EP2036973A1 - Surfactant systems - Google Patents

Abstract

Use of a surfactant (Q) comprising nitrogen containing compound (I) or alkane oxy compound (IV), in combination with an ethoxylated fatty alcohol compound (V), for improving the washability of the detergents at = 30[deg] C, preferably 20[deg] C, is claimed. Use of a surfactant (Q) comprising nitrogen containing compound (I) of formula ((R 1>CO-N(R 2>)-(A)-N +>(R 3>)(R 4>)-R 5>)(X ->)) (II) or ((R 6>-N(CH 2-CH 2-O) nH)-R 7>) (III) or alkane oxy compound of formula (R7a-(CH 2-CH 2-O) x(CH 2-CHCH 3-O) yH) (IV), in combination with an ethoxylated fatty alcohol compound of formula (R 8>-(CH 2-CH 2-O) r-H) (V), for improving the washability of the detergents at = 30[deg] C, preferably 20[deg] C, is claimed. R 1>optionally saturated, ethoxylated 16-22C-hydroxyacyl residue with 1-50 ethylene oxide units; A : 1-6C-alkyl; R 2>-R 4>1-4C-alkyl or H; R 5>an alkyl- or benzyl- residue; X : halo, alkyl sulfate or alkyl phosphate; R 6>optionally saturated 8-24C-alkyl; R 7>(CH 2CH 2-O) mH or optionally saturated 8-24C-alkyl; R7a, R 8>optionally saturated 6-22C-alkyl; and n, m, x, y, r : 1-10. Independent claims are included for: (1) a surfactant mixture comprising (Q) and (V), where the weight ratio of (Q) and (V) is 4:1-1:4, preferably 1:1; and (2) a detergent comprising 0.1-25 wt.% of the surfactant mixture.

Description

The present invention relates to the use of selected surfactant systems to improve the cold wash properties of detergents. Furthermore, detergents containing these surfactant systems are also included.

For detergents, there is a clear trend towards lower wash temperatures on the part of consumers. Due to the high energy prices, a lowering of the temperature during washing is required. In this case, the lowest possible temperatures should be achieved, preferably water should be directly unheated from the line are suitable to achieve the usual washing performance that requires the consumer of detergents. The detergent manufacturers have already taken this trend into account by using special enzymes, soil-release polymers or new bleach activators. However, e.g. Bleach activators can only be used in powdery products or granules and their effect is limited to specific soils. Also with the enzymes one finds only a limited effect spectrum on special soiling. In addition, the enzyme activity is a function of temperature, so that at lower temperatures, especially around 20 ° C around, the effect of enzyme systems decreases significantly. In particular, lipophilic stains, e.g. Skin fat, motor oil, fats and waxes or cosmetics, there is a clear need for improvement in washing systems, which at lower temperatures, i. at temperatures below 30 ° C, preferably at temperatures of 20 ° C and less can still achieve a sufficient washing result. The per se widespread and powerful combination of alkylbenzenesulfonates sulfates with ethoxylated fatty alcohols is also not enough to solve this task completely.

Thus, there is a constant interest in the art in improving existing wash systems in terms of their cryogenic performance.

It has now been found that the combination of certain selected quaternized or nonionic surfactants with ethoxylated fatty alcohols are suitable for providing washing systems which produce a satisfactory washing result even at lower temperatures of 20 ° C. and less.

wobei R¹CO einen gesättigten oder ungesättigten, ethoxylierten Hydroxyacylrest mit 16 bis 22 C-Atomen und 1 bis 50 Ethylenoxid-Einheiten bedeutet, A für einen linearen oder verzweigten Alkylrest mit 1 bis 6 C-Atomen, R², R³, und R⁴ unabhängig voneinander einen Alkylrest mit 1 bis 4 C-Atomen, oder für ein Wasserstoffatom stehen, R⁵ einen Alkyl- oder Benzylrest bedeutet und X für Halogen, Alkylsulfat oder Alkylphosphat steht;

in der R⁶ für einen geradkettigen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 24 C-Atomen steht und R⁷ entweder für einen Rest -(CH₂CH₂-O)_mH oder für einen verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 24 C-Atomen steht, und n und m jeweils unabhängig voneinander Zahlen von 1 bis 10 bedeuten kann;

