WO1993010208A1 - Aqueous detergent mixtures - Google Patents

Abstract

The invention concerns aqueous detergent mixtures containing a) alkyl and/or alkenyl oligoglycoside sulphates, b1) fatty-alcohol sulphates or b2) fatty-alcohol ether sulphates and, optionally, c1) alkyl and/or alkenyl oligoglycosides or c2) alkyl sulphosuccinates. Such mixtures have synergistic foaming, wetting, washing and revitalizing properties and are suitable for use in the manufacture of hand washing-up agents, washing powders and textiles conditioners.

Description

 Aqueous mixtures of detergents

Field of the Invention

The invention relates to aqueous detergent mixtures containing alkyl and / or alkenyl oligoglycoside sulfates, fatty alcohol sulfates or fatty alcohol ether sulfates and, where appropriate, further anionic or nonionic surfactants and the use of the aqueous detergent mixtures for the production of manual dishwashing detergents, powder detergents and fabric softeners.

State of the art

Alkyl oligoglycoside sulfates and in particular alkyl oligoglucoside sulfates are known anionic surfactants which can be obtained, for example, by reacting glucose with sulfuric acid and fatty alcohols [US 1.951.784] and sulfating alkyl oligoglucosides in dimethylformamide with sulfur trioxide [EP 0 186 242 AI] or a sulfur trioxide-amine complex [EP 0 363 601 A2]. The gas sulfonation of alkenyl glycosides in inert solvents is also described in DE 39 18 135 AI. From international patent application WO 88/01640 it is known that combinations of alkyl oligoglycosides and alkyl oligoglycoside sulfates are suitable for the production of manual dishwashing detergents. According to the teaching of US Pat. No. 4,483,787, alkyl oligoglycoside sulfates can also be used in liquid detergents. Finally, detergent mixtures with good skin tolerance containing alkyl oligoglycoside sulfates, amphoteric or zwitterionic surfactants and other anionic surfactants are known from international patent application WO 91/00584.

Alkyl oligoglycoside sulfates have the disadvantage that they have only average detergent properties as individual surfactants, but also in a mixture with alkyl oligoglycosides, which make their use in marketable surface-active products possible only to a limited extent. Even the combinations with non-ionic fatty alcohol polyglycol ethers, otherwise a proven means of improving the application properties of anionic surfactants, either lead to little or no success.

The object of the invention was therefore to develop detergent mixtures containing alkyl oligoglycoside sulfates which are free from the disadvantages described.

Description of the invention

The invention relates to aqueous detergent mixtures comprising a) alkyl and / or alkenyl oligoglycoside sulfates b1) fatty alcohol sulfates or

 b2) fatty alcohol ether sulfates and optionally c1) alkyl and / or alkenyl oligoglycosides or

 c2) alkyl sulfosuccinates.

Surprisingly, it was found that the detergent properties of alkyl and / or alkenyl oligoglycoside sulfates can be increased significantly if they are combined with fatty alcohol sulfates or fatty alcohol ether sulfates. The detergent mixtures according to the invention show a synergistic increase in the wetting, foaming and washing capacity over a wide range of mixtures. For certain application problems, the performance can be further improved by adding further anionic or nonionic surfactants.

Alkyl and / or alkenyl oligoglycoside sulfates which are constituents of the aqueous detergent mixtures according to the invention follow the formula (I),

R ¹ -O- [G] pSO ₃ X (I) in the R ^{1 represents} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms,

 [G] for a glycose unit with 5 or 6 carbon atoms, p for a number from 1 to 10 and

 X represents an alkali or alkaline earth metal.

The substances are usually prepared by reacting the corresponding alkyl and / or alkenyl oligoglycosides with gaseous sulfur trioxide in inert solvents and subsequent neutralization with aqueous alkali metal hydroxides. If one starts from alkyl oligoglucosides, an exclusive sulfation of free hydroxyl groups on the sugar body takes place during the reaction; if the carbon chain is unsaturated, sulfonate groups may also be present due to a subordinate electrophilic addition of sulfur trioxide to the double bond.

