WO1999010463A1

WO1999010463A1 - Aqueous agents for washing dishes by hand

Info

Publication number: WO1999010463A1
Application number: PCT/EP1998/005201
Authority: WO
Inventors: Hermann Hensen; Bernd Fabry; Karl Heinz Schmid; Michael Elsner; Hans-Christian Raths
Original assignee: Cognis Deutschland Gmbh
Priority date: 1997-08-25
Filing date: 1998-08-17
Publication date: 1999-03-04

Abstract

The invention relates to novel aqueous agents for washing dishes by hand, containing a) fatty acid polyglycol ester sulphates, b) anionic tensides and c) non-anionic and/or amphoteric or zwitterionic tensides. The inventive agents are characterised not only by their excellent dish-washing properties but also in that they are especially foam-stable, even when the liquor is burdened with a large quantity of fat, and in that they demonstrate excellent cosmetic skin properties and a low tendency to cause allergic reactions.

Description

Aqueous hand dishwashing liquid

Field of the Invention

The invention relates to aqueous hand dishwashing detergents containing fatty acid polyglycol ester sulfates and other surfactants, and to the use of these mixtures for producing manual hand dishwashing detergents.

State of the art

Concentrated surfactant solutions are usually used for manual cleaning of soiled dishes, to which a whole series of very different requirements are made today. The funds should

have the highest possible active substance content, be liquid or at least flowable and have the lowest possible low cloud point, even in concentrated form dermatologically harmless, d. H. not be irritating to the skin, develop a strong, stable foam even with a high fat load in the liquor and at the same time naturally have a high dishwashing capacity.

Even though there are a large number of products on the market today, there is an intense interest on the part of the raw material suppliers and the manufacturers of the agents as well as on the part of the customers in preparations that perform the required complex task better than the products of the prior art . The object of the invention was to meet this need. Description of the invention

The invention relates to aqueous dishwashing detergents containing

(a) fatty acid polyglycol ester sulfates,

(b) anionic surfactants and

(c) nonionic and / or amphoteric or zwitterionic surfactants.

Surprisingly, it was found that the agents according to the invention are also highly concentrated, flowable, have a low cloud point, largely irrespective of the concentration, are not irritating to the skin and at the same time still have a voluminous foam which is stable even under high fat loads and an excellent dishwashing capacity. The invention includes the finding that mixtures of fatty acid polyglycol ester sulfates with alkyl sulfates, alkyl ether sulfates, monoglyceride sulfates, sulfosuccinates, alkyl oligoglucosides and / or betaines leads to a further improvement in the desired properties.

Fatty acid polyglycol ester sulfates

Fatty acid polyglycol ester sulfates which may be present as component (a) preferably follow the formula (I),

in the R ¹ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x for numbers from 1 to 3 on average and AO for a CH2CH2O-, CH2CH (CH3) 0- and / or CH (CH3) CH ₂ 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, and are usually prepared by sulfation of the corresponding fatty acid polyglycol ester. These in turn can be obtained using the relevant preparative processes in organic chemistry. For this purpose, ethylene oxide, propylene oxide or a mixture thereof - in random or block distribution - is added to the corresponding fatty acids, this reaction being acid-catalyzed, but preferably in the presence of bases, such as, for example, sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol. The sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se with chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion. For example, if molar amounts of fatty acid polyglycol ester to sulfating agent of 1: 0.5 to 1: 0.95 are selected, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained, which are also advantageous for a whole range of applications. In order to avoid hydrolysis, it is very important to carry out the neutralization at a pH in the range from 5 to 9, preferably 7 to 8. Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above. Fatty acid polyglycol ester sulfates of the formula (I) are preferably used in which R ¹ CO stands for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CH2CH2θ group and X for sodium or ammonium, such as lauric acid + 1 EO sulfate sodium salt, lauric acid + 1 EO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium salt, tallow fatty acid + 1 EO sulfate sodium salt, tallow fatty acid + 1 EO sulfate Ammonium salt and mixtures thereof.

