EP0647260B1 - Washing and cleaning agents in liquid to paste form - Google Patents

Abstract

Described are liquid to pasty washing and cleaning agents containing anionic or anionic and non-ionic surfactants in quantities from 20 to 70 % by wt., and including as anionic surfactants 2 to 25 % by wt. of sulphonated fatty-acid glycerin esters. Such washing and cleaning agents suffer no loss in washing performance compared with liquid to pasty washing- and cleaning-agent formulations usually containing surfactants. The invention enables alkylbenzene sulphonates to be completely or at least partly replaced. Preferred agents contain as anionic surfactants a mixture of sulphonated fatty-acid glycerin esters, fatty-alkyl sulphate and fatty-acid soaps or a mixture of sulphonated fatty-acid glycerin esters, alkane sulphonate and fatty-acid soaps.

Description

The invention relates to a washing and cleaning agent in liquid to pasty form which contains anionic surfactants which consist entirely or at least to a large extent of oleochemical and thus renewable raw materials.

The use of oleochemical surfactant compounds, which are obtained from renewable vegetable and / or animal raw materials and which have high ecological compatibility, is of great and rapidly increasing importance. Examples of such oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which are produced by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular the corresponding alkali metal salts, and the known α-sulfofatty acid alkyl esters (ester sulfonates), which are prepared by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in particular the corresponding alkali salts , and their disalts obtainable by hydrolysis.

Examples of further oleochemical surfactant compounds are sulfated fatty acid glycerol esters, for example sulfated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.

The anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates. A disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials.

It was therefore the task of creating a detergent in liquid to pasty form which contains anionic surfactants which either consist entirely or at least to a large extent of native, that is to say renewable, fat-chemical raw materials. These anionic surfactants are said to be able to completely or at least partially replace alkylbenzenesulfonates in otherwise customary detergent and cleaning agent formulations without sacrificing washing performance.

The invention accordingly relates to a washing and cleaning agent in liquid to pasty form which contains anionic and nonionic surfactants, the surfactant content of the agent being 20 to 70% by weight, and sulfated fatty acid glycerol esters in amounts of 2 to 25 as anionic surfactants Wt .-% are included and the medium nonionic surfactants in amounts of 10 to 65 wt .-%.

Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. If one starts from fats and oils, that is, natural mixtures of different fatty acid glycerol esters, their fatty acid components usually build up partly from saturated and partly from unsaturated fatty acids. Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, lard or rape oil rich in oleic acid. The sulfonation can take place in accordance with international patent application W0 91/6532.

However, preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one again starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, that is to say iodine numbers less than 5, advantageously Harden less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO 91/9009 is specified.

The sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure. In the context of this invention, sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active constituents, but without aqueous components.

The total surfactant content of the compositions is preferably 25 to 65% by weight and, in particular, concentrated liquid to pasty compositions which have at least 30% by weight of anionic and nonionic surfactants are preferred. The agents preferably contain 5 to 20% by weight of sulfonated fatty acid glycerol esters, in particular fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, 10 to 65% by weight of nonionic surfactants as prescribed, and preferably further anionic surfactants, for example alkyl sulfates , preferably fatty alkyl sulfates, alkane sulfonates, soaps or mixtures thereof. The agents can also contain small amounts of alkylbenzenesulfonates, for example about 1 to 5% by weight of alkylbenzenesulfonate; especially preferred detergents and cleaning agents in liquid to pasty form are, however, free of alkylbenzenesulfonates.

The anionic surfactants used are preferably alkali metal salts, in particular sodium or potassium salts. The anionic surfactants used in addition to the sulfonated fatty acid glycerol esters are preferably surfactants from the class of the sulfonates and sulfates.

