EP0370312A2 - Washing and cleaning agent containing a surfactant mixture of alkyl glycosides and anionic surfactants - Google Patents

Abstract

Washing and cleansing agents with improved detergency contain, in addition to an alkylglycoside, at least one anionic tenside consisting of (a) a fatty alkylsulphate, (b) an alpha -sulphoester or an alpha -sulphocarbonate, (c) a secondary sulphohydroxyester or a secondary sulphohydroxycarbonate, (d) a secondary dialkylether sulphate or (e) mixtures thereof. The weight ratio of alkylglycoside to anionic tenside is between 1:9 and 9:1.

Description

The invention relates to detergents and cleaning agents based on alkyl glycosides and synthetic anionic surfactants.

The surface-active alkyl glycosides, which are acetals from sugars and fatty alcohols with at least 8 carbon atoms, can be produced entirely from renewable raw materials, namely fat on the one hand and sugars or starches on the other hand. The terms alkyl oligoglycoside, alkyl polyglycoside, alkyl oligosaccharide and alkyl polysaccharide refer to those alkylated glycoses in which 1 acetal-like alkyl radical is assigned to more than one glycose radical, that is to say to a poly or oligosaccharide radical. These terms are considered to be synonymous with each other. Accordingly, alkyl monoglycoside means the acetal of a monosaccharide. Since the reaction products from the sugars and the alcohols are generally mixtures, the term alkyl glycoside means both alkyl monoglycosides and alkyl poly (oligo) glycosides, unless the structural differences are important.

Surface-active alkyl glycosides, which are substantially C _i2 - to CwAlkyl- or contain alkenyl radicals, and belong to the class of non-ionic surfactants are already known for over 50 years as detergent raw materials. Austrian Patent No. 135 333 describes the production of lauryl glucoside and cetyl glucoside from acetobromglucose and the respective fatty alcohol in the presence of a base. Direct synthesis from glucose and lauryl alcohol with hydrogen chloride as an acid catalyst is also mentioned. According to the teaching of German patent 611 055, alkyl glucosides are prepared from pentaacetyl glucose and the fatty alcohol in the presence of anhydrous zinc chloride. The German patent 593 422 discloses the maltosides and lactosides of aliphatic alcohols with more than 8 carbon atoms and their use as emulsifying, cleaning and wetting agents. For example, by adding cetyl maltoside to ordinary soap, which was the main component of the detergents at the time, the washing effect of the soap is improved, which is explained by the effect of the cetyl maltoside as a lime soap dispersant. From the 1960s and 1970s, several proposals for improved production processes for alkyl glycosides came either by direct reaction of the glycose, usually in the form of glucose, with an excess of the fatty alcohol and an acid as a catalyst (direct synthesis), or with the use of a lower alcohol or glycol as Solvents and reactants (transacetalization). For example, US Pat. No. 3,547,828 (Mansfield et al) describes the preparation of a ternary mixture of alkyl oligoglucosides, alkyl monoglucosides and the corresponding C ₁₁ -C ₃₂ -alkanols by the transacetalization process with butanol. First, the glucose with butanol and an acid catalyst, e.g. B. sulfuric acid, converted to butyl glucoside, the water of reaction being separated at the reflux temperature. 2 to 6 moles of butanol per mole of glucose are used. The fatty alcohol is then added in amounts of 0.5 to 4 moles per mole of glucose and the excess butanol and the butanol formed in the transacetalization reaction are distilled off. The transacetalization reaction is optionally stopped, so that parts of the butyl glucoside remain in the reaction mixture. In this way, products with low viscosity can be produced. The acidic catalyst is then neutralized by adding sodium hydroxide solution. Then the excess fatty alcohol is largely removed to the desired level in a vacuum.

Such ternary alkyl glycoside mixtures have already been used in combination with other known anionic or nonionic surfactants.