Alkyl and / or alkenyl oligoglycoside sulfates, which can be used with particular advantage, are derived from aldoses or ketoses. Because of their better reactivity, alkyl and / or alkenyl oligoglycoside sulfates based on reducing saccharides, the aldoses, are preferred. Among the aldoses, glucose is particularly suitable as a starting material because of its easy accessibility and technical availability. The preferred alkyl and / or alkenyl oligoglycosides are therefore the alkyl and / or alkenyl oligoglucoside sulfates.

The index number p in the general formula (I) indicates the degree of oligomerization, ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and can in particular assume the values p = 1 to 6, the value p for a certain alkyl and / or alkenyl oligoglycoside sulfate is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycoside sulfates with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. Those alkyl and / or alkenyl oligoglycoside sulfates whose degree of oligomerization is less than 1.7 and in particular between 1.1 and 1.4 are particularly preferred.

The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadolyl alcohol, behenyl alcohol, erucyl alcohol and natural oils, palm oil, and coconut oil, and their technical blends, palm oil based on palm oils and natural oils or beef tallow.

Alkyl and / or alkenyl oligoglycoside sulfates which can be used with particular advantage in the detergent mixtures according to the invention follow the formula (I) in which R ¹ for an alkyl radical having 12 to 18 carbon atoms, [G] for a glucose radical and p for numbers from 1 to 3, in particular 1.1 to 1.7. The alkyl and / or alkenyl oligoglycoside sulfates are preferably used in the form of their sodium or potassium salts. Fatty alcohol sulfates are also known substances which are produced on an industrial scale by sulfating primary alcohols, for example with sulfur trioxide or chlorosulfonic acid. Fatty alcohol sulfates which can be used for the purposes of the invention follow the formula (II),

R ² -O-SO ₃ X (II) in the

R ^{2 is} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms and

 X represents an alkali or alkaline earth metal.

Typical examples are the sulfates of Capronalkohols, Caprylalkohols, capric alcohol, lauryl alcohol, Myristylalkohols, cetyl alcohol, Palmoleylalkohols, stearyl alcohol, oleyl alcohol, Elaidylalkohols, Petroselinylalkohols, Arachylalkohols, Gadoleylalkohols, behenyl alcohol and Erucylalkohols and their technical mixtures, such as for example in the high-pressure hydrogenation of technical fatty acid methyl ester based palm oil, palm kernel oil, coconut oil, turnip oil, sunflower oil, olive oil or beef tallow.

Fatty alcohol sulfates, which can also be used in the context of the invention, are derived from oxo alcohols which are accessible by hydrogenation of aldehydes from Roelen's oxosynthesis and have a proportion of 5 to 25% by weight of branched species. Saturated fatty alcohol sulfates with 12 to 18 carbon atoms in the form of their sodium or potassium salts are preferably used.

Fatty alcohol ether sulfates are produced on an industrial scale by sulfating fatty alcohol polyglycol ethers with sulfur trioxide or chlorosulfonic acid and follow the formula (III),

R ³ -O- (CH ₂ CH ₂ O) _n -O0 ₃ X (III) in the

R ^{3 represents} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms,

n for numbers from 1 to 10 and

X represents an alkali or alkaline earth metal,

Typical examples are the sulfation products of adducts of 1 to 10 moles of ethylene oxide with 1 mole of caprone alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol and technical alcohol, erucyl alcohol, gadyl alcohol, gadyl alcohol, gadyl alcohol . Sulfates of adducts of 2 to 7 moles of ethylene oxide with saturated coconut oil alcohols having 12 to 18 carbon atoms in the form of their sodium or potassium salts are preferred. Alkyl and / or alkenyl oligoglycosides which are suitable as further optional constituents of the aqueous ditergen mixtures according to the invention are to be understood as acetals of glycoses with fatty alcohols which follow the formula (IV)

R ⁴ -O- [G] p (IV) in the

R ^{4 represents} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms,

 [G] for a glycose unit with 5 or 6 carbon atoms and

 p represents a number from 1 to 10.

