alkoxylated Triglycerides, alk (en) yloligoglycosides, fatty acid glut camiden, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates is formed. 5. Aqueous detergent mixtures according to claims 1 and 2, characterized in that they ent sign cationic surfactants hold, which are selected from the group of quaternary ammonium compounds and quaternized difatty acid trialkanolamine esters is formed. 6. Aqueous detergent mixtures according to claims 1 and 2, characterized in that they amphoteric or zwitter Contain ionic surfactants selected from Group derived from alkylbetaines, alkylamidobetaines, Ami nopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines is formed.   7. Aqueous detergent mixtures according to claims 1 to 6, characterized in that they are the alkyl and / or Al kenyloligoglycoside isethionates in amounts of 1 to 99 % By weight, based on the solids content of the mixtures, contain. 8. Powdered universal detergent containing 10 to 30 Wt .-% - based on the means - a mixture of Alkyl and / or alkenyl oligoglycoside isethionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and given if necessary further auxiliaries and additives. 9. Universal liquid detergents containing 10 to 70 Wt .-% - based on the mean - a mixture of Alkyl and / or alkenyl oligoglycoside isethionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and given if necessary further auxiliaries and additives. 10. Liquid mild detergents containing 10 to 50% by weight - based on the agent - a mixture of alkyl and / or alkenyl oligoglycoside isethionates and anio niche, nonionic, cationic and / or amphoteric ren or zwitterionic surfactants and optionally other auxiliaries and additives. 11. Liquid cleaners and disinfectants containing 10 to 30 wt .-% - based on the mean - a Mi tion of alkyl and / or Alkenyloligoglykosidisethio and anionic, nonionic, cationic and / or  amphoteric or zwitterionic surfactants and gege if necessary, further auxiliaries and additives. 12. Hair shampoos, containing 10 to 30 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic cationic and / or amphoteric or zwitterio nischen surfactants and optionally further auxiliary and Additives. 13. Hair rinses containing 10 to 30 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic cationic and / or amphoteric or zwitterio nischen surfactants and optionally further auxiliary and Additives. 14. foam baths containing 10 to 30 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic cationic and / or amphoteric or zwitterio nischen surfactants and optionally further auxiliary and Additives. 15. syndet soaps containing 10 to 50 wt .-% - based on the agent - a mixture of alkyl and / or alkenyl oligoglycosidisethionates and anionic, nonionic cationic and / or amphoteric or zwitterio nischen surfactants and optionally further auxiliary and Additives.   16. Collector for the flotation of non-sulfidic ores, ent holding 10 to 95 wt .-% - based on the means - one Mixture of alkyl and / or alkenyl oligoglycosidase thionates and anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants and optionally further auxiliaries and additives. 17. Use of detergent mixtures according to claim 1 for Production of washing, rinsing, cleaning and flota tion aids and hair and body products maintenance.