EP1099748A2 - Surfactant containing detergent compositions - Google Patents

Abstract

Solid or liquid to gel-type laundry and other detergents, containing surfactants and other detergent constituents. Solid or liquid to gel-type laundry and other detergents, containing surfactants and other detergent constituents, contain surfactant(s) from the group of di-, tri- and polycarboxylic esters with alkoxylated 8-22 carbon (C) alcohols.

Description

The present invention relates to solid or liquid to gel-like washing and Detergents containing surfactants and other detergent ingredients, the Use of these agents for cleaning hard surfaces and for washing Textiles.

The surfactants are one of the most important ingredients in detergents and cleaning agents. In addition to the conventional soaps, a variety of synthetic surfactants were also used developed a wide variety of physical properties, such as ionic, non-ionic or non-thermal surfactants. These surfactants differ in their "Physical states" at processing and storage temperature in their solubility in Water and its affinity for the substrates to be cleaned.

Anionic surfactants show a good affinity for the substrates to be cleaned and one excellent washing and cleaning effect, which indicates the interactions between the negatively charged anionic surfactant and the positively charged Soiling is attributable. The disadvantage, however, is that sensitive substrates, especially textiles, damage with frequent washing with anionic surfactants can take.

The nonionic surfactants known as "mild surfactants" are usually as Liquids before. The liquid nonionic surfactants are excellent as Solvents in liquids, however, they pose problems when used in solids Means should be incorporated, as they lead to a deterioration in pourability of these funds can lead. The nonionic surfactants are soluble in water, form gel phases on contact with water, which make dissolving difficult. Further is however, the affinity because of its uncharged hydrophilic part to be cleaned Substrate or soiling less than that of the anionic surfactants.

The present invention had for its object to find surfactants that quickly are soluble and do not form a gel phase when dissolved and have a good affinity for them have cleaning substrates.

Surprisingly, it was found that the esters of di-, tri- and Polycarboxylic acids with alkoxylated fatty alcohols are anionic surfactants, which are a have good affinity for the substrate, but is delayed in the washing process hydrolyze alkoxylated fatty alcohol and a di- or polycarboxylic acid, in other words to a nonionic surfactant and to compounds that have cobuilder properties demonstrate. These esters are liquids that work very well in solid media to let.

The present invention accordingly relates to solid or liquid to gel-form detergents and cleaning agents containing surfactants and other detergent components, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols is} contained .

The esters of di-, tri- and polycarboxylic acids used according to the invention are Compounds which are known from the acids with the corresponding alcohols can be obtained.

Examples of the di-, tri- and polycarboxylic acids used as starting compounds for Preparation of the esters used according to the invention can be used all aliphatic and aromatic carboxylic acids with at least two acid groups and optionally at least one hydroxy group in the molecule. examples for aliphatic di-, tri- and polycarboxylic acids are malic acid, tartaric acid, citric acid, Propane tricarboxylic acid, maleic acid, fumaric acid, succinic acid, etc. Examples of suitable aromatic carboxylic acids are phthalic acid, terephthalic acid, Trimellitic acid, pyromellitic acid and mellitic acid. Citric acid will particularly preferably used because citric acid or its salts Have cobuilder properties and the surfactant used according to the invention in in this case a nonionic surfactant and a cobuilder, i.e. two active washing components, hydrolyzed.

The alcohols used are alkoxylated C _8-22 alcohols, which are also known as nonionic surfactants and are referred to as fatty alcohol _alkoxylates . Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 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 can be linear or preferably methyl-branched in the 2-position or linear are particularly suitable and may contain methyl-branched radicals in the mixture, as are usually present in oxo alcohols. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols 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 to 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7EO. 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 narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Furthermore, the agents according to the invention can all usually be used in detergents and cleaning agents substances contained, such as other surfactants, in particular anionic surfactants, and builder substances, inorganic salts, bleaching agents, Bleach activators, enzymes, enzyme stabilizers, graying inhibitors, Foam inhibitors, silicone oils, soil release compounds, color transfer inhibitors, Salts of polyphosphonic acids, optical brighteners, fluorescent agents, fragrances, Dyes, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agents, UV absorbers or mixtures thereof are included.

The agents _{according to the} invention can the esters from the di-, tri- and polycarboxylic _acids with alkoxylated C _{8-22 alcohols} in an amount of 0.5 to 60% by weight, preferably 3 to 15% by weight, based on the finished funds included.

In addition to the ester surfactants used according to the invention, the compositions can include further agents Surfactants selected from the non-ionic, anionic, cationic and amphoteric Contain surfactants.

Examples of nonionic surfactants are non-esterified alkoxylated fatty alcohols, Sugar surfactants, especially dialkyl and alkenyl oligogliycosides and Polyhydroxy fatty acid amides, alkoxylated fatty acid methyl esters, and amine oxides in Consideration.

The sugar surfactants that can be used in process step A come especially the alkyl and alkenyl oliglycosides and polyhydroxy fatty acid amides in Consideration.