The European patent application 75 995 describes mixtures of alkyl polysaccharides and other nonionic surfactants. European patent application 105 556 discloses cleaning agents which contain alkyl polysaccharides, another nonionic surfactant and an anionic surfactant from the group consisting of glyceryl ether sulfonates, ethoxylated alkylphenol ether sulfates, alkyl sulfates and alkylbenzenesulfonates. According to European patent application 70 074, alkyl glycoside mixtures are combined with anionic surfactants and, if appropriate, other conventional detergent and cleaning agent components. Preferred anionic surfactants are saturated or unsaturated soaps, which can be hydroxylated or sulfonated in the a-position, and in particular alkylbenzenesulfonates. The alkyl poly (oligo) glycosides used contain about 1.5 to 10 glycose units per molecule. This value is an average value and also takes into account the presence of alkyl monoglycosides in a corresponding proportion. However, alkyl glucosides with a degree of oligomerization of 2 or higher are found to be particularly suitable.

The economically most important anion surfactant, which is also used most frequently in combination with ternary alkyl glycoside mixtures, belongs to the surfactant class of alkyl benzene sulfonates.

The disadvantage, however, is the production of the alkylbenzenesulfonates from petrochemical raw materials be considered.

The object of the present invention is to create a washing and cleaning agent which contains a combination of nonionic surfactants and an anionic surfactant from the group of sulfates and sulfonates, which can be obtained entirely from native, ie renewable, fat-chemical raw materials. This combination is also intended to substitute those surfactant mixtures in which the anionic surfactants, which are based exclusively on petrochemical, that is to say non-renewable, raw materials, for example surfactants from the class of the alkylbenzenesulfonates. Substitution in reduced phosphate detergents and cleaning agents is of particular interest. "Reduced phosphate" means in the following those washing and cleaning agents which contain at most 30% by weight, preferably less than 20% by weight, of phosphates, calculated as alkali metal tripolyphosphates, and in particular are free of phosphates.

• (A) einem Alkylglykosid und
• (B) einem anionischen Tensid sowie weitere Bestandteile von festen oder flüssigen Wasch-und Reinigungsmitteln, dadurch gekennzeichnet, daß das Alkylglykosid (A) der allgemeinen Formel (I) gehorcht, RO-(G)_x (I)

in der R einen primären oder sekundären aliphatischen Rest mit 8 bis 22, vorzugsweise 10 bis 18 C-Atomen bedeutet, G ein Symbol ist, das für eine von einem reduzierenden Saccharid abgeleitete Glykose-Einheit mit 5 oder 6 C-Atomen steht, und der Oligomerisierungsgrad x zwischen 1 und 10 liegt, das anionische Tensid (B) mindestens ein Sulfat oder Sulfonat ist, das ganz oder überwiegend aus (a) R₁-OSO₃M (11),

(e) Mischungen der Verbindungen gemäß Formeln (11) bis (V) besteht, wobei M ein Wasserstoff-, Alkali-, Erdalkali- oder Ammoniumkation bedeutet, R, einen aliphatischen linearen Fettalkyl- oder Fettalkenyl-Rest mit 6 bis 26 C-Atomen und

das Derivat einer gesättigten Fettsäure mit 8 bis 22 C-Atomen darstellen, R₃ und R₄ unabhängig voneinander für Wasserstoff oder einen linearen oder verzweigten Alkylrest mit 1 bis 6 C-Atomen stehen, y gleich 0 oder eine Zahl von 1 bis 17, z eine Zahl 1 bis 18 und die Summe (y + z) eine Zahl von 4 bis 18 sein kann, Rs einen aliphatischen linearen oder verzweigten, gesättigten Alkylrest mit 1 bis 18 C-Atomen, R₆ einen aliphatischen linearen, gesättigten Alkylrest mit 6 bis 16 C-Atomen bedeutet und die Summe (Rs + Rε) 7 bis 28 C-Atome beträgt, wobei p eine Zahl von 1 bis 30 und n eine Zahl von 2 bis 4 sein kann, und das Gewichtsverhältnis (A) : (B) zwischen 1 : 9 und 9 : 1, vorzugsweise zwischen 1 : 5 und 5 : 1 liegt.The invention accordingly relates to a washing and cleaning agent containing a surfactant mixture