They can be prepared from mono- or poly-sugars, such as glucose or starch, which are acetalized with fatty alcohols in the presence of acidic catalysts either directly or via the intermediate stage of lower alkyl and / or alkenyl glycosides. As representative of the extensive literature on this subject, reference is made here to European patent applications EP 0 301 298 A1 and EP 0 362 671 A1.

Typical examples are lauryl oligoglucoside, myristyl oligoglucoside, cetyloligoglucoside, stearyl oligoglucoside, oleyl oligoglucoside, behenyl oligoglucoside and erucyl oligoglucoside as well as their technical mixtures, whose average degree of oligomerization p is in the range from 1.1 to 3.0. Preferred is the use of alkyl oligoglycosides of the formula (IV) in which R ^{4 is} an alkyl radical having 12 to 18 carbon atoms, [G] is a glucose radical and p is a number from 1.1 to 1.7.

Finally, further optional components are alkyl sulfosuccinates which follow the formula (V)

in der

in the

R ⁵ and R ^{6 are} independently linear or branched

 Alkyl radicals with 6 to 22 carbon atoms and

 X represents an alkali or alkaline earth metal.

Alkyl sulfosuccinates are usually prepared by adding sodium bisulfite to maleic acid ester. Typical examples are the sulfitation products of maleic acid di-octyl ester or maleic acid di-2-ethylhexyl ester. Products of the formula (V) in which R ⁵ and R ^{6 are} alkyl radicals having 8 to 12 carbon atoms and X is sodium or potassium are preferred.

The aqueous detergent mixtures according to the invention can contain the individual components in the following amounts: Alkyl and / or alkenyl oligoglycoside sulfates 2 to 50%

Fatty alcohol sulfates 15 to 98%

Fatty alcohol ether sulfates 15 to 95%

Alkyl and / or alkenyl oligoglycosides 20 to 80%

Alkyl sulfosuccinates 40 to 80%

All percentages are to be understood as% by weight and in each case relate to the solids content of the detergent mixtures.

Aqueous detergent mixtures with particularly advantageous performance properties contain the alkyl and / or alkenyl oligoglycoside sulfates in amounts of 5 to 15% by weight, the fatty alcohol sulfates or fatty alcohol ether sulfates in amounts of 10 to 50% by weight and optionally the alkyl and / or Alkenyl oligoglycosides or the alkyl sulfosuccinates in amounts of 60 to 80% by weight.

The aqueous detergent mixtures can be prepared by simple mechanical mixing of the aqueous solutions of the components, if appropriate at elevated temperatures of 30 to 50 ° C; a chemical reaction does not take place here.

In a preferred embodiment of the invention, detergent mixtures containing alkyl oligoglycoside sulfates and fatty alcohol sulfates can also be prepared in situ by subjecting mixtures of alkyl oligoglycosides and fatty alcohols, such as are produced as an intermediate in the production of alkyl oligoglycosides, to cosulfation. With regard to the details, reference is made here to German patent application DE 40 06 841 A1. The detergent mixtures according to the invention show a pronounced foaming, wetting and cleaning ability, give textiles a pleasant soft feel and are completely biodegradable.

Another object of the invention therefore relates to the use of aqueous detergent mixtures of the composition mentioned for the production of surface-active agents, in particular manual dishwashing detergents, powder detergents and fabric softening agents, in which they are present in amounts of 0.1 to 25, preferably 1 to 10% by weight. based on the funds - may be included.