Particularly suitable sulfonates are sulfonates based on oleochemistry, such as the esters of α-sulfo fatty acids, the sulfo group being in its salt form (mono salt), for example the α-sulfonated methyl esters, the hydrogenated coconut, palm kernel or tallow fatty acids. Also suitable are the readily biodegradable alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating. A disadvantage of alkanesulfonates, however, is that they are obtained from petrochemical raw materials. Their proportion in the liquid to pasty washing and cleaning agents according to the invention is therefore preferably not more than about 5 to 15% by weight. It has been found that agents which contain mixtures of alkanesulfonates and sulfonated fatty acid glycerol esters, the proportion of sulfated fatty acid glycerol esters in these mixtures being 10 to 80% by weight, have no loss in washing performance compared to only alkanesulfonate-containing mixtures. Depending on the recipe, it is even possible to replace alkane sulfonates as a whole with sulfated fatty acid glycerol esters without having to accept any loss in washing performance. The same applies analogously to the above-mentioned alkylbenzenesulfonates and mixtures of alkylbenzenesulfonates and sulfonated fatty acid glycerol esters.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols. Suitable fatty alkyl sulfates are the sulfuric acid monoesters of the C ₁₂ -C ₁₈ fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and those obtained from coconut oil, palm and palm kernel oil Fatty alcohol mixtures, which may also contain proportions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C ₁₂ , 18 to 30% by weight on C ₁₄ , 5 to 15% by weight on C ₁₆ , are preferred 3% by weight on C ₁₀ and less than 10% by weight on C _{18 are} distributed. The proportion of fatty alkyl sulfates in the compositions is preferably 1 to 20% by weight and in particular 3 to 15% by weight.

Further preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are particularly preferred.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 3 to 25% by weight, in particular in amounts of 5 to 20% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The salts of saturated and unsaturated fatty acids with C ₁₂ -C ₁₈ chain lengths in the form of their mixtures are particularly suitable. A preferably used soap mixture is formed from sodium oleate and the sodium salts of the saturated C ₁₂ -C ₁₆ fatty acid mixtures. The proportion of C ₁₂ -C ₁₄ fatty acids in the saturated component is advantageously at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the portions with 10 or fewer carbon atoms are largely separated. As usual with technical fatty acid cuts, the oleic acid and the Coconut fatty acid still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should be at most 25% by weight, preferably less than 20% by weight. A soap mixture of sodium oleate and the sodium salt of lauric acid is also preferred. The weight ratio of the unsaturated to the saturated component is preferably 2: 1 to 1: 2.

Particularly preferred detergents and cleaning agents in liquid to pasty form contain 15 to 35% by weight of a mixture of sulfated fatty acid glycerol esters and other anionic surfactants in a weight ratio of 1: 3 to 3: 1. In particular, anionic surfactant mixtures which contain sulfated fatty acid glycerol esters, fatty alkyl sulfates are preferred and fatty acid soaps or sulfated fatty acid glycerol esters, alkane sulfonates and fatty acid soaps.

The preferred nonionic surfactants are liquid ethoxylated and / or propoxylated, preferably ethoxylated fatty alcohols, in particular primary alcohols preferably having 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or in 2-position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 EO. The preferred ethoxylated alcohols include, for example, in particular C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO.

The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE). The content of liquid nonionic surfactants in the agents according to the invention is preferably 15 to 65% by weight.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position and G denotes the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. The content of alkyl glycosides in the agents according to the invention is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight.

The washing and cleaning agents according to the invention can contain, as organic solvents, mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms, preferably with 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof. The compositions preferably contain 2 to 20% by weight and in particular 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 detergents and cleaning agents according to the invention in liquid to pasty form either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or alone polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600 in amounts contain from 2 to 17 wt .-%.

The washing and cleaning agents according to the invention in liquid to pasty form can be aqueous or essentially water-free agents. In the context of this invention, "essentially anhydrous" means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form. In some cases, small amounts of free water are tolerable, especially in amounts up to 5% by weight. Preferred essentially water-free detergents and cleaning agents in liquid to pasty form contain 20 to 65% by weight of liquid nonionic surfactants and water in amounts of 0 to 5% by weight. The anionic surfactants mentioned and, for example, bleaches, thickeners, builders, inorganic salts, foam inhibitors, enzymes, optical brighteners, and colorants can be used as further ingredients Fragrances may be included, as described, for example, in international patent application WO 92/2610. Among the compounds used as peroxy bleaching agents and providing H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H ₂ O ₂ -producing peracid salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. Examples of thickeners which can be used are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, 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 in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of these are the polymers obtainable under the name Carbopol ^(R) 940 and 941. The crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.