The alkyl and alkenyl oliglycosides have the general formula R ¹ O (G) _x in which R ^{1 is} a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 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.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.Polyhydroxy fatty acid amides which can be used are those having the formula (II).

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.

The polyhydroxy fatty acid amides are known substances that usually by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a Fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained can. With regard to the processes for their production, reference is made to the US patents US-A-1,985,424, US-A-2,016,962 and US-A-2,703,798 and the International Patent application WO-A-92/06984 referenced. Preferably the derive Polyhydroxy fatty acid amides of reducing sugars with 5 or 6 carbon atoms, especially on the glucose.

The sugar surfactants can be in the form of aqueous solutions, such as those from the Manufacturing processes are obtained, used. Other forms of use are Granules or steam-dried products.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ _ ₁₈ - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.

In the detergent tablets according to the invention, all can builders usually used in detergents and cleaning agents, in particular, therefore, zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H 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 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not from ecological Reasons should be avoided. Among the variety of commercially available Phosphates have the alkali metal phosphates with particular preference for Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the Detergent and cleaning agent industry the greatest importance.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists without water and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the washing and Detergent tablets, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic Cobuilder (see below) and phosphonates are used. These substance classes are described below.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of to call this.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.

The (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used. The content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.

Further preferred copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Polymeric aminodicarboxylic acids are also further preferred builder substances. to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. there is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which a DE out of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide is also suitable, a product oxidized at the C _{6 of} the saccharide ring being particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt used, the disodium salt neutral and the tetrasodium salt alkaline (pH 9) responds. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as Hepta and Octa sodium salt of DTPMP, used. As a builder, the Class of phosphonates preferably uses HEDP. The aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, it is preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or phthaloiminoperacids such as phthaliminopercaproic acid. Organic peracids, alkali perborates and / or alkali percarbonates are preferably used in amounts of 0.1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 25% by weight.

As bleach activators can be compounds that are under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Suitable substances are the O- and / or N-acyl groups of the named C number of carbon atoms and / or optionally substituted benzoyl groups. Prefers are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6-tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, isatoic anhydride and / or succinic anhydride, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the known from German patent applications DE 196 16 693 and DE 196 16 767 Enol esters as well as acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine or gluconolactone, triazole or triazole derivatives and / or particulate Caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam, which results from the international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known. The from the German patent application DE-A-19616 769 known hydrophilically substituted acylacetals and those in the German Patent application DE-A-19616 770 and international patent application WO-A-95/14075 Acyllactams described are also preferably used. Also the Combinations known from German patent application DE-A-44 43 177 conventional bleach activators can be used. You can also Nitrile derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives are used become. Preferred bleach activators are sodium 4- (octanoyloxy) benzene sulfonate, Undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), Decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12) and N-methylmorpholinum acetonitrile (MMA). Such bleach activators are in the usual range of 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total Means included.

The bleach activator can be coated with coating substances in a known manner or if necessary, using auxiliaries, in particular methyl celluloses and / or Carboxymethyl celluloses, granulated or extruded / pelleted and if desired, contain further additives, for example dye, the Dye has no coloring effect on the textiles to be washed. Preferably contains such granules over 70% by weight, in particular from 90 to 99% by weight Bleach activator. A bleach activator is preferably used, the under Washing conditions forms peracetic acid.

In addition to the conventional bleach activators listed above or other You can also use those from European patent specifications EP-A-0 446 982 and EP-A-0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those known from German patent application DE-A-195 29 905 Manganese, iron, cobalt, ruthenium or molybdenum salt complexes and their from German patent application DE-A-196 20 267 known N-analog compounds which German patent application DE-A-195 36 082 known manganese, iron, cobalt, Ruthenium or molybdenum carbonyl complexes described in the German patent application DE-A-196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium-amine complexes, which are described in German patent application DE 4416 438 Manganese, copper and cobalt complexes described in the European Patent application EP-A-0 272 030 described cobalt complexes, which come from the European Patent application EP-A-0 693 550 known manganese complexes, which from the European patent EP-A-0 392 592 known manganese, iron, cobalt and Copper complexes and / or those in European Patent EP-A-0 443 651 or European patent applications EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 and EP-A-0 544 519 Manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are for example from the German patent application DE-A-196 13 103 and the international patent application WO-A-95/27775. Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in one Amount up to 1 wt .-%, in particular from 0.0025 wt .-% to 0.25 wt .-% and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.

Enzymes in particular come from the hydrolase class, such as Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains, such as protein, greasy or starchy stains, and graying. Cellulases and others Glycosyl hydrolases can be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Oxidoreductases can also be used to inhibit color transfer.

Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, in particular, however, mixtures containing protease and / or lipase or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as ceilulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight.

The detergents and cleaning agents according to the invention can be both in solid and are in liquid to gel form. The fixed funds include e.g. Powder, Granules and also pressed products, such as moldings, e.g. B. tablets, each do not have to represent uniform products, but from individual components, so-called compounds. You can in a manner known per se getting produced.