         R⁷-(CH₂CH₂-O)_x(CH₂CHCH₃-)_yH     (III)

wobei R⁷ für einen gesättigten, ungesättigten, verzweigten oder unverzeigten Alkylrest mit 6 bis 22 C-Atomen steht und x und y jeweils Werte von 1 bis 10 einnehmen kann; in Kombination mit ethoxylierten Fettalkoholen der allgemeinen Formel (IV)

         R⁸-(CH₂CH₂-O)_rH     (IV)

wobei R⁸ für einen gesättigten, ungesättigten, verzweigten oder unverzeigten Alkylrest mit 6 bis 22 C-Atomen steht, und der Index r Zahlen von 1 bis 10 bedeutet;
zur Verbesserung der Waschkraft von Waschmitteln bei Temperaturen von kleiner/gleich 30 °C, vorzugsweise kleiner/gleich 20 °C.A first subject of the present application therefore relates to the use of surfactants according to the general formulas (I), (II) and / or (III)

where R ¹ CO is a saturated or unsaturated, ethoxylated hydroxyacyl radical having 16 to 22 C atoms and 1 to 50 ethylene oxide units, A is a linear or branched alkyl radical having 1 to 6 C atoms, R ² , R ³ , and R ⁴ independently of one another are an alkyl radical having 1 to 4 C atoms, or are a hydrogen atom, R ^{5 is} an alkyl or benzyl radical and X is halogen, alkyl sulfate or alkyl phosphate;

in which R ^{6 is} a straight-chain or branched, saturated or unsaturated alkyl radical having 8 to 24 C atoms and R ^{7 is} either a radical - (CH ₂ CH ₂ -O) _m H or a branched, saturated or unsaturated alkyl radical 8 to 24 carbon atoms, and n and m each independently represent numbers from 1 to 10;

R ⁷ - (CH ₂ CH ₂ -O) _x (CH ₂ CHCH ₃ -) _y H (III)

wherein R ^{7 is} a saturated, unsaturated, branched or unbranched alkyl radical having 6 to 22 carbon atoms and x and y can each have values of 1 to 10; in combination with ethoxylated fatty alcohols of the general formula (IV)

R ⁸ - (CH ₂ CH ₂ -O) _r H (IV)

wherein R ^{8 is} a saturated, unsaturated, branched or unbranched alkyl radical having 6 to 22 carbon atoms, and the subscript r is from 1 to 10;
to improve the washing power of detergents at temperatures of less than or equal to 30 ° C, preferably less than or equal to 20 ° C.

The aim of the present invention is to provide detergents (in liquid or solid form) which have improved detergency, even at low temperatures of less than or equal to 30 ° C and especially less than or equal to 20 ° C. that such detergents preferably show the same washing results, such as detergents which contain the per se known surfactant combination of alkylbenzene sulphate (ABS) and ethoxylated fatty alcohols in a weight ratio of 1 :. The surfactant systems according to the invention thus act as so-called "boosters"; they can therefore be incorporated into existing recipes in an additive or, preferably as the sole surfactant system, replace the usual combination of ABS and fatty alcohol ethoxylates. The detergency is determined by comparing the remission of soiled test fabrics before and after the washing process.

Preferred temperature ranges in which the surfactant systems should lead to an improvement in the washing performance are in the range of less than or equal to 30 ° C. Preferably, the range of less than or equal to 30 ° C to 10 ° C, wherein the temperature range of 10 to 25 ° C and especially from 10 to less than / equal to 20 ° C is particularly preferred. A particularly preferred range is between 10 and 20 ° C.

As a reference for the surfactant systems of the invention preferably serves the mixture of dodecylbenzenesulfonate and an average of 7 ethylene oxide containing fatty alcohol having 12 to 18 carbon atoms in the ratio (w / w) of 1: 1.