Anionic surfactants

Typical examples of anionic surfactants which can be considered as component (b) are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfate, mono ether sulfate, monoglyme sulfate, monoglyme sulfate , fatty acid amide (ether) sulfates, mono- and Dialkylsulfo- succinate, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Alkyl sulfates, alkyl ether sulfates and / or sulfosuccinates are preferably used. The agents according to the invention can contain components (a) and (b) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 15:85 and in particular 60:40 to 25:75. Nonionic and amphoteric surfactants

Typical examples of nonionic surfactants which can be considered as component (c) are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxyated triglycerides, alk (en) yl oligoglycosides, especially fatty acid-N-alkyl-vegetable protein gluamides, fatty acid-N-vegetable-alkyl-fatty acids Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines are preferably used. The agents according to the invention can contain components (a) and (c) in a weight ratio of 90:10 to 10:90, preferably 75:25 to 25:75 and in particular 60:40 to 40:60 and components (a), (b) and (c) in the weight ratio (10 to 90): (5 to 85): (5 to 85) and in particular (20 to 80): (10 to 50): (10 to 50), with the proviso that add the weight information to 100% by weight.

Alkyl and / or alkenyl oligonucleotides

In a preferred embodiment of the invention, the nonionic surfactants used are alkyl and alkenyl oligoglycosides which follow the formula (II)

R ² 0- [G] _p (II)

in which R ^{2 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW-Journal Issue 8, 598 (1995).

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglycosides. The index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and especially here can assume the values p = 1 to 6, the value p is for a particular alkyl oligo glycoside is an analytically calculated value that usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization -p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ² can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of the chain length CS-CIQ (DP = 1 to 3) are preferred which are obtained as a preliminary step in the separation of technical Cβ-Ciδ coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of C12 alcohols and Alkyl oligoglucosides based on technical Cg / n oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyial alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and the technical mixtures described above. Alkyl oligoglucosides based on hardened Ci2 are preferred. .4 coconut alcohol with a DP of 1 to 3.

Fatty acid N-alkyl polyhydroxyalkvamide

Another group of preferred nonionic surfactants which can form component (c) are fatty acid N-alkylpolyhydroxyalkylamides which follow the formula (III)

R4

in the R ³ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁴ for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984 directed. An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Deterg. 25, 8 (1988).

The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (IV):

R ⁴ OH OH OH

I I I I

R3CO-N-CH ₂ .CH-CH-CH-CH-CH ₂ OH (IV)

I.

OH

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R ^{4 is} an alkyl group and R ³ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14-coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Betaine

In a further preferred embodiment of the invention, surfactants of the betaine type can form component (c). Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids, such as acrylic acid, is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to U.PIoog's contribution in Seifen-Öle-Fette-Wwachs, 108, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Surf.Det. 23, 309 (1986), R.Bilbo et al. in Soap Cosm. Chem. Spec, Apr. 46 (1990) and P.EIIis et al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (V) R ⁶

I R5-N- (CH ₂ ) _n COOX (V)

IR ⁷

in which R ^{5 represents} alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R ^{6 represents} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{7 represents} alkyl radicals having 1 to 4 carbon atoms, n represents numbers from 1 to 6 and X for a alkali and / or alkaline earth metal or ammonium Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Ci2 / i4-Kokosal- kyldimethylamin, Myπstyldimethylamin, cetyldimethylamine, Stearyidimethylamin, Stearylethylmethyl- amine, Oleyldimethylamm , Ci6 / 18-tallow alkyl dimethyl amine and their technical mixtures. Also suitable are carboxyalkylation products of amidoamines which follow the formula (VI),

IR ⁸ CO-NH- (CH2) _m -N- (CH ₂ ) nCOOX (VI)

IR ⁷

in which R ⁸ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ⁶ , R ⁷ , n and X have the meanings given above. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, including caproic, caprylic acid, Capπnsaure, lauric acid, Myπstmsaure, palmitic tinsaure, Palmoleinsaure, stearic acid, Isosteannsaure, oleic acid, Elaidmsaure, Petroselmsaure linoleic acid, linolenic acid, Elaeosteannsaure, Arachmsaure, Gadoleinsaure, behenic acid and erucic acid and their Technical mixtures with NN-dimethylaminoethylamine, N, N-dimethylamino-propylamine, N, N-dimethylamine-methylamine and N, N-dimethylamino-propylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of Cβ / .β-coconut fat - Thylammopropylamide with Natπumchloracetat Furthermore come as suitable starting materials for the purposes of the invention taking betaines also imidazolines which follow the formula (IX),

in which R ^{9 is} an alkyl radical having 5 to 21 carbon atoms, R ^{10 is} a hydroxyl group, an OCOR ⁹ or NHCOR ⁹ radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanoiamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again Ci2 / 14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Industrial applicability

The invention further relates to the use of the surfactant mixtures according to the invention for the production of hand dishwashing detergents. In this connection, the mixtures may contain minor amounts of other customary auxiliaries and additives, such as foam boosters, fragrances, etc. The agents usually have an active substance or surfactant content - based on components (a), (b) and (c) - of 10 to 50 and preferably 15 to 35% by weight.