The water-containing liquid to pasty washing and cleaning agents are preferably free of peroxy bleaching agents. They preferably contain 10 to 35% by weight of nonionic surfactants and 20 to 55% by weight and in particular 25 to 45% by weight of water. In a preferred embodiment, liquid to pasty agents contain 10 to 20% by weight of ethoxylated fatty alcohols, preferably a primary C ₁₂ -C ₁₈ fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are liquid to pasty concentrates containing 20 to 35% by weight of nonionic surfactants, in particular 22 to 32% by weight of a primary C ₁₂ -C ₁₈ fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of fatty alcohol, 28 to Contains 40 wt .-% water and 5 to 17 wt .-% mono- and / or polyfunctional alcohols with 2 to 4 carbon atoms. The agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application 367 049. These partially esterified polymers are obtained by copolymerizing (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% of C ₁ -C ₂₈ alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 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, the partial esterification of the copolymers being carried out to the extent that 5 to 50% of the carboxyl groups of the copolymers are esterified. Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic acid anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. The copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution. The copolymers not only contribute to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent. The use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces. Preferably the concentrated ones include aqueous liquid detergents partially esterified copolymers in amounts of 5 to 15 wt .-% and in particular in amounts of 8 to 12 wt .-%.

The pH of the concentrated agents according to the invention, which are particularly preferred, is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate. The washing and cleaning agents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities between 150 and 5000 mPas are preferred for the essentially water-free agents. The viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas.

In addition to the ingredients mentioned, the aqueous compositions can contain known additives commonly used in detergents and cleaning agents, for example salts of polycarboxylic acids, for example citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, Contain opacifiers or pearlescent agents.

The salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate in amounts of 0.1 to 1.5% by weight.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight 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, the use of 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 pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes. As mentioned above, the use of sulfonated unsaturated fatty acid glycerol esters is also preferred.

Examples

Production of sulfated saturated fatty acid glycerol esters with iodine numbers less than 5.

In a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO ₃ gassing, about 5 mol of a fatty acid glycerol ester with an iodine number less than 5 (see Table 1) at 80 ° C with about 15 moles of gaseous sulfur trioxide reacted. The fatty acid glycerol ester was sprayed into the reactor through a nozzle with an opening of 0.2 cm in such a way that the starting material formed a continuous fine film with a layer thickness of less than 0.1 cm along the tube wall. The sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head. After leaving the sulfonation reactor, the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes. The acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution. Table 1: Average composition of the fatty acid glycerol esters used after curing, in% by weight fatty acid HK HPK Caproic acid 1 1 Caprylic acid 8th 4th Capric acid 7 5 Lauric acid 48 50 Myristic acid 17th 15 Palmitic acid 9 7 Stearic acid 10th 18th Iodine number 2nd 2nd Legend: HK = hardened coconut oil
HPK = hardened palm kernel oil

Waschprogramm:

Buntwaschprogramm (ohne Vorwäsche) bei 40 °C

Dosierung:

180 g oder 200 g pro Maschine

Wasserhärte:

16 °d

Textilproben:

3,5 kg saubere Füllwäsche (normale Haushaltswäsche)

Bestimmungen:

3fach

Meßtechnische Bedingungen:

künstliche Anschmutzungen:

RFC 3/24 (465 nm, Ausblendung des Aufheller-Effektes)

natürliche Anschmutzungen:

Lange-Gerät (Y-Filter)

Remissionsunterschiede von 2 % und mehr sind als signifikant anzusehen.The following examples describe the tests carried out to test the washing power of the detergents according to the invention in a household washing machine (type: Miele W 717) under the following conditions:

Washing program:

Color wash program (without prewash) at 40 ° C

Dosage:

180 g or 200 g per machine

Water hardness:

16 ° d

Textile samples:

3.5 kg clean filling laundry (normal household laundry)

Regulations:

3 times

Measurement conditions:

artificial soiling:

RFC 3/24 (465 nm, suppression of the brightener effect)

natural soiling:

Lange device (Y filter)

Differences in remission of 2% and more can be regarded as significant.