The surfactant systems of the present invention give a detergent a detergency of 20 ° C which is comparable to the same detergent but which contains the reference system but whose laundering performance was measured at 60 ° C. The washing performance is defined here in particular by remission difference measurements on washed and non-washed textiles, e.g. made of cotton or polyester or mixed fabrics and different stains.

The compounds of the formula (I) are known per se, for example from the EP 0 992 488 A2 , These are quaternized amidoamines, for example prepared from ethoxylated castor oil and dimethylaminopropyl. In the EP 1 642 887 A1 Such surfactants and their use in cosmetics are described. In the EP 0 992 448 A2 is also a process for their preparation of the compounds of formula (I) described in which preferably a) castor oil and / or hydrogenated castor oil with diamines, b) the resulting amidoamines with benzyl halides or alkyl halides, sulfates or phosphates with 1 to Quaternized 4 carbon atoms, and c) the resulting quaternized products with - based on the hydroxyl groups in the acyl radical - 1 to 50 moles of ethylene oxide ethoxylated. The ethoxylation can also be carried out at the stage of amidoamines or quaternary ammonium compounds. Preferably, however, the triglycerides are placed in a stirred autoclave together with 0.5 to 2.5% by weight of catalyst (eg, sodium methylate or calcined hydrotalcite), evacuated, and added at temperatures in the range of 120 to 180 ° C within 1 to 2 h, the desired amount of ethylene oxide, preferably 5 to 10 moles of ethylene oxide - based on the hydroxyl groups in the acyl radical - on, wherein the autogenous pressure can rise to 5 bar. Then allowed to react for about 30 minutes, the reactor is cooled, relaxed and neutralized the basic catalyst z. B. by the addition of lactic acid or phosphoric acid. Optionally, insoluble catalysts are separated via a filter press. The amidation of the triglycerides can be carried out in a manner known per se. Preferably, diamines are used for this purpose. The amidation can be carried out in the presence of customary for this purpose alkaline catalysts such. For example, sodium hydroxide, Potassium hydroxide or sodium methylate; the catalyst concentration is usually 0.1 to 2 wt .-% - based on the starting materials. The concomitant use of small amounts of alkali borohydrides or hypophosphorus acid as co-catalysts is recommended when it comes to producing light-colored products as possible. The reaction temperature is 100 to 150, and preferably 120 to 140 ° C. If desired, work under nitrogen blanketing. To convert the preferably already ethoxylated amidoamines into the quaternary ammonium compounds, a condensation of the amino function with a benzyl halide, a C 1 -C 4 -alkyl halide, a C 1 -C 4 -alkyl sulfate or C 1 -C 4 -alkyl phosphate takes place. Preferably, benzyl chloride, methyl chloride or dimethyl sulfate are used. Like the ethoxylation and the amidation, the quaternization is carried out in a manner known per se, ie, the amidoamine is condensed in bulk, in aqueous or alcoholic solution with the alkylating agent at temperatures in the range of 70 to 100 ° C. The reactants are used in an approximately stoichiometric ratio, ie 1: 0.95 to 1: 1.05. It is advisable to keep the pH during the condensation by adding an aqueous base in the alkaline range and to adjust the final product by the addition of mineral acid slightly acidic. Reference is made in particular to paragraph [0040] of the EP 0 992 448 A2 , and the two manufacturing examples H1 and H2 disclosed therein, which thus also belong to the scope of disclosure of the present application.

wobei hierin R für einen Alkyl- oder Alkenylrest mit 11 Kohlenstoffatomen, R' und R" für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R''' für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen, R'''' für Wasserstoff oder eine Methylgruppe, A für eine lineare oder verzweigte Alkylengruppe mit 2 bis 6 Kohlenstoffatomen, n für Zahlen von 1 bis 25 und X für Halogen oder Alkylsulfat steht.The compounds of the formula (I) can also preferably be described by the following formula:

wherein herein R is an alkyl or alkenyl radical having 11 carbon atoms, R 'and R "are hydrogen or alkyl radicals having 1 to 4 carbon atoms, R''' is an alkyl radical having 1 to 4 carbon atoms, R '''' is hydrogen or a Methyl group, A for one linear or branched alkylene group having 2 to 6 carbon atoms, n represents numbers of 1 to 25 and X represents halogen or alkyl sulfate.

