EP0158203A2 - Washing agent - Google Patents

Abstract

Washing agents with controlled foaming and a phosphate content not exceeding 35 % by weight, preferably not exceeding 25 % by weight, contain 3 to 15 % by weight of a non-ionic surfactant combination consisting of three different alkylaromatic polyethylene glycol ether derivatives which contain 8 to 10 carbon atoms in the alkyl radical and contain 1 to 4, 4 to 7 and 7 to 12 ethylene glycol ether groups respectively. The ratio of the less ethoxylated to the more ethoxylated polyglycol ether derivative in each case is 1 : 1 to 1 :8. A further 85 to 97 % by weight is composed of customary washing agent ingredients which may be present in washing agents which can be used in machines.

Description

The invention relates to a textile detergent with a reduced phosphate content and a substantial content of nonionic surfactants.

The effect of modern detergents was largely due to their high sodium triphosphate content. The advantageous properties of sodium triphosphate include the complex binding capacity for calcium, magnesium, iron and other heavy metal ions, the synergistic influence on the interfacial activity of soaps and synthetic surfactants, the dirt-carrying capacity and the ability to detach and peptize dirt particles as well as the neutralization of acidic dirt. However, the high sodium triphosphate content of detergents is known to the public in connection with environmental issues. criticized for contributing greatly to the eutrophication of surface waters. Numerous phosphate substitutes have therefore already been determined or attempts have been made to compensate for the reduced phosphate content by changing the surfactant composition.

The object of the invention was therefore to develop detergents which have a lower triphosphate content than the known agents, but which are not inferior in their washing and cleaning properties.

It is known that ethoxylated nonylphenols have very good effectiveness as detergent ingredients, especially when it comes to washing out greasy soils. There are agents on the market that mix, e.g. containing nonylphenol + 9 EO and nonylphenol + 6 EO (x EO = x mol ethylene oxide per mol nonylphenol).

A disadvantage of the nonylphenol ethoxylates in detergents is their tendency to develop foaming agents during rinsing, especially in the presence of the anionic surfactants essential for detergents, e.g. the alkylbenzenesulfonates, which limits both the amount of these nonionic surfactants and the anionic surfactants used.

It has now been shown that the use of certain combinations of three alkyl, especially nonylphenol ethoxylates, on the one hand further increases the fat washability of detergents with a lower phosphate content and, on the other hand, the foam safety of the combination of alkylphenol ethoxylates / alkylbenzenesulfonates can be considerably improved.

• a) 3 - 15, vorzugsweise 3 - 10 Gew.-% einer Kombination aus drei voneinander verschiedenen alkylaromatischen Polyethylenglykolderivaten mit 8 - 10, vorzugsweise 9 Kohlenstoffatomen im Alkylrest und mit Ethoxylierungsgraden von 1 bis 4, 4 bis 7 und von 7 bis 12, wobei das Mischungsverhältnis der jeweils niedriger ethoxylierten Verbindungen zu der jeweils höher ethoxylierten Verbindung l : 1 bis 1 : 8 beträgt, und
• b) 85 - 97, vorzugsweise 90 - 97 Gew.-% an sonstigen üblichen Bestandteilen maschinell anwendbarer Waschmittel,

The detergent according to the invention is characterized by a content of

• a) 3-15, preferably 3-10 wt .-% of a combination of three different alkyl aromatic polyethylene glycol derivatives with 8-10, preferably 9 carbon atoms in the alkyl radical and with degrees of ethoxylation of 1 to 4, 4 to 7 and from 7 to 12, wherein the mixing ratio of the respectively lower ethoxylated compounds to the respectively higher ethoxylated compound is 1: 1 to 1: 8, and
• b) 85-97, preferably 90-97% by weight of other customary components of machine-applicable detergents,

wherein the phosphate content of the agent is at most 35, preferably at most 25,% by weight and relates to sodium triphosphate and / or the phosphorus-containing organic complexing agents.

The other usual components of the detergents according to the invention are e.g. Alkaline detergents, organic complexing agents, dirt carriers, bleaching components, non-complexing builders, optical brighteners, enzymes, antimicrobial substances, colors and fragrances.