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

Examples Ia. Surfactants used

T1) C _12/14 coconut alkyl oligoglucoside sulfate Na salt T2) C _12/14 coconut fatty alcohol sulfate Na salt

T3) C _16/18 tallow fatty alcohol sulfate Na salt

Sulfopon ^(R) T (Henkel KGaA)

T4) C _12/14 coconut fatty alcohol-2 EO sulfate Na salt Texapon ^(R) N (Henkel KGaA)

T5) C _12/14 cocoalkyl oligoglucoside

T6) Di-n-octylsulfosuccinate Na salt

Texapon ^(R) DOS (Henkel KGaA)

T7) Dodecylbenzenesulfonate Na salt

Maranil ^(R) A55 (Henkel KGaA)

Ib. Preparation of C _12/14 coconut alkyl oligoglycoside sulfate Na salt

53 g (0.13 mol) of C _12/14 cocoalkyl oligoglucoside (p = 1.3) were dissolved in 150 ml of 1,2-dichloroethane at 25 ° C. with vigorous stirring. The dissolved starting material was transferred to a 500 ml sulfonation reactor with jacket cooling and gas inlet tube and reacted at 30 ° C. with 13 g (0.17 mol) of gaseous sulfur trioxide, which was released from a corresponding amount of 65% by weight oleum by means of a nitrogen stream and was introduced into the solution within 12 min. The crude sulfonation product was stirred into 100 ml of water and neutralized with aqueous 25% by weight sodium hydroxide solution. The solvent was then distilled off at a temperature of 30 ° C. and a reduced pressure of 0.1 bar on a rotary evaporator. An aqueous paste remained which had the following characteristics:

Anionic surfactant content: 33.8% by weight

 Unsulphated parts: 4.1% by weight

inorganic sulfate: 1.1% by weight

Water: 61.0% by weight

The anionic surfactant content as well as the unsulfonated contents were determined according to the DGF standard methods, Stuttgart 1959 - 1984, H-III-10 and G-III-6b. II. Assessment of dish washing capacity

The determination of the dishwashing capacity was carried out with the aid of the dish test [Fette, Seifen, Anstrichmitt., 74, 163 (1972)]. For this purpose, plates with a diameter of 14 cm each with a) 1.9 g beef tallow (melting point 40-42 ° C, acid number 9-10) or

 b) 1.9 g of a mixed contamination of protein, fat and carbohydrates soiled and stored at a temperature of 0 to 5 ° C for 15 h.

The plates with the beef tallow dirt ("RiTa") were then rinsed at 45 ° C, the plates with the mixed soiling ("Mino") at 50 ° C with tap water with a hardness of 16 ° d. The test mixtures were used with a dosage of 0.15 ("RiTa") or 0.12 g / 1 water ("Mino"). The rinsing attempt was terminated as soon as the foam cover tore open on the surface and the fleet underneath became visible.

The results of the rinsing tests are summarized in Tab. 1.

II. Assessment of washing power

The investigation of the washing ability was carried out in a launderometer on a dust-skin fat stain (A) or a lipstick stain (B) on polyester-cotton (refined) fabric. The lightening of the washed tissue was assessed by photometric reflectance measurement using an Elrepho RFC-3/24 device against a barium sulfate standard, the reflectance of which was set at 100%. The information is given in% remission (% -R).

Liquor: 250 ml

 Fleet loading: 1 part by weight of tissue / 30% by weight of water

Dosage: 10 g / 1

 Water hardness: 16 ° d

 Destination: Average of 3 destinations

The results of the washing tests are summarized in Table 2.

III. Beurteilung der Avivagewirkung

III. Assessment of the aviva effect

Repeated washing of hardened cotton fabric (Molton) was carried out using the padding process with the detergent mixtures of Examples 19 to 21 and the individual surfactants according to Comparative Examples V14 to V17. The following requirements apply:

Concentration: 30 g / 1

 Fleet absorption: approx. 80% by weight based on dry tissue

Drying: 3 min at 180 ° C

The soft grip was assessed subjectively by 6 experienced people who were able to assign grades on a scale from 0 = "hard and rough" to 4 = "soft and voluminous". The test results are summarized in Tab. 3.