Also in the compounds according to formula (II) are known substances. Details of the structure and production are, for example, the DE 3603579 A1 , or the WO 95/27768 refer to. For the purposes of the present technical teaching, preference is given to those compounds of the formula (II) in which R ^{7 is} a radical - (CH ₂ CH ₂ -O) _m H and m can be from 1 to 10.

The same applies to the fatty alcohol alkoxylates according to the formulas (III) and (IV). Particularly preferred is the use of ethoxylated fatty alcohols gem. of the formula (IV) in which R ^{8 is} a linear, saturated alkyl radical having 12 to 18 carbon atoms and the index r has a value of 4 to 8.

Preference is furthermore given to the use of surfactants of the formula (III), where those are selected in which R ^{7 is} an alkyl radical having 10 to 16 C atoms and the index x is a number from 4 to 8 and y is a number from 1 to 3 stands. A further preferred embodiment of the present technical teaching relates to the use of at least one surfactant gem. of the formula (I) and at least one surfactant of the formula (II) or (III) side by side and in each case in combination with a surfactant gem. of the formula (IV), wherein the weight ratio among the surfactants of the formula (I) and (II) or (III) is preferably in the range of 3: 1 to 1: 3, and more preferably 2: 1 to 1: 2, and more preferably at 1: 1.

It may likewise be preferred to use surfactants of the formulas (I) to (III) in a weight ratio of 1: 4 to 4: 1 and in particular of 1: 2 to 2: 1 to the alkoxylated fatty alcohols of the formula (IV). Furthermore, it is possible and preferred that the surfactants of the formulas (I) to (IV) are used together with further structurally different surfactants.

As further surface-active substances, it is possible structurally to contain different nonionic, anionic, cationic and / or amphoteric or amphoteric surfactants compared to the compounds of the general formulas (I) to (IV).

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable based wheat products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (in particular vegetable products Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

The surfactant systems described in the context of the present technical teaching are suitable for use in solid, liquid or gel-form detergents, wherein the It is possible to use surfactant systems in amounts of from 0.1 to 25% by weight, based on the total detergent. Preferred amounts of the surfactant system are from 1 to 20% by weight and 5 to 15% by weight. In addition to the surfactant system according to the invention, it is also possible for further structurally different surfactants to be present in the detergents. The total amount (surfactant system plus other surfactants) can vary from 5 to 60 weight percent.

Liquid detergents may have a non-aqueous content in the range of 5 to 50% by weight and preferably 10 to 50% by weight, in particular 15 to 35% by weight. Preferably, they contain water, in particular in amounts of 10 to 90 wt .-%, preferably 20 to 80 wt .-% and especially 25 to 65 wt .-%. In the simplest case, these are aqueous solutions of said surfactant mixtures.

However, the liquid detergents may also be substantially anhydrous agents. In this context, "essentially anhydrous" in the context of this invention means that the agent preferably contains no free water, not bound as water of crystallization or in comparable form. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight.

In addition to the surfactants of the surfactant system according to the invention and optionally other structurally different surfactants, the liquid detergents may contain further typical ingredients such as solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrance - And dyes, provided that they are sufficiently stable in the aqueous environment. Suitable organic solvents are, for example, monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof. The compositions preferably contain from 2 to 20% by weight and in particular from 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or, in particular, of ethanol and glycerol. It is also possible that the preparations either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or polyethylene glycol alone having a molecular weight between 200 and 2000, preferably to 600 in amounts of 2 to 17 wt .-%. As hydrotrope, for example, toluene sulfonate, xylene sulfonate, cumene sulfonate or mixtures thereof can be used. Among the compounds serving as bleaches, which yield hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxycarbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25 wt .-%. Preference is given to the use of sodium perborate monohydrate in amounts of from 10 to 20% by weight and in particular from 10 to 15% by weight. Its ability to bind free water to form tetrahydrate contributes to increasing the stability of the agent. Preferably, however, the preparations are free of such bleaching agents.

Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, e.g. the neutral reacting sodium salts of 1-hydroxyethane-1,1-diphosphonate, which may be present in amounts of 0.5 to 5, preferably 1 to 2 wt .-%.

As viscosity regulators, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5 wt .-% and in particular in amounts of 0.5 to 2 wt .-%, for example, sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and especially copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1000 and 100,000, those of the copolymers between 2000 and 200,000, preferably between 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a molecular weight of more than one million are also suitable. Examples of these are the thickening polymers available under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight. The agents may additionally contain about 5 to 20% by weight of a partially esterified copolymer. These partially esterified polymers are prepared by copolymerization of (a) at least one C ₄ -C ₂₈ olefin or mixtures of at least one C ₄ -C ₂₈ olefin with up to 20 mol% C ₁ -C ₂₈ alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic anhydrides having 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers having K values of 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C ₁ -C ₁₃ -alcohols, C ₈ -C ₂₂ -fatty acids, C ₁ -C ₁₂ alkylphenols, secondary C ₂ -C ₃₀ amines or mixtures thereof with at least one C ₂ -C ₄ alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, wherein the partial esterification of the copolymers is carried out so far that 5 to 50% of the carboxyl groups of the copolymers are esterified. Preferred copolymers contain ethylenically unsaturated dicarboxylic anhydride maleic anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. Advantageously, the copolymers are used in the form of an aqueous solution, in particular in the form of a 40 to 50 wt .-% solution. The copolymers not only make a contribution to the primary and secondary washing performance of the liquid detergent and cleaning agent, but also cause a desired viscosity reduction of the concentrated liquid detergent. By using these partially esterified copolymers concentrated aqueous liquid detergents are obtained, which are flowable under the sole influence of gravity and without the action of other shear forces. Preferably, the concentrated aqueous liquid detergents contain partially esterified copolymers in amounts of 5 to 15 wt .-% and in particular in amounts of 8 to 12 wt .-%.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases, glycosidases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Their proportion can be about 0.2 to about 2 wt .-%. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents may contain other enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, it is particularly advantageous to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ ).

Suitable soil repellent polymers are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5,000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure. Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc). Another preferred copolymer is in EP 1767554 described.

When used in automatic washing processes, it may be advantageous to add the usual auxiliaries and additives to the means. For this purpose, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-type foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

The pH of the agents is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. The setting of higher pH values, for example above 9, can be achieved by using small amounts of caustic soda or alkaline salts such as sodium carbonate or sodium silicate. The liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Bmokfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). In this case, viscosities of between 150 and 5000 mPas are preferred for the substantially anhydrous agents. The viscosity of the aqueous compositions is preferably below 2000 mPas and is in particular between 150 and 1000 mPas.

If the surfactant mixtures according to the invention are used for the preparation of solid, preferably powder detergents, the surfactants mentioned above and, moreover, the surfactant system according to the invention may contain further typical ingredients such as builders, bleaches, bleach activators, detergency boosters, enzymes, enzyme stabilizers, grayness inhibitors, optical agents Brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and dyes.