Finally, proportions of naturally occurring and synthetic anionic surfactants such as soaps and alkyl or alkylaryl sulfates and sulfonates should also be present. Their amount can be 0.3: 1 to 1: 0.3, based on the nonionic surfactants.

The detergents according to the invention can be used as full, pre-wash and mild detergents. Preparations that are to be used as prewashing agents, like the full detergents or cooking detergents, have a pH of between about 9.5 and 11.5 in 1% aqueous solution, which is achieved by adding washing alkalis. Preparations suitable as mild detergents are less alkaline; in 1% aqueous solution they have a pH between about 8.5 and 9.5. The detergents or heavy-duty detergents also differ from the other preparations by the content of a bleaching component which consists of an inorganic or organic peroxy compound as active oxygen carrier, in particular sodium perborate or magnesium monoperphthalate, stabilizers and, if appropriate, activators for the peroxy compound, and the 1 to 30, preferably Can make up 2 to 25 wt .-% of the total detergent.

Suitable alkylaromatic polyethylene glycol derivatives which can be used according to the invention are the addition products of 1-4, 4-7 and 7-12 moles of ethylene oxide with in each case 1 mole of alkyl, preferably nonylphenol. They were made in a known manner from nonylphenol. The combination of the ethoxylation products with 3 different degrees of ethoxylation used according to the invention was obtained by mixing the separately prepared ethoxylation products.

• a) 1 Mol Nonylphenol und 1 - 4 Mol Ethylenoxid,
• b) 1 Mol Nonylphenol und 4 - 7 Mol Ethylenoxid und
• c) 1 Mol Nonylphenol und 7 - 12 Mol Ethylenoxid.

The reaction products of:

• a) 1 mole of nonylphenol and 1-4 moles of ethylene oxide,
• (b) 1 mole of nonylphenol and 4-7 moles of ethylene oxide and
• c) 1 mole of nonylphenol and 7-12 moles of ethylene oxide.

1 to 4% by weight of a), 1 to 7% by weight of b) and 1 to 7% by weight of c) were used. The minimum amount of nonionic compounds was therefore 3% by weight, but the maximum amount was limited to 15% by weight; a total of 3 to 10% by weight was preferably used.

The detergents according to the invention can be in the form of liquids, pastes or powders. In the simplest case, the powdered preparations can be produced by mixing the components. Usually, an aqueous batch of the components which are insensitive to water and heat is first prepared in a manner known per se, e.g. on hot surfaces or in a hot air stream, dried and the powder obtained in this way, the hydrolysis- and heat-sensitive or volatile or liquid or pasty further constituents are subsequently mixed in. These include, where appropriate, the polyethylene glycol derivatives from the above definition, in any case the active oxygen carriers, enzymes, antimicrobials, foam inhibitors, colors and fragrances. In the subsequent admixture, it is advantageous, in particular for the gentle incorporation of small amounts of active ingredients, to convert them first into a dry powdery precursor by mixing with a solid carrier substance, for example by spraying on sodium sulfate, so that they adhere to the powder or agglomerate - or granulate particles stick as small discrete particles.

The other usual constituents contained in the detergents according to the invention, sorted by classes of active substance, are described in more detail below.

Suitable soaps are in particular the sodium salts, but optionally also the potassium, magnesium, ammonium or alkanolamine salts of saturated and unsaturated fatty acids with 8 to 22, preferably 10 to 18, carbon atoms in the molecule.

Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Sulfated fatty acid alkanolamides and fatty acid monoglycerides or the sulfated reaction products of about 1 to 5 moles of ethylene oxide per mole of primary or secondary fatty alcohol or alkylphenol are also suitable.

Suitable surfactants of the sulfonate type are alkylbenzenesulfonates (Cg-C ₁₅ alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C ₁₅ -C ₁₈ monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent ones receives alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtainable from C ₁₀ -C ₂₂ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.

The sulfonate and sulfate type surfactants can be present in the form of their sodium, potassium and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.