Cotton terry fabrics were finished under the same conditions. The evaluation of the soft grip showed comparable results to the molton fabric.

Claims

Claims 1. Aqueous detergent mixtures containing a) alkyl and / or alkenyl oligoglycoside sulfates b1) fatty alcohol sulfates or  b2) fatty alcohol ether sulfates and optionally c1) alkyl and / or alkenyl oligoglycosides or  c2) alkyl sulfosuccinates. 2. Aqueous detergent mixtures according to claim 1, characterized in that they contain alkyl and / or alkenyl oligoglycoside sulfates which are derived from alkyl and / or alkenyl oligoglycosides of the formula (I), R ¹ -O- [G] pSO ₃ X (I) in the R ^{1 represents} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms, [G] for a glycose unit with 5 or 6 carbon atoms,  p for a number from 1 to 10 and X represents an alkali or alkaline earth metal. 3. Aqueous detergent mixtures according to claims 1 and 2, characterized in that they contain fatty alcohol sulfates of the formula (II), R ² -O-SO ₃ X (II) in the R ² for a linear or branched alkyl or Alkenyl radical having 6 to 22 carbon atoms and  X represents an alkali or alkaline earth metal, 4. Aqueous detergent mixtures according to at least one of claims 1 to 3, characterized in that they contain fatty alcohol ether sulfates of the formula (III), R ³ -O- (CH ₂ CH ₂ O) _n -SO ₃ X (III) in the R ^{3 represents} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms,  n for numbers from 1 to 10 and  X represents an alkali or alkaline earth metal. 5. Aqueous detergent mixtures according to at least one of claims 1 to 4, characterized in that they are alkyl and / or contain alkenyl oligoglycosides of the formula (IV), R ⁴ -O- [G] p (IV) in the R ^{4 represents} a linear or branched alkyl or alkenyl radical having 6 to 22 carbon atoms,  [G] for a glycose unit with 5 or 6 carbon atoms and  p represents a number from 1 to 10. 6. Aqueous detergent mixtures according to at least one of claims 1 to 5, characterized in that they contain alkyl sulfosuccinates of the formula (V),

in the R ⁵ and R ⁶ independently of one another for linear or branched alkyl radicals having 6 to 22 carbon atoms and X for an alkali or alkaline earth metal stands . 7. Aqueous detergent mixture according to at least one of claims 1 to 6, characterized in that it contains the alkyl and / or alkenyl oligoglycoside sulfates in amounts of 2 to 50% by weight, based on the solids content of the mixtures. 8. Aqueous detergent mixture according to at least one of claims 1 to 7, characterized in that it contains the fatty alcohol sulfates in amounts of 15 to 98% by weight, based on the solids content of the mixtures. 9. Aqueous detergent mixture according to at least one of claims 1 to 8, characterized in that it contains the fatty alcohol ether sulfates in amounts of 15 to 95% by weight, based on the solids content of the mixtures. 10. Aqueous detergent mixture according to at least one of claims 1 to 9, characterized in that it contains the alkyl and / or alkenyl oligoglycosides in amounts of 20 to 80 wt .-% - based on the solids content of the mixtures. 11. Aqueous detergent mixture according to at least one of claims 1 to 10, characterized in that it Alkyl sulfosuccinates in amounts of 40 to 80 wt .-% - based on the solids content of the mixtures - contain. 12. Use of aqueous Detergensgemnisehen according to claims 1 to 11 for the production of surface-active agents. 13. Use according to claim 12, characterized in that the aqueous detergent mixtures are used in manual dishwashing detergents. 14. Use according to claim 12, characterized in that the aqueous detergent mixtures are used in powder detergents. 15. Use according to claim 12, characterized in that the aqueous detergent mixtures are used in fabric softeners.