• (A) an alkyl glycoside and
• (B) an anionic surfactant and further constituents of solid or liquid washing and cleaning agents, characterized in that the alkyl glycoside (A) obeys the general formula (I), RO- (G) _x (I)

in which R is a primary or secondary aliphatic radical having 8 to 22, preferably 10 to 18, carbon atoms, G is a symbol which represents a glycose unit derived from a reducing saccharide and has 5 or 6 carbon atoms, and the Degree of oligomerization x is between 1 and 10, the anionic surfactant (B) is at least one sulfate or sulfonate which is wholly or predominantly composed of (a) R ₁ -OSO ₃ M (11),

(e) Mixtures of the compounds according to formulas (11) to (V), where M is a hydrogen, alkali, alkaline earth or ammonium cation, R, an aliphatic linear fatty alkyl or fatty alkenyl radical having 6 to 26 carbon atoms and

represent the derivative of a saturated fatty acid with 8 to 22 carbon atoms, R ₃ and R ₄ independently of one another represent hydrogen or a linear or branched alkyl radical with 1 to 6 carbon atoms, y is 0 or a number from 1 to 17, z a number 1 to 18 and the sum (y + z) can be a number from 4 to 18, Rs is an aliphatic linear or branched, saturated alkyl radical having 1 to 18 C atoms, R _{6 is} an aliphatic linear, saturated alkyl radical having 6 to 16 C atoms and the sum (Rs + Rε) is 7 to 28 C atoms, where p can be a number from 1 to 30 and n can be a number from 2 to 4, and the weight ratio (A): (B) is between 1: 9 and 9: 1, preferably between 1: 5 and 5: 1.

The washing and cleaning agents according to the invention show a significantly better biodegradability in comparison to agents containing alkylbenzenesulfonate and also a significantly better skin ver indolence.

Furthermore, phosphate-reduced detergents according to the invention have better washability than commercially available phosphate-reduced detergents based on alkylbenzenesulfonate.

The products according to the invention remain liquid at a content of 60% washing active substance, whereas products based on alkylbenzenesulfonates already form precipitates at this content and can no longer be pumped.

Alkyl glycosides suitable for the purposes of this invention are described, for example, in US Pat. Nos. 3,547,828 and 3,839,318. Alkyl glycosides used with particular preference are the process products described in German patent applications 37 23 826 and P 38 33 780.0, which have an alkyl monoglycoside content of over 70% by weight (based on the total amount of alkyl mono- and alkyl oligoglycosides) and an average degree of oligomerization x of less than 1.5, preferably 1.1 to 1.4. While x must always be an integer in a given compound, and especially the numbers x = 1 to 6 come into question here, the value x for a special alkylglycoside process product is an analytically determined arithmetic quantity, which is usually a fractional number.

The sugar component comes from the usual aldoses or ketoses, such as. B. glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose. Because of the better reactivity, the reducing saccharides, the aldoses, are preferably used. Among the aldoses, glucose is particularly suitable due to its easy accessibility and availability in technical quantities. The alkyl glycosides used with particular preference in the invention are therefore the alkyl glucosides. The term "alkyl" in alkylglycoside broadly encompasses the remainder of an aliphatic alcohol of any chain length, preferably a primary aliphatic alcohol having 8 to 22 carbon atoms and in particular a fatty alcohol having 10 to 18 carbon atoms obtainable from natural fats, so that the The term saturated and unsaturated radicals and their mixture including those with different chain lengths in the mixture.

Typical alkyl glycosides are those in which alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and mixtures thereof. Particularly suitable alkyl glycosides contain a coconut fatty alkyl residue, i.e. H. Decyl, dodecyl and tetradecyl residues.

For the purposes of the invention, it is also possible to use alkyl glycosides whose alkyl radical is derived from synthetic primary alcohols, in particular the so-called oxo alcohols, which have a certain percentage, usually 20 to 40%, of branched isomers with a 2-methyl radical , derives. However, such surfactants are less preferred if the focus is also on the intended use of surfactants with a natural raw material base of the hydrophobic part.

When the alkyl glycosides are represented by the formula RO (G) _x , the percentage of fatty alcohol is neglected. This excess of fatty alcohol originating from the reaction can be removed from the product by distillation except for residual values which are less than 5% of the total.