As a solid builder in particular fine-crystalline, synthetic and bound water-containing zeolite such as zeolite NaA is used in detergent quality. Also suitable, however, are zeolite NaX and mixtures of NaA and NaX. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22 wt .-% of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 is and preferred values for x are 2, 3 or 4. The powder detergents according to the invention preferably contain from 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, with mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain from 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the compositions are water-soluble amorphous silicates; Preferably, they are used in combination with zeolite and / or crystalline layer silicates. Particular preference is given to agents which contain, above all, sodium silicate with a molar ratio (modulus) of Na ₂ O: SiO _{2 of} from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content of the amorphous sodium silicate compositions is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates may also be present in small amounts in the compositions be. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the compositions may additionally contain phyllosilicates of natural and synthetic origin. Useful organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof , Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is generally from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which biodegradable polymers, for example terpolymers containing as monomers acrylic acid and maleic acid or salts thereof and vinyl alcohol or vinyl alcohol derivatives or as monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof and sugar derivatives. Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples thereof are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate. The content of the bleach-containing agents in bleach activators is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Graying inhibitors have the task of keeping suspended from the fiber debris suspended in the fleet and thus to prevent graying. Water-soluble colloids of mostly organic nature are suitable for this purpose, 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. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof and polyvinylpyrrolidone, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted diphenylstyrene may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brightener can be used. Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example 10 ^-6 to 10 ^-3 wt .-%, preferably by 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).

Solid detergents also include pressed-form detergents, e.g. as a tablet or similar forms.

1. (a) mindestens ein Tensid gemäß der allgemeinen Formeln (I), (II) oder (III) und
2. (b) mindestens ein Tensid der allgemeinen Formel (IV),

wobei das Gewichtsverhältnis zwischen (a) und (b) im Bereich von 4 : 1 bis 1 : 4, vorzugsweise von 2 : 1 bis 1 : 2 und insbesondere 1 : 1 liegt.Another object of the present teaching relates to containing surfactant mixtures

1. (A) at least one surfactant according to the general formulas (I), (II) or (III) and
2. (b) at least one surfactant of the general formula (IV),

wherein the weight ratio between (a) and (b) is in the range from 4: 1 to 1: 4, preferably from 2: 1 to 1: 2 and especially 1: 1.

The surfactant systems are generally prepared by simple mixing, if necessary with stirring.

Furthermore, a detergent is claimed that a surfactant mixture gem. the above description (ie the sum of ingredients a) and b)) in amounts of 0.1 to 35 wt .-%. Preferably, these detergents contain the surfactant mixtures in amounts of 5 to 25 wt .-%. The detergent may be solid or liquid, or gel. Gels are generally dimensionally stable, easily deformable, liquid-rich, disperse systems of at least two components, usually composed of a solid, colloidally divided substance with long or highly branched particles (eg gelatin, silicic acid, montmorillonite, bentonites, polysaccharides, pectins, special polymers, such as polyacrylates, and other gelling agents, often referred to as thickeners) and a liquid (usually water) as a dispersing agent. In this case, the solid substance is coherent, ie it forms a spatial network in the dispersion medium, wherein the particles stick together by secondary or major valences at different points (adhesion points).

In general, the application relates to the use of surfactant mixtures gem. the above description as detergent boosters for detergents at temperatures of 20 ° C and less. The surfactant systems can also be used for the preparation of cold wash detergents, cold wash detergents being understood to mean those solid, liquid or gel-form detergents which have a detergency at temperatures of less than or equal to 30 ° C., preferably less than or equal to 20 ° C. such as detergents which contain a mixture of dodecylbenzenesulfonate and an average of 7 ethylene oxide units containing fatty alcohol having 12 to 18 carbon atoms in the ratio (w / w) of 1: 1 and which are used at 60 ° C.

Examples

There were 4 different detergents containing surfactants of the invention (E1 to E4) prepared according to the information in Table 1. The detergency of these systems was compared to the reference recipe (V1) determined by measuring the emission of the individual washed test monitors. Reference system V1 was a 1: 1 mixture of an alkylbenzenesulfonate and fatty alcohol ethoxylate

Maranil^® A 55

Dodecylbenzolsulfonat

Dehydol^® LT 7

Fettalkohol C12/C18 mit 7 EO

Dehyquart^® HPD

quaterinsiertes Amidoamin aus ethoxylierten Ricinusöl und dimethylaminopropylamin gemäß Formel (I).