If the agents according to the invention are in liquid to gel form, it can these are aqueous or non-aqueous systems. The production of Liquid to gel preparations can be carried out continuously or batchwise simple mixing of the components, if necessary at elevated temperature.

Solvents used in the liquid to gel compositions can come, for example, from the group of mono- or polyvalent Alcohols, alkanolamines or glycol ethers, provided they are specified in the Concentration range are miscible with water. Preferably the Solvents selected from ethanol, n- or i-propanol, butanols, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or - ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Solvents can be used in the invention liquid to gel detergents in amounts between 0.1 and 20 % By weight, but preferably less than 15% by weight and in particular less than 10% by weight be used.

The composition according to the invention can be used to adjust the viscosity or several thickeners or thickening systems can be added. The viscosity of the Compositions according to the invention can be prepared using customary standard methods (e.g. Brookfield RVD-VII viscometer at 20 rpm and 20 ° C, spindle 3) be measured and is preferably in the range of 100 to 5000 mPas. Preferred compositions have viscosities of 200 to 4000 mPas, where Values between 400 and 2000 mPas are particularly preferred.

Suitable thickeners are inorganic or polymeric organic compounds. This mostly organic high molecular substances, which are also called swelling agents, usually absorb the liquids and swell them, eventually turning into viscous to pass real or colloidal solutions.

The inorganic thickeners include, for example, polysilicic acids, Clay minerals like montmorillonie, zeolites, silicic acids and bentonites.

The organic thickeners come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.

Natural polymers that are used as thickeners for example agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, Polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and Casein.

Modified natural products mainly come from the group of modified starches and celluloses, for example carboxymethyl cellulose and others Cellulose ether, hydroxyethyl and propyl cellulose as well as core meal ether called.

A large group of thickeners that are widely used in the Find the most diverse fields of application are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, Polyethers, polyimines, polyamides and polyurethanes.

The thickeners can be present in an amount of up to 5% by weight, preferably from 0.05 to 2% % By weight, and particularly preferably from 0.1 to 1.5% by weight, based on the finished product Composition.

The washing and cleaning agents according to the invention are suitable both for cleaning hard surfaces including dishes and for washing textiles.

Another object of the present invention is accordingly an agent for cleaning hard surfaces containing surfactants and other detergent components, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols is} contained .

Cleaning hard surfaces in the sense of the present invention excludes this Cleaning all surfaces in the household and in the commercial area including floors, wall and cabinet surfaces and windows. Likewise is includes cleaning dishes. The cleaning process also includes steps for Pre- and post-treatment, like a rinsing process.

In a preferred embodiment, an agent according to the invention for cleaning hard surfaces contains 0.5 to 15% by weight of the surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} , from 0.5 to 10 % By weight of further surfactants, up to 10% by weight of organic solvent (hydrophilizing agent), optionally complexing agent and water.

Another object of the present invention is accordingly a textile detergent containing surfactants and other detergent components, which is characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols is} contained.

The textile detergents can be used depending on their special recipe Pre-treatment of laundry, for washing and post-treatment, i.e. as a fabric softener, etc. are used.

In a preferred embodiment, a textile _{detergent according to the} invention, which is in solid form, contains 3 to 15% by weight of a surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} , 2.5% by weight. % to 20% by weight of anionic surfactant, 1% by weight to 20% by weight of further nonionic surfactant, 30% by weight to 55% by weight of water-insoluble inorganic builder, up to 25% by weight, in particular 1 % By weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight. % to 15% by weight of inorganic salts, in particular alkali carbonate, sulfate and / or silicate, and up to 2% by weight, in particular 0.4% to 1.2% by weight of enzyme.

In a further preferred embodiment, a textile _{detergent according} to the invention which is in liquid form contains 3 to 60% by weight of a surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} , up to 15% by weight. %, in particular 3% by weight to 10% by weight, of anionic surfactants, up to 15% by weight, in particular 3% by weight to 10% by weight, of further nonionic surfactants, up to 18% by weight, in particular 4% by weight to 16% by weight of soap, 0.5% by weight, up to 20% by weight of water-soluble organic builder, up to 20% by weight, in particular 0.1% by weight to 5 % By weight of water-insoluble inorganic builders, and up to 60% by weight, in particular 10% by weight to 50% by weight of water and / or water-miscible solvent, enzyme and up to 10% by weight, in particular 0.01 % By weight to 7.5% by weight of enzyme stabilizer system.

Examples

The solubility of detergent _{formulations which} contained the _{surfactants used according to} the invention from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} was tested. The composition of the compositions and the results of the solubility test are shown in Table 1. component Example 1 (invent.) [% By weight] Example 2 (comp.) [% By weight] Tower powder (see Table 2) 66 66 Sodium perborate monohydrate 20th 20th PEG 4000 7 7 C _12/18 -FA x 7 EO - 7 Citric acid C _12/18 FA x 7 EO ester 7 - L test (residue%) 7.