Particularly preferred embodiments of the alkyl glycosides contain more than 70% by weight, in particular 75 to 90% by weight, of alkyl monoglycoside, based on the total amount of alkyl monoglycoside and alkyl oligoglycoside. Essentially, alkyl glycoside mixtures consist of 30 to 90% by weight, preferably 50 to 90% by weight alkyl monoglycoside, 2 to 40% by weight, preferably 3 to 25% by weight alkyl oligoglycoside, 0.5 to 5% by weight. %, preferably 1 to 4% by weight of residual fatty alcohol and 3 to 25% by weight, preferably 5 to 15% by weight of polyglycose. The latter are formed in a side reaction in the alkylation reaction by condensation of the glycose molecules with one another. The average molecular weight of these polyglycoses is from 2000 to 10,000. Surprisingly, contrary to the general teaching, it was found that the presence of these polyglycoses does not impair the stability of the product and, moreover, has a positive effect on the surfactant action of the alkylglycoside.

The alkyl sulfates used for the purposes of the invention as anionic surfactants according to formula (11) are preferably derived from fatty alcohols which are obtained from natural fatty acids or fatty acid mixtures. They are in the form of the alkali, alkaline earth or ammonium salts, ammonium salts also being understood to mean the salts of organic ammonium bases. Suitable alkyl sulfates have a linear alkyl or alkenyl group R, having 6 to 26, preferably 10 to 22, carbon atoms. Alkyl or alkenyl radicals having 16 to 22 carbon atoms, that is to say sulfates, whose fatty alkyl groups consist, for example, of coconut, tallow, lauryl, myristyl, palmityl, stearyl and oleyl radicals and mixtures thereof, are particularly preferred. Sulfates of fatty alcohol mixtures which are derived from natural, linear fatty alcohols and have a C chain distribution of 0 to 3% by weight of C12, 5 to 14% by weight of C14, 25 to 35% by weight of Ci ₆ , 17 are particularly preferred up to 27% by weight of C ₁₈ , 10 to 20% by weight of C ₂₀ and 10 to 20% by weight of C ₂₂ , a hydroxyl number between 210 and 220 and an iodine number of less than 1.0.

Anionic surfactants according to formula (111) are obtained by reacting saturated fatty acids and fatty acid esters, which are in turn predominantly based on natural raw materials, by reacting with S0 ₃ and then converting them to the alkali metal, alkaline earth metal or ammonium salts. Suitable a-sulfoesters and sulfo-acid disalts are derived from fatty acids with 8 to 22, preferably 12 to 18, carbon atoms. In the case of the esters, R ₃ consists of linear or branched alkyl chains with 1 to 6, preferably 1 to 4, carbon atoms. Particularly preferred embodiments are the methyl esters, e.g. B. the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. During the reaction with lye and the formation of the sulfonate, partial saponification to form disalts can take place at the same time. In such mixtures, the disalt can have a proportion of 10% to 50%. Its presence does not adversely affect the wash-active properties of the a-sulfoesters.

The secondary sulfohydroxy esters contained as anionic surfactant components according to formula (IV) in at least one of the surfactant combinations according to the invention are derived from unsaturated fatty acids in which y is 0 or a number from 1 to 17, z is a number from 1 to 18 and the sum (y + z ) can be a number from 4 to 18, from. Preferred secondary sulfohydroxy esters are obtained if unsaturated fatty acids are used for the sulfonation, in which the sum (y + z) is a number from 8 to 18, preferably 8 to 14 and R _{4 is} a linear or branched alkyl radical having 1 to 6, preferably 1 represents up to 4 carbon atoms. Suitable fatty acids are therefore, for example, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid and erucic acid, as well as mixtures of these and various oleate cuts obtainable from tallow fats. A particularly preferred embodiment is an ester according to the invention with y and z equal to 7, where R _{4 is} a branched alkyl radical with 4 carbon atoms, for example a secondary sulfohydroxy ester based on oleic acid isobutyl ester.