Examples

The foaming power was determined by the Ross Miles method using 1% by weight surfactant solutions at 20 ° C. in the presence of 1 g / l of dispersed olive oil. The base foam and the foam height are given after 5 minutes. The determination of the dishwashing capacity was carried out with the help of the dish test [Fette, Seifen, Anstrichmitt., 74, 163 (1972)]. For this purpose, plates with a diameter of 14 cm were soiled with 2 cm ^{3 of} beef tallow (acid number 9-10) and stored for 24 hours at room temperature. The plates were then rinsed at 50 ° C. with 5 liters of tap water with a hardness of 16 ° d. The test mixtures were used at a dosage of 0.15 g active substance / l. The rinsing attempt was stopped as soon as the foam had completely disappeared. To determine the skin cosmetic tolerance, the skin tolerance of the comparison formulation V1 was selected as the standard according to the zeintest and all the information related to it. Formulations 1 to 8 are according to the invention, formulations V1 and V2 are used for comparison. The results are summarized in Table 1.

Table 1

Properties of surfactant mixtures (quantities as% by weight)

Claims

claims

1. Aqueous hand dishwashing liquid containing

(a) fatty acid polyglycol ester sulfates,

(b) anionic surfactants and

(c) nonionic and / or amphoteric or zwitterionic surfactants.

2. Composition according to claim 1, characterized in that they contain fatty acid polyglycol ester sulfates of the formula (I),

in which R ¹ CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x is an average of 1 to 3 and AO is a CH2CH2O-, CH ₂ CH (CH ₃ ) 0- and / or CH ( CH ₃ ) CH 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

3. Composition according to claims 1 and 2, characterized in that they contain anionic surfactants which are selected from the group consisting of alkyl sulfates, alkyl ether sulfates, monoglyceride sulfates and sulfosuccinates.

4. Composition according to claims 1 to 3, characterized in that they contain the components (a) and (b) or (a) and (c) in a weight ratio of 90:10 to 10:90.

5. Composition according to claims 1 to 4, characterized in that they contain nonionic and / or amphoteric or zwitterionic surfactants which are selected from the group formed by fatty alcohol polyglycol ethers, alkyl oligoglucosides, fatty acid N-alkyl glucamides and / or betaines.

6. Composition according to claims 1 to 5, characterized in that they are alkyl and alkenyl oligoglycosides of the formula (II) as nonionic surfactants,

R ² 0- [G] _p (II)

in which R ^{2 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.

7. Compositions according to claims 1 to 6, characterized in that they contain fatty acid-N-alkylpolyhydroxyalkylamides of the formula (III) as nonionic surfactants,

R ⁴

I.

R ³ CO-N- [Z] (III)

in which R ³ C0 is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{4 is} an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.

8. Composition according to claims 1 to 7, characterized in that they contain betaines of the formula (V) as amphoteric surfactants,

R6

IR ⁵ -N- (CH ₂ ) _n COOX (V)

IR ⁷

in which R ^{5 represents} alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R ^{6 represents} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{7 represents} alkyl radicals having 1 to 4 carbon atoms, n represents numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium.

9. Composition according to claims 1 to 8, characterized in that they contain betaines of the formula (VI) as amphoteric surfactants,

R6

I.

R8CO-NH- (CH ₂ ) mN- (CH ₂ ) nCOOX (VI)

IR ⁷

in which R ⁸ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ⁶ , R ⁷ , n and X have the meanings given above.

10. Composition according to claims 1 to 9, characterized in that they contain the components (a), (b) and (c) in a weight ratio (10 to 90): (5 to 85): (5 to 85) with which Provided that the weight specifications add up to 100% by weight.

n

11. Composition according to claims 1 to 10, characterized in that they have a surfactant content - based on components (a), (b) and (c) - of 10 to 50 wt .-%.

12. Use of the compositions according to claim 1 for the production of hand dishwashing detergents.