• 1. die carboxymethylierten, wenigstens 2 Carboxylgruppen im Molekül enthaltenden mehrwertigen C₂ -C₆ -Alkohole und C₃ - C ₆-Hydroxycarbonsäuren, wie z.B. die Ver-- bindungen Dicarboxymethylethylenglykol und -diethylenglykol, Tricarboxymethylglycerin, Mono- und Dicarboxymethylglycerinsäure, Carboxymethyltartronsäure, Carboxymethylmethyltartronsäure, Carboxymethyläpfelsäure, ferner die carboxymethylierten Derivate der Glutarsäure, Zuckersäure, Schleimsäure, Gluconsäure, des Erythrits, Pentaerythrits, 2,2-Dihydroxymethylpropanols, Sorbits, Mannits, Xylits usw.;
• 2. die polymeren Carbonsäuren mit Molekulargewichten über 350, wie z.B. Polyacrylsäure, Poly-c(-hydroxyacryl- säure, die aus Mischpolymerisaten des Maleinsäureanhydrids mit Ethylen bzw. Propylen, Isobutylen oder Styrol, bzw. mit Vinylmethylether oder Furan, und/oder Acrylsäure erhältlichen Polycarbonsäuren, sowie die aus Acrolein und Acrylsäure mit H₂0₂ und Cannizzaro-Reaktion erhältlichen Polyhydroxycarbonsäuren;
• 3. die Phosphonoalkanpolycarbonsäuren mit 1 und 2 Phosphono- und 2 und 3 Carboxylgruppen, wie z.B. 1-Phosphonoethan-1,2-dicarbonsäure, 2-Phosphono- propan-2,3-dicarbonsäure, 1,1-Diphosphonopropan-2,3-dicarbonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure, 2-Phosphonobutan-2,3,4-tricarbonsäure;
• 4. die amino- und hydroxysubstituierten Alkanpolyphosphonsäuren, wie z.B. 1-Aminoethan-1,1-diphosphonsäure, Aminotrimethylentriphosphonsäure, Methylamino- oder Ethylaminodimethylendiphosphonsäure, Ethylendiaminotetramethylentetraphosphonsäure, Dimethylaminomethandiphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure;
• 5. die Aminopolycarbonsäuren, wie z.B. Nitrilotriessigsäure, Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure sowie höhere Homologe.

In addition to sodium triphosphate and for its further reduction in quantity, the preparations according to the invention can also contain organic complexing agent salts as builder substances. These preferably include the water-soluble salts, in particular the alkali salts, of the following compounds:

• 1. the carboxymethylated, at least 2 carboxyl groups in the molecule containing polyhydric C ₂ -C ₆ alcohols and C ₃ - C ₆ hydroxycarboxylic acids, such as the compounds - dicarboxymethylethylene glycol and diethylene glycol, tricarboxymethylglycerol, mono- and dicarboxymethylglyoxymethyl acid carboxy acid, carbox , Carboxymethyl malic acid, also the carboxymethylated derivatives of glutaric acid, sugar acid, mucic acid, gluconic acid, erythritol, pentaerythritol, 2,2-dihydroxymethyl propanol, sorbitol, mannitol, xylitol, etc .;
• 2. The polymeric carboxylic acids with molecular weights above 350, such as, for example, polyacrylic acid, poly-c (-hydroxyacrylic acid), which are obtainable from copolymers of maleic anhydride with ethylene or propylene, isobutylene or styrene, or with vinyl methyl ether or furan, and / or acrylic acid Polycarboxylic acids, and also the polyhydroxycarboxylic acids obtainable from acrolein and acrylic acid with H ₂ 0 ₂ and Cannizzaro reaction;
• 3. the phosphonoalkane polycarboxylic acids with 1 and 2 phosphono and 2 and 3 carboxyl groups, such as 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 1,1-diphosphonopropane-2,3- dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid;
• 4. the amino- and hydroxy-substituted alkane polyphosphonic acids, such as 1-aminoethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, methylamino- or ethylaminodimethylene diphosphonic acid, ethylene diaminotetramethylene tetraphosphonic acid, dimethylaminomethane diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid;
• 5. the aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologues.

The amounts of the substances in groups 1 to 5 can be 0.1 to 10, preferably 1 to 4% by weight of the composition.

The synthetic, bound water-containing sodium aluminosilicates of the zeolite A type are also particularly suitable as water-insoluble inorganic builders. You can replace the polymer phosphates in whole or in part, i.e. their use also enables the production of phosphate-free agents.