The process for the preparation of the secondary sulfohydroxy esters is described in detail using the example of oleic acid lower alkyl ester sulfonates in the earlier application P 38 28 892.3. The sulfonation of the oleate cuts used can be carried out with gaseous sulfur trioxide in conventional sulfonation reactors, in particular of the falling film type, at temperatures in the preferred range from 15 to 30 ° C.

mit gasförmigem Schwefeltrioxid und anschließender Neutralisation mit wäßrigem Alkali-, Erdalkali- oder Ammoniumhydroxid gut zugänglich. Rε bedeutet dabei einen aliphatischen linearen oder verzweigten, gesättigten Alkylrest mit 1 bis 18, vorzugsweise 1 bis 8, insbesondere 4 bis 8C-Atomen, während Rs einen aliphatischen linearen, gesättigten Alkylrest mit 6 bis 16, vorzugsweise 6 bis 14 und insbesondere 10 bis 12 C-Atomen bedeutet, wobei die Summe (Rs + Rε) mindestens 7 und maximal 28 beträgt und vorzugsweise zwischen 14 und 18 C-Atomen liegt. p kann eine Zahl von 1 bis 30, vorzugsweise von 1 bis 10, und n eine ganze Zahl von 2 bis 4 sein. Vorzugsweise steht n für die Zahl 2.Secondary dialkyl ether sulfates of the formula (V) can be obtained by reacting secondary hydroxydialkyl ethers of the general formula (VI)

with gaseous sulfur trioxide and subsequent neutralization with aqueous alkali, alkaline earth or ammonium hydroxide. Rε here means an aliphatic linear or branched, saturated alkyl radical having 1 to 18, preferably 1 to 8, in particular 4 to 8C atoms, while Rs is an aliphatic linear, saturated alkyl radical having 6 to 16, preferably 6 to 14 and in particular 10 to 12 C atoms means, the sum (Rs + Rε) being at least 7 and a maximum of 28 and preferably being between 14 and 18 C atoms. p can be a number from 1 to 30, preferably from 1 to 10, and n can be an integer from 2 to 4. N is preferably the number 2.

beschrieben. Dabei erfolgt die Umsetzung von Verbindungen der allgemeinen Formel (VII) mit Verbindungen der allgemeinen Formel (VIII) bei erhöhter Temperatur unter Schutzgas in Gegenwart eines Katalysators.The process for the preparation of secondary hydroxydialkyl ethers of the formula (VI) from epoxides of the general formula (VII) and alcohol alkoxylates of the general formula (VIII) is described in detail in the earlier application P 37 23 323.8

described. The reaction of compounds of the general formula (VII) with compounds of the general formula (VIII) is carried out at elevated temperature under a protective gas in the presence of a catalyst.

Suitable further components of liquid or solid detergents and cleaning agents are, for the purposes of this invention, for. B. builder substances, bleaching agents, foam stabilizers, complexing agents, optical brighteners, thickening agents, dirt suspending agents, graying inhibitors, dyes, perfume oils, enzymes, bactericides, fungicides, etc.

Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline salts, in particular alkali salts, which are able to precipitate or complex calcium ions to tie. Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, in particular pentasodium triphosphate, are of particular importance in addition to the alkali ortho- and alkali pyrophosphates. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.

Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkanephosphonic acids, amino and hydroxyalkanephosphonic acids and phosphonopolycarboxylic acids such as. B. methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acids, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.

Of the organic framework substances, the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions, which also include polymers containing carboxyl groups, are of particular importance. Are suitable for. B. citric acid and tartaric acid. Polycarboxylic acids containing ether groups are also suitable, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, e.g. B. biscarboxymethylethylene glycol, carboxymethyloxy succinic acid, carboxymethyl tartronic acid and carboxymethylated or oxidized polysaccharides. Polymeric carboxylic acids with a molecular weight of at least 350 in the form of water-soluble salts are also suitable. Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000 and in particular in the range from 10,000 to 100,000. These compounds include, for example, polyacrylic acid, polyhydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as vinyl methyl ether . The water-soluble salts of polyglyoxylic acid are also suitable.

As water-insoluble inorganic builders are, for. B. the finely divided, synthetic bound water containing sodium aluminosilicates of the zeolite A type described in DE-OS 24 12 837 as phosphate substitutes for detergents and cleaning agents. The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form. They have practically no particles larger than 30 µm and preferably consist of at least 80% particles smaller than 10 µm. Your calcium binding capacity, which is determined according to the details of DE-OS 24 12 837, is in the range of 100 to 200 mg CaO / g. Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.

Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates, which are also referred to as "washing alkalis". Of the alkali silicates, especially the sodium silicates with a ratio of Na ₂ 0: Si0 ₂ such as 1: 1 to 1: 3.5 can be used.

The detergents according to the invention can additionally contain bleaching agents and bleach activators. Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate (NaB0 ₂ .H ₂ 0 ₂ .3H ₂ 0) and monohydrate (NaB0 ₂ .H ₂ 0 ₂ ) are of particular importance. However, other borates which supply H ₂ 0 _{2 can also} be used, e.g. B. the Perborax Na ₂ B ₄ .0 ₇ . 4H ₂ 0 ₂ . These compounds can be partially or completely by other active oxygen carriers, in particular by peroxypyrophosphates, citrate perhydrates, urea / H ₂ 0 ₂ - or melamine / H ₂ 0 ₂ compounds as well as by H ₂ 0 ₂ delivering peracid salts such as. As caroates (KHSOs), perbenzoates or peroxyphthalates can be replaced.

As a further component, the detergents and cleaning agents can contain dirt carriers which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. For this purpose, water-soluble colloids, usually of an organic nature, are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.

Further surfactants can also be added to the mixtures, provided that they do not interfere with the positive effect of the washing and cleaning agents according to the invention.

EXAMPLES

• Waschprogramm: Einlaugenprogramm bei 30 °C₁ 30 Min.
• Dosierung: 86 g Waschpulver/Maschine
• Wasserhärte: 16 ' d
• Textilproben: 3 kg saubere Füllwäsche
• Bestimmungen: 3-fach
• Meßtechnische Bedingungen:
• künstliche Anschmutzungen: RFC 3/24 (465 nm)
• natürliche Anschmutzungen: Lange-Gerät (Y-Filter)

Examples 1 to 8 below describe the tests carried out to test the washing power of the washing and cleaning agents according to the invention in a household washing machine (type: Miele W 760) under the following conditions:

• Washing program: soaking program at 30 ° C ₁ 30 min.
• Dosage: 86 g washing powder / machine
• Water hardness: 16 'd
• Textile samples: 3 kg clean laundry
• Determinations: 3-fold
• Measurement conditions:
• artificial soiling: RFC 3/24 (465 nm)
• natural soiling: Lange device (Y filter)

• 13,5 Gew.-% Natriumdodecylbenzolsulfonat
• 1,5 Gew.-% C₁₆-C₁₈-Fettalkohole mit 5 - 10 Mol Ethylenoxid
• 1,5 Gew.-% Seife (C₁₂-C₁₈-Fettsäuren)
• 2,5 Gew.-% Wasserglas
• 20,0 Gew.-% Zeolith NaA
• 3,5 Gew.-% Sokalan CP5 (Acrylsäure-Maleinsäure-Copolymer Na-Salz)
• Rest anorganische Salze, Wasser und weitere Zusatzstoffe

The composition of the P-free comparison formulation V1 was:

• 13.5% by weight sodium dodecylbenzenesulfonate
• 1.5% by weight of C ₁₆ -C ₁₈ fatty alcohols with 5-10 moles of ethylene oxide
• 1.5% by weight of soap (C ₁₂ -C ₁₈ fatty acids)
• 2.5% by weight water glass
• 20.0 wt% zeolite NaA
• 3.5% by weight Sokalan CP5 (acrylic acid-maleic acid copolymer Na salt)
• Balance inorganic salts, water and other additives

In Examples 1 to 8, a proportion of 15.0% by weight, consisting of 13.5% by weight of sodium dodecylbenzenesulfonate and 1.5% by weight of C ₁₆ -C ₁₈ , was in each case in the P-free comparison formulation V1 -Fatty alcohol with 5 to 10 moles of ethylene oxide, replaced by various surfactant combinations: anionic surfactant: nonionic surfactant used in the specified mixing ratios. Mixtures with the composition (a) in the examples include dodecylbenzenesulfonate and C ₁₆ -C ₁₈ fatty alcohol with 5 to 10 moles of ethylene oxide. The mixtures in experiment (b) contain the surfactant mixtures to be tested, consisting of anionic surfactant according to the formulas (II) to (V) and alkyl glycoside (I). A coconut alkyl glucoside (C ₁₂ / C ₁₄ ) was used as the alkyl glycoside.
Composition (GC analysis): 62.8% by weight monoglucoside, 15.4% by weight diglucoside, 5.8% by weight triglucoside, 3% by weight residual fatty alcohol, 8% by weight polyglucose; Degree of oligomerization x = 1.3.