SW-B

Staub-Wollfett auf Baumwolle

SH-BV

Staub-Hautfett auf veredelter Baumwolle

SH-P

Staub-Hautfett auf Polyester

SH-PBV

Staub-Hautfett auf einem Gemisch aus Polyester und veredelter Baumwolle

BMR-B

Blut, Milch und Ruß auf Baumwolle

R-BV

Rotwein auf veredelter Baumwolle

T-BV

Tee auf veredelter Baumwolle

LS-PBV

Lippenstift auf einem Gemisch aus Polyester und veredelter Baumwolle

MU-PBV

Make-up auf einem Gemisch aus Polyester und veredelter Baumwolle

The stains were:

SW-B

Dust-wool grease on cotton

SH-BV

Dust-skin fat on refined cotton

SH-P

Dust skin grease on polyester

SH-PBV

Dusty skin fat on a mixture of polyester and refined cotton

BMR-B

Blood, milk and soot on cotton

R-BV

Red wine on refined cotton

T-BV

Tea on refined cotton

LS-PBV

Lipstick on a mixture of polyester and refined cotton

MU-PBV

Make-up on a mixture of polyester and refined cotton

The basic compositions of the aqueous liquid detergents were (data in% by weight): M1 M2 13.0 "Anionic surfactant" 5.0 15.0 "Non-ionic surfactant" 12.0 6.0 Oleic acid soap, technical 7.0 7.0 Coconut fatty acid soap 8.0 5.0 Triethanolamine --- 0.5 Citric acid (calculated as free acid) 0.5 7.0 Ethanol 7.0 5.0 Glycerin 5.0 rest water rest

• M1/V, M1/3 und M2/V    C₉-C₁₃-Alkylbenzolsulfonat
• M1/1 und M2/1    sulfiertes HK
• M1/2 und M2/2    sulfiertes HPK

und "Niotensid" in

• M1/V, M1/1, M1/2, M2/V, M2/1 und M2/2    C₁₂-C₁₈-Fettalkohol mit 7 EO
• M1/3    eine Mischung aus C₁₂-C₁₈-Fettalkohol mit 7 EO und sulfiertem HK im Gewichtsverhältnis 1 : 1

"Anionic surfactant" means in

• M1 / V, M1 / 3 and M2 / V C ₉ -C ₁₃ alkylbenzenesulfonate
• M1 / 1 and M2 / 1 sulfated HK
• M1 / 2 and M2 / 2 sulfated HPK

and "nonionic surfactant" in

• M1 / V, M1 / 1, M1 / 2, M2 / V, M2 / 1 and M2 / 2 C ₁₂ -C ₁₈ fatty alcohol with 7 EO
• M1 / 3 a mixture of C ₁₂ -C ₁₈ fatty alcohol with 7 EO and sulfated HK in a weight ratio of 1: 1

Example 1:

The agents M1 / V, M1 / 1 and M1 / 2 were tested against each other at a dosage of 180 g per machine. The results are shown in Table 2. Table 2 medium % Remission when soiled SW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU / PBV M1 / V 57.2 76.1 69.1 72.4 42.2 39.1 38.6 68.3 M1 / 1 58.1 76.3 68.8 73.4 43.7 39.9 38.9 68.8 M1 / 2 58.6 77.4 68.5 71.9 43.5 41.8 42.7 70.1

Example 2:

The agents M2 / V, M2 / 1 and M2 / 2 were tested against each other at a dosage of 180 g per machine. The results are shown in Table 3. Table 3: medium % Remission when soiled SW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU / PBV M2 / V 54.1 74.9 66.8 70.1 48.9 49.6 37.1 69.4 M2 / 1 57.4 76.1 68.0 71.5 48.6 48.1 37.6 69.4 M2 / 2 58.1 73.6 68.1 71.1 48.5 51.6 43.1 69.5

Example 3:

The agents M1 / V and M1 / 3 were tested after storage for 6 weeks at 40 ° C. The results are summarized in Table 4. It is shown that a partial replacement of conventional nonionic surfactants (50%) by sulfonated fatty acid glycerol esters is possible without having to accept a reduction in washing performance. The effects were sometimes even greater in the launderometer: here, in some cases, even the full replacement of the nonionic surfactants with sulfated fatty acid glycerol esters led to detergents that had an equally good to sometimes slightly better detergency. Table 4: Machine tests after 6 weeks storage at 40 ° C medium % Remission when soiled SW-B SH-P T-BV LS-PBV MU-PBV BMR-B M1 / V 58.2 68.2 38.2 42.3 67.7 31.7 M1 / 3 56.5 67.1 39.6 41.5 64.3 31.7

Claims (11)

1. A detergent in liquid to paste-like form containing anionic and nonionic surfactants, characterized in that the surfactant content of the detergent is 20 to 70% by weight, sulfonated fatty acid glycerol esters being present as anionic surfactants in quantities of 2 to 25% by weight and nonionic surfactants being present in quantities of 10 to 65 % by weight.
2. A detergent as claimed in claim 1, characterized in that it contains 5 to 20% by weight of sulfonated fatty acid glycerol esters obtained from fatty acid glycerol esters with iodine values below 5, preferably from mono-, di- and triglycerides or mixtures thereof with iodine value below 5, which contain fatty acids with 6 to 22 carbon atoms, by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases.
3. A detergent as claimed in any of claims 1 or 2, characterized in that it contains mono- and/or polyhydric alcohols with 1 to 6 carbon atoms in quantities of 2 to 20% by weight and preferably 5 to 15% by weight as organic solvents. 3
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains 20 to 65% by weight of liquid nonionic surfactants and water in quantities of 0 to 5% by weight.
5. A detergent as claimed in any of claims 1 to 3, characterized in that it contains 10 to 35% by weight and preferably 20 to 35% by weight of nonionic surfactants and 20 to 55% by weight, preferably 25 to 45% by weight and more preferably 28 to 40% by weight of water.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it is free from alkylbenzenesulfonates.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains alkylsulfates, preferably fatty alkylsulfates, alkanesulfonates, soap or mixtures thereof as further anionic surfactants.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains 0.5 to 8% by weight and preferably 1 to 5% by weight of alkyl glycoside.
9. A detergent as claimed in any of claims 1 to 3 and 5 to 8, characterized in that it contains 15 to 35% by weight of a mixture of sulfonated fatty acid glycerol esters and other anionic surfactants, more particularly soap, in a ratio by weight of 1:3 to 3:1 and 10 to 20% by weight of a primary C_12-18 fatty alcohol containing on average 1 to 12 moles of ethylene oxide.
10. A detergent as claimed in any of claims 1 to 3 and 5 to 8, characterized in that it contains 15 to 35% by weight of a mixture of sulfonated fatty acid glycerol esters and other anionic surfactants in a ratio by weight of 1:3 to 3:1, 22 to 32% by weight of a primary C_12-18 fatty alcohol containing on average 1 to 12 moles of ethylene oxide and 5 to 17% by weight of monohydric and/or polyhydric alcohols containing 2 to 4 carbon atoms.
11. A detergent as claimed in claim 9 or 10, characterized in that it contains a mixture of sulfonated fatty acid glycerol esters, fatty alkylsulfate and fatty acid soaps or a mixture of sulfonated fatty acid glycerol esters, alkanesulfonate and fatty acid soaps as anionic surfactants.