The zeolites are used in the usual hydrated, finely crystalline form, ie they have practically no particles larger than 30 microns and preferably consist of at least 80% particles of a size of less than 10 microns. Their calcium binding capacity, which is determined according to DE 24 12 837, is in the range of 100-200 mg CaO / g. The zeolite NaA can be used in particular, also the zeolite NaX and mixtures of NaA and NaX.

Other neutral or alkaline inorganic or organic water-soluble salts can be used. These include primarily the inorganic, non-complexing salts referred to as washing alkalis from the group of carbonates, bicarbonates, borates and silicates of alkalis; Of the alkali silicates, especially the sodium silicates with a Na ₂ O: SiO ₂ ratio of 1: 1 to 1: 3.5 can be used. Recently, non-complexing layered silicates such as talcum have also been used as neutral fillers. Of the neutral-reacting alkali sulfates, sodium sulfate is particularly important as a solid carrier substance for the production of free-flowing powder preparations. The free-flowing properties of the powder preparations can also be improved by adding small amounts of pyrogenic or precipitated microcrystalline silicon dioxide.

Other substances that are usually used as hydrotropes in liquid agents are the salts of the non-capillary, 2-9 C-containing sulfonic acids, carboxylic acids and sulfocarboxylic acids, e.g. the alkali salts of benzene, toluene, xylene or cumene sulfonic acid, sulfobenzoic acid , Sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.

Dirt carriers or graying inhibitors may be present in the preparations according to the invention to improve the dirt-carrying capacity of the wash liquor, especially in relation to cotton textiles, carboxymethyl celluloses or other cellulose ether carboxylic acids or cellulose ether sulfonic acids. Many of the compounds mentioned above as organic complexing agents for calcium ions also have a dirt-carrying capacity. Other suitable graying inhibitors are polyanionic polymers such as e.g. Polyesters or polyamides which are obtainable from tri- or tetracarboxylic acids and diols, diamines or N-alkyldialkanolamines and contain free carboxyl groups capable of salt formation, or the alkali metal salts of polymeric sulfonic acids, e.g. of polyvinylsulfonic acids, polyesters and polyamides of sulfosuccinic acid, sulfonated phenol-formaldehyde condensates or the products obtainable from polyesters from dicarboxylic acids and N-alkyldialkanolamines by reaction with sultones or haloalkanesulfonic acids.

Also suitable as dirt carriers are nonionic water-soluble or water-dispersible polymers, such as methyl cellulose, hydroxyethyl cellulose, ethoxylated starch, polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone, polyglycol, polyacrylamide and polyethylene imine, and partially alkylated or reacted with substoichiometric amounts of dicarboxylic acids.

Among the known active oxygen carriers which serve as bleaching agents and which supply H ₂ 0 ₂ in water, sodium perborate and H ₂ 0 ₂ supplying inorganic or organic peracid salts, such as, for example, caroates (KHSO ₅ ), perbenzoates or, in particular, peroxyphthalates such as the magnesium salt of peroxyphthalic acid, are special Importance.

It is advisable to incorporate conventional water-soluble and / or water-insoluble stabilizers for the peroxy compounds, such as, for example, magnesium silicates, into the detergents together with these.

In order to achieve a satisfactory bleaching action when washing at temperatures below 80 ° C., in particular in the range from 60 to 40 ° C., bleaching components containing activator are preferably incorporated into the preparations.

As activators for supplying water in H ₂ 0 ₂ peroxy compounds certain are, with this H ₂ 0 ₂ which form organic peracids N-acyl, O-acyl compounds, in particular acetyl, propionyl or benzoyl, and carbonic acid or pyrocarbonic acid esters and Esters of phenols, aliphatic mono- and polyhydric alcohols. Useful compounds are, for example, N-diacylated and N, N'-tetraacylated amines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, sugar esters, such as glucose pentaacetate, acylated glycolurils, such as tetraacetylglycoluril.

Activation of the peroxy compounds can be seen even when amounts of 0.05 mol of activator are used per g-atom of active oxygen; 0.1-1 mol of activator per g-atom of active oxygen is preferably used. Activation of the peroxy compounds produces carboxylic acids, e.g. Acetic acid, propionic acid, benzoic acid, so that it is advisable to add basic salts to bind these carboxylic acids.