1st example:

Surfactant mixture (a) from 12.5% by weight fatty alcohol ethoxylate and 2.5% by weight dodecylbenzenesulfonate, surfactant mixture (b) from 12.5% by weight (I) and 2.5% by weight alkyl sulfate (II) , consisting of a mixture of C ₁₂ -C ₂₂ alkyl sulfates with a C chain distribution of 2% by weight C ₁₂ , 10% by weight C ₁₄ , 31% by weight C ₁₆ , 21% by weight cis, 19% by weight of C ₂₀ and 17% by weight of C ₂₂ . In the case of fat-pigment soiling, standard soiling was used.

The reflectance values were determined photometrically (Zeiss reflectometer, for lipstick and make-up with a Y filter). Remission differences of 2% and more are significant.

2nd example:

Surfactant mixture (a) from 12.5% by weight of dodecylbenzenesulfonate and 2.5% by weight of fatty alcohol ethoxylate, surfactant mixture (b) from 12.5% by weight of saturated a-sulfoesters (III), consisting of a mixture of the sodium salts of a-Sulfotalgfettsäuremethylestern, and 2.5 wt .-% (I).

3rd example

Surfactant mixture (a) of 7.5% by weight of dodecylbenzenesulfonate and 7.5% by weight of alcohol ethoxylate, surfactant mixture (b) of a-sulfoester (III) and alkyl glycoside (I) in the same ratio.

4th example

Surfactant mixture (a) as in Example 1, surfactant mixture (b) consisting of 2.5% by weight of a-sulfoester (III) and 12.5% by weight of alkyl glycoside (1).

Different remission values for the same soiling with the same anionic surfactant / nonionic surfactant ratio result from several washes with different initial degrees of soiling. However, the values within a table can be compared directly with one another.

Surfactant mixture (a) as in Example 1, surfactant mixture (b) from 12.5% by weight (I) and 2.5% by weight of a secondary hydroxysulfonate of the oleic acid isobutyl ester (IV) in the form of the Na salt.

6. Example:

• (b) R₅ = C₈H₁₇
• R₆ ⁼ C₁₀H₂₁
• n = 2
• p = 4
• (c) R₅ = CH₃
• R₆ = C₁₀H₂₁
• n= 2
• p=4 4
  

Surfactant mixture (a) as in Example 2, surfactant mixtures (b) and (c) from 2.5% by weight (I) and 12.5% by weight of secondary dialkyl ether sulfates (V) in the form of the Na salts

• (b) R ₅ = C ₈ H ₁₇
• R ₆ ⁼ C ₁₀ H ₂₁
• n = 2
• p = 4
• (c) R ₅ = CH ₃
• R ₆ = C ₁₀ H ₂₁
• n = 2
• p = 4 4
  

7th example

Example 6 was repeated with a mixing ratio in (a) and (b) of 7.5% by weight to 7.5% by weight.

8. Example

Example 7 was repeated with a mixing ratio in (a) and (b) of 12.5% by weight nonionic surfactant to 2.5% by weight anionic surfactant.

Different remission values for the same soiling with the same anionic surfactant / nonionic surfactant ratio result from several washes with different initial degrees of soiling. However, values within a table can be compared directly with one another.

Example 9: Dishwashing capacity of surfactant mixtures of (I) and secondary dialkyl ether sulfates (V)

To test the cleaning performance, saucers were coated with 2 g of mixed water, protein, fat and carbohydrates mixed with water. Then 8 liters of tap water (16 d) and 8 liters of softened water (3 d), each at 45 ° C., were placed in a bowl. To clean the soiled plates, 1.2 g of a cleaning agent consisting of an anionic surfactant according to formula (V) (DAES) and / or a C ₁₂ / C ₁₄ -alkyl glucoside (APG) used according to formula (I) were added and the plates washed until the foam of the solution disappears. The mixing ratio was varied as indicated in Table 9.