Dehyquart^® AU 39

Mischung aus Dehyquart HPD und Eumulgin PA 12 (1:1 w/w)

Dehydol^® 980

Fettalkohol C10/C16, ethoxyliert und propoxyliert gemäß Formel (III)

Eumulgin^® PA 12

Fettalkoholamin (ethoxyliert mit 12 EO), gemäß Formel (II)

Tabelle 1 (alle Mengenangaben in Gew.-% Aktivsubstanz): Produkt V1 E1 E2 E3 E4 Maranil A 55 10 Dehydol LT 7 10 10 10 10 10 Dehyquart AU 39 10 Dehyquart HPD 10 Dehydol 980 10 Eumulgin PA 12 10 Seife 9 9 9 9 9 NaOH (50 %ig) 3,4 3,4 3,4 3,4 3,4 Propylenglykol 5 5 5 5 5 Ethanol 3 3 3 3 3 Borax 20 %ig 0,2 0,2 0,2 0,2 0,2 Enzyme¹ 1 1 1 1 1 Zitronensäure 3 3 3 3 3 Wasser Rest auf 100 % Rest auf 100 % Rest auf 100 % Rest auf 100 % Rest auf 100 % Protease und Lipase The names in the table stand for the following substances:

Maranil ^® A 55

dodecylbenzenesulfonate

Dehydol ^® LT 7

Fatty alcohol C12 / C18 with 7 EO

Dehyquart® ^® HPD

quaterated amidoamine of ethoxylated castor oil and dimethylaminopropylamine according to formula (I).

Dehyquart ^® AU 39

Mixture of Dehyquart HPD and Eumulgin PA 12 (1: 1 w / w)

Dehydrol® ^® 980

Fatty alcohol C10 / C16, ethoxylated and propoxylated according to formula (III)

Eumulgin ^® PA 12

Fatty alcoholamine (ethoxylated with 12 EO), according to formula (II)

<u> Table 1 (all amounts in wt .-% active substance): </ u> product V1 E1 E2 E3 E4 Maranil A 55 10 Dehydrol LT 7 10 10 10 10 10 Dehyquart AU 39 10 Dehyquart HPD 10 Dehydol 980 10 Eumulgin PA 12 10 Soap 9 9 9 9 9 NaOH (50%) 3.4 3.4 3.4 3.4 3.4 propylene glycol 5 5 5 5 5 ethanol 3 3 3 3 3 Borax 20% 0.2 0.2 0.2 0.2 0.2 Enzymes ¹ 1 1 1 1 1 citric acid 3 3 3 3 3 water Rest on 100% Rest on 100% Rest on 100% Rest on 100% Rest on 100% Protease and lipase

The results of the detergency measurements are shown in Tables 2a and 2b. Since different qualities of the test fabric were used, the values are divided into two blocks a) and b).

The investigation was carried out in a household washing machine of the type Bauknecht WAK 9660. With standardized artificial soiling of the WFK; CFT and EMPA. 17 different monitors of size 10x10cm were sewn onto a carrier fabric made of cotton size 50x60.

Two of these test sets were washed together with a 3.5 kg load of clean accompanying laundry consisting of terry toweling, barley grain towels, pillows and undershirts. The detergent to be tested was added at 75 g; The water hardness was 16 ° d. It was ensured that the incoming water had a temperature <20 ° C. At the end of the washing program, which ended with a sling step, the test sets were dried by mangling. The individual test monitors were equipped with a Minolta Chromameter ^® CR 300 in the Y; x; measure the mode. As a measure of the washing power, the brightness Y was used.

The numerical values of Tables 2a and 2b are not directly comparable with each other. The reference system was reassessed in both test series with the associated test tissue quality. <u> Table 2a (all figures in% remission) </ u> soiling V1 E1 E2 20 ° C 60 ° C 20 ° C 20 ° C Chlorophyll / vegetable oil (PE) 59 58 74 75 Lipstick (PE) 26 37 33 25 Pigment / oil (PE) 60 64 76 68 Skin fat / soot (CO) 38 38 40 41 Skin fat / soot (CO / PE) 36 37 36 35 Pigment / wool fat (PE) 56 72 62 41 soiling V1 E3 E4 20 ° C 20 ° C 20 ° C Chlorophyll / vegetable oil (PE) 58 64 71 Pigment / oil (PE) 60 58 61 Skin fat / soot (CO) 39 31 35 Skin fat / soot (CO / PE) 36 31 34 PE polyester fabric, CO = cotton fabric

It turns out that the surfactant mixtures according to the invention have comparable to better values of the washing performance at 20 ° C., compared with the standard at 60 ° C.