The enzyme preparations to be used are usually a mixture of enzymes with different effects, for example proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureas, isomerases, lyases, transferases, desmolases or nucleases. Of particular interest are those obtained from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus Enzymes, especially proteases or amylases, which are relatively resistant to alkali, per compounds and anionic surfactants and are still effective at temperatures up to 70 ° C. Enzyme preparations are usually marketed by the manufacturers as aqueous solutions of the active ingredients or as powders, granules or as cold atomized products. They often contain sodium sulfate, sodium chloride, alkali ortho-, pyro- or polyphosphates, in particular tripolyphosphate, as blending agents. Particular emphasis is placed on dust-free preparations; they are obtained in a manner known per se by incorporating oily or pasty nonionics or by granulating with the help of melts of salts containing water of crystallization in their own water of crystallization.

Enzymes that are specific for a certain type of dirt can be incorporated, for example proteases or amylases or lipases; Combinations of enzymes with different effects are preferably used, in particular combinations of proteases and amylases.

The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds which have a instead of the morpholino group Carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryldiphenyl type may also be present; e.g. the compound 4,4'-Bls (4-chloro-3-sulfostyryl) diphenyl.

Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of the same structure which instead of the sulfamoyl group z. B. carry the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group. Useful polyamide brighteners are also the substituted aminocoumarins, e.g. B. the 4-methyl-7-dimethylamino or the 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-eenzimidazolyl) -2- (1-hydroxyethyl-2-benzimiaazolyl) ethylene and 1-lthyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners. The brighteners for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoaxazolyl) thiophene, 2- (2-benzoaxazolyl) naphtho [2,3-b] thiophene and 1,2- Di- (5-methyl-2-benzoaxazolyl) ethylene suitable. Mixtures of the aforementioned brighteners can also be used.

Example

• "ABS": Alkylbenzolsulfonat, Na-Salz "NP-2E", "NP-5", "NP-6", "NP-EO", "NP-9EO", "OCA-5EO", "OCA-10EO", "OCA-14EO": die Anlagerungsprodukte von 2, 5, 6, 8, 9 bzw. 14 Mol Ethylenoxid (EO) an jeweils 1 Mol technisches Nonylphenol (NP) bzw. Oleyl/Cetylalkohol (OCA);
• "EDTA" bzw. "NTA": die Salze der Ethylendiamintetraessigsäure bzw. der Nitrilotriessigsäure;
• "Perborat": ein etwa 10 % Aktivsauerstoff enthaltendes Produkt der ungefähren Zusammensetzung NaB0₂ . H₂O₂ · 3 ^H ₂ ⁰;
• "CMC": das Salz der Carboxymethylcellulose, Substitutionsgrad 0,7 - 0,8;
• "Enzyme": ein handelsübliches festes Enzymkonzentrat einer Protease, durch Zusatz von Natriumsulfat auf die Aktivitäten von 125 000 LVE/g eingestellt.
• "Sokalan CP 5" = Copolymeres aus Polyacrylsäure und Maleinsäureanhydrid; Na-Salz (BASF)
• "Aufheller I" = 4,4'-Bis-(3-sulfostyryl)-diphenyl; Ka-Salz
• "Aufheller II" = 4,4'-Bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbendisulfonsäure-2,2'; Na_-Salz

The examples describe compositions of some preparations according to the invention. Their salt-like components were used as sodium salts. The following terms and abbreviations are used:

• "ABS": alkylbenzenesulfonate, sodium salt "NP-2E", "NP-5", "NP-6", "NP-EO", "NP-9EO", "OCA-5EO", "OCA-10EO" , "OCA-14EO": the addition products of 2, 5, 6, 8, 9 and 14 mol ethylene oxide (EO) with 1 mol technical nonylphenol (NP) or oleyl / cetyl alcohol (OCA);
• "EDTA" or "NTA": the salts of ethylenediaminetetraacetic acid or nitrilotriacetic acid;
• "Perborate": an approximately 10% active oxygen-containing product of the approximate composition NaB0 ₂ . H ₂ O ₂ .3 ^H ₂ ⁰ ;
• "CMC": the salt of carboxymethyl cellulose, degree of substitution 0.7-0.8;
• "Enzymes": a commercially available solid enzyme concentrate of a protease, adjusted to the activities of 125,000 LVU / g by adding sodium sulfate.
• "Sokalan CP 5" = copolymer of polyacrylic acid and maleic anhydride; Na salt (BASF)
• "Brightener I" = 4,4'-bis (3-sulfostyryl) diphenyl; Ka salt
• "Brightener II" = 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene disulfonic acid 2,2 '; Na _- salt