• Temperatur: 45°C
• Aktivsubstanz: 0,15 g/I
• Wasserhärte: 3 d bzw. 16 ° d
  

While DAES had only a very moderate rinsing capacity per se and APG per se only a medium rinsing capacity, a mixture of both components led to an increase in activity of a maximum of 100%, based on C ₁₂ / C ₁₄ alkyl glucoside used alone, the level of the standard sodium dodecylbenzenesulfonate ( ABS) was reached.

• Temperature: 45 ° C
• Active substance: 0.15 g / l
• Water hardness: 3 d or 16 ° d
  

Claims (8)

1. Washing and cleaning agent containing a surfactant mixture (A) an alkyl glycoside and (B) an anionic surfactant
as well as further constituents of solid or liquid washing and cleaning agents, characterized in that the alkyl glycoside (A) obeys the general formula (I),
RO- (G) _x (I)
in which R is a primary or secondary aliphatic radical having 8 to 22, preferably 10 to 18, carbon atoms, G is a symbol which represents a glycose unit derived from a reducing saccharide and has 5 or 6 carbon atoms, and the Degree of oligomerization x is between 1 and 10, the anionic surfactant (B) is at least one sulfate or sulfonate, which consists entirely or predominantly of (a) R ₁ -OSO ₃ M (11),

(e) Mixtures of the compounds of the formulas (II) to (V), where M is a hydrogen, alkali, alkaline earth or ammonium cation, R _{1 is} an aliphatic linear fatty alkyl or fatty alkenyl radical having 6 to 26 carbon atoms and

represent the derivative of a saturated fatty acid with 8 to 22 carbon atoms, Rs and R ₄ independently of one another represent hydrogen or a linear or branched alkyl radical with 1 to 6 carbon atoms, y is 0 or a number from 1 to 17, z a Number from 1 to 18 and the sum (y + z) can be a number from 4 to 18, Rs is an aliphatic linear or branched, saturated alkyl radical having 1 to 18 carbon atoms, R _{6 is} an aliphatic linear, saturated alkyl radical having 6 to 16 C atoms and the sum (Rs + R _G ) is 7 to 28 C atoms, where p can be a number from 1 to 30 and n can be a number from 2 to 4, and the weight ratio (A): (B ) between 1: 9 and 9: 1. 2. Composition according to claim 1, characterized in that the weight ratio (A): (B) 1: 5 to 5: 1. is. 3. Composition according to claim 1 or 2, characterized in that the amount of alkyl monoglycoside, based on the total amount of alkyl monoglycoside and alkyl oligoglycoside, in the nonionic surfactant according to formula (I) is over 70% by weight and x is less than 1.5, preferably Is 1.1 to 1.4. 4. Composition according to claim 1, 2 or 3, characterized in that the alkyl glycoside is derived from the glucose. 5. Composition according to one or more of claims 1 to 4, characterized in that the alkyl sulfates according to formula (II) have a C chain distribution of 0 to 3% by weight C ₁₂ , 5 to 14% by weight C ₁₄ , 25 up to 35% by weight of C ₁₆ , 17 to 27% by weight of C ₁₈ , 10 to 20% by weight of C ₂₀ and 10 to 20% by weight of C ₂₂ , a hydroxyl number between 210 and 220 and an iodine number of less have than 1.0. 6. Composition according to one or more of claims 1 to 4, characterized in that the secondary sulfohydroxy esters of the formula (IV) are derived from a linear C ₁₈ fatty acid and R _{4 is} a linear or branched alkyl radical having 4 carbon atoms. 7. Composition according to one or more of claims 1 to 4, characterized in that it contains a secondary dialkyl ether sulfate according to formula (V), wherein R ₅ 1 to 8, preferably 4 to 8 C atoms and R ₆ 6 to 14, preferably 10 to 12 carbon atoms means (R ₅ + R ₆ ) is between 14 and 18 carbon atoms, p is a number from 1 to 10 and n is 2. 8. Composition according to one or more of claims 1 to 4, characterized in that it contains an α-sulfomethyl ester according to formula (III) in which the alkyl radical R _{2 has} 10 to 16 carbon atoms.