Claims (10)

Use of surfactants according to the general formulas (I), (II) and / or (III)

where R ¹ CO is a saturated or unsaturated, ethoxylated hydroxyacyl radical having 16 to 22 C atoms and 1 to 50 ethylene oxide units, A is a linear or branched alkyl radical having 1 to 6 C atoms, R ² , R ³ , and R ⁴ independently of one another are an alkyl radical having 1 to 4 C atoms, or are a hydrogen atom, R5 is an alkyl or benzyl radical and X is halogen, alkyl sulfate or alkyl phosphate;

in which R ^{6 is} a straight-chain or branched, saturated or unsaturated alkyl radical having 8 to 24 C atoms and R ^{7 is} either a radical - (CH ₂ CH ₂ -O) _m H or a branched, saturated or unsaturated alkyl radical 8 to 24 carbon atoms, and n and m each independently represent numbers from 1 to 10;

R ⁷ - (CH ₂ CH ₂ -O) _x (CH ₂ CHCH ₃ -O) _y H (III)

wherein R ^{7 is} a saturated, unsaturated, branched or unbranched alkyl radical having 6 to 22 carbon atoms and x and y can each have values of 1 to 10;
in combination with ethoxylated fatty alcohols of the general formula (IV)

R ⁸ - (CH ₂ CH ₂ -O) _r H (IV)

wherein R ^{8 is} a saturated, unsaturated, branched or unbranched alkyl radical having 6 to 22 carbon atoms, and the subscript r is from 1 to 10;
to improve the washing power of detergents at temperatures of less than or equal to 30 ° C, preferably less than or equal to 20 ° C. Use according to claim 1, characterized in that an ethoxylated fatty alcohol according to formula (IV) is used, in which R ^{8 is} a linear, saturated alkyl radical having 12 to 18 carbon atoms, and the index r assumes values of 4 to 8 , Use according to at least one of claims 1 or 2, characterized in that the surfactants of the formula (III) are selected from those in which R ^{7 is} an alkyl radical having 10 to 16 carbon atoms, and x is a number from 4 to 8 and y is a number from 1 to 3. Use according to at least one of claims 1 to 3, characterized in that at least one surfactant according to formula (I) and at least one surfactant according to formula (II) or (III) must be present side by side, wherein the weight ratio between the surfactants of the formulas (I) and (II) or (III) is preferably in the range of 2: 1 to 1: 2, and more preferably 1: 1. Use according to at least one of Claims 1 to 4, characterized in that the surfactants of the formulas (I), (II) and / or (III) have a weight ratio to the alkoxylated fatty alcohols of the formula (IV) of from 1: 4 to 4: 1 exhibit. Use according to at least one of claims 1 to 5, characterized in that in addition to at least one of the surfactants of the formulas (I) to (IV) further structurally different anionic, nonionic and / or amphoteric surfactants are used. Use according to at least one of claims 1 to 6, characterized in that the surfactants or their mixtures in solid, liquid or gel detergent, preferably in amounts of 0.1 to 25 wt .-% are used. Containing surfactant mixture (A) at least one surfactant according to the general formulas (I), (II) or (III) and (b) at least one surfactant of the general formula (IV), wherein the weight ratio between (a) and (b) in the range of 4: 1 to 1: 4, preferably from 2: 1 to 1: 2 and in particular 1: 1. Detergent containing a surfactant mixture according to claim 8 in amounts of 0, 1 to 25 wt .-%. Use of surfactant mixtures according to claim 8 as detergency booster for detergents at temperatures of 20 ° C and less.