Example 1:

• 5.0% by weight of C ₉ - C 15 ^- ABS
• 1.0 wt% NP - 2 EO
• 2.0 wt% NP - 5 EO
• 2.0 wt% NP - 8 EO
• 10.0% by weight of trisodium phosphate
• 5.0 wt% Na ₂ CO ₃
• 3.0% by weight Sokalan C P 5
• 0.5 wt% CMC
• 5.0% by weight Na ₂ O · SiO ₃
• 10.0% by weight sodium aluminum silicate
• 0.22 wt% EDTA
• 28.0% by weight perborate
• 2.0% by weight magnesium silicate
• 0.22% by weight of brightener I
• 0.53 wt% enzyme
• 0.1% by weight silicone oil emulsion K 3 G B (DegussaERD) remainder sodium sulfate, water.

Example 2:

• 5.5% by weight of C ₉ - C ₁₅ - ABS
• 4.0 wt% NP - 1 EO
• 4.0% by weight NP - 4 EO
• 4.0 wt% NP - 7 EO
• 0.3% by weight EDTA
• 18.0% by weight sodium triphosphate
• 13.0% by weight sodium aluminum silicate
• 4.0% by weight Na ₂ O.3.3 Si0 ₂
• 30.0% by weight perborate
• 2.5% by weight magnesium silicate
• 1.2 wt% CMC
• 0.3% by weight of brightener I
• 0.2% by weight of paraffin oil (Witcodur 263, Witco Chem./NL) balance sodium sulfate, water.

Example 3:

• 6.5% by weight of C ₉ - C ₁₅ -ABS
• 2.5 wt% NP - 2 EO
• 2.5 wt% NP - 6 EO
• 2.5 wt% NP - 9 EO
• 4.0% by weight coconut fatty acid soap
• 15.0% by weight sodium triphosphate
• 2.5% by weight 2-phosphonobutane-1,2,4-tricarboxylate
• 4.0% by weight Na ₂ 0. 3.3 SiO ₂
• 26.5% by weight perborate
• 2.0% by weight magnesium silicate
• 4.0% by weight of tetraacetylglycoluril
• 0.3% by weight of brightener I
• Balance sodium sulfate, water.

Example 4:

• 3.0 wt% Cg - C ₁₅ ABS
• 5.0 wt% NP - 4 EO
• 5.0 wt% NP - 5 EO
• 5.0 wt% NP - 12 EO
• 5.0% by weight tallow fatty acid soap
• 10.0% by weight sodium triphosphate
• 16.0% by weight Na ₂ CO ₃
• 10.0% by weight sodium aluminum silicate
• 3.0 wt% NTA
• 4.0 wt .-% Na ₂ O · 2 Si0 ₂
• 1.5 wt% CMC
• 2.0% by weight polyacrylate Alcosperse 175 (Alco Chemical
• 0.3 wt% Enzyme Corp. UNITED STATES)
• 20.0% by weight perborate
• 3.0 wt% tetraacetylethylenediamine
• Balance sodium sulfate, water ..

Example 5:

• 5.0 wt% C ₉ - C ₁₅ ABS
• 2.0 wt% NP - 2 EO
• 2.0 wt% NP - 5 EO
• 2.0 wt% NP - 8 EO
• 3.0% by weight of C ₁₂ -C ₁₄ fatty acid, Na salt
• 18.0% by weight sodium triphosphate
• 10.0 wt .-% polycarboxylate of maleic anhydride-ethylene copolymer, MW 2 - 3000
• 0.4 wt% enzyme
• 4.0% by weight Na ₂ O: 3.3 SiO ₂
• 1.5 wt% CMC
• Balance sodium sulfate, water.

Example 6:

• 2.0 wt% NP - 2 EO
• 5.5% by weight Cg - C ₁₅ -ABS
• 4.0 wt% NP - 6 EO
• 4.0 wt% NP - 9 EO
• 3.0% by weight tallow fatty acid soap
• 25.0% by weight Na ₂ O.2.4 SiO ₂
• 24.0% by weight sodium triphosphate
• 4.0% by weight Sokalan CP 5
• 0.5 wt% enzyme
• 1.0 wt% CMC
• Balance sodium sulfate, water

Example 7:

• 8.0 wt% ABS
• 2.0 wt% NP - 2 EO
• 2.5 wt% NP - 6 EO
• 2.5 wt% NP - 8 EO
• 3.0 wt% soap
• 20.0% by weight sodium aluminum silicate
• 10.0% by weight of water glass
• 3.0 wt% NTA
• 1.0 wt% hydroxyethane diphosphonic acid; Na salt
• 1.5% by weight methyl cellulose
• 0.2% by weight of brightener II
• 15.0% by weight perborate
• 2.0% by weight glucose pentaacetate
• 0.4 wt% enzyme
• Balance sulfate water

If in the examples the lower and higher ethoxylated nonylphenols used there were replaced by corresponding ethoxylated fatty alcohols or oxo alcohols, which were also propoxylated at times, no comparable results could be achieved with these preparations because the detergents would foam too much when washed in the machine and / or the fat washability was insufficient.

The detergents according to the invention have a lower phosphorus content than known preparations based on triphosphate or are even phosphate-free. Even when washing in hard water, the agents according to the invention achieved a good degree of whiteness compared to the known agents with a high triphosphate content and no additional formation of laundry incrustations or deposits on washing machine parts was observed. The preparations according to the invention in particular have an excellent washability of fat such as skin fat or fatty cosmetic stains such as lipstick, make-up or mascara. This was shown e.g. on the collars and cuffs of blouses and shirts, in particular those made of easy-care cotton or cotton-polyester mixed textiles and on greasy table and professional linen, such as those of kitchen staff, butchers, people working at petrol stations and in car workshops, etc.

V e r g l e i c h s v e r s u c h e

In a washing machine of the Miele 429 type, in a two-eyed process at 90 ° C and a water hardness of 10 ° d or 16 ° d, 3.5 kg of clean laundry made of polyester / cotton (65/35) or pure cotton was washed through Fat-based lipstick, mascara and make-up had been artificially stained, the dosage being 45/90 g of detergent for the pre-wash and main wash. The composition of the detergents is shown in the table below. A and B are analytically determined market products. The composition of Examples 1 and I to III correspond to the teaching of the present invention, while Examples a to e also served for comparison purposes.

The evaluation of the washing results showed, by visual sampling and measurement in the ELREPHO device, that recipes 1 and II to IV were clearly superior to recipes A and B in the removal of mascara and make-up. The lipstick soiling completely disappeared. The foam behavior was the best for recipe II.

If you work with recipes A and B, ie without low ethoxylated nonylphenol, the foam behavior is not acceptable despite the higher soap content. Foam attenuation has already been achieved by adding, for example, propoxylated EO adducts to secondary, aliphatic alcohols, but this does not result in a simultaneous increase in fat washability.

Claims (4)

1. Detergent, characterized by a content of a) 3-15% by weight of a combination of three different alkyl aromatic polyethylene glycol derivatives with 8-10, preferably 9 carbon atoms in the alkyl radical and with degrees of ethoxylation of 1-4, 4-7 and 7-12, the mixing ratio being lower in each case ethoxylated compounds to the higher ethoxylated compound is 1: 1 to 1: 8, and b) 85-97% by weight of other usual constituents of machine-applicable detergents, the phosphate content of the agent being at most 35, preferably at most 25% by weight, and referring to sodium triphosphate and / or the phosphorus-containing organic complexing agent salts. 2. Detergent according to claim 1, characterized by a content of washing alkalis, organic complexing agents, dirt carriers, bleaching components, non-complexing builders, optical brighteners, enzymes, antimicrobial substances, colors and fragrances as other common constituents. 3. Detergent according to claim 1 and 2, characterized by a content of 3 - 10 wt .-% of the surfactant combination a) from lower and higher ethoxylated compounds. 4. Detergent according to claim 1 to 3, characterized by a content of anionic surfactants as a component of component b), their amount, based on the nonionic surfactants according to a), being 0.3: 1 to 1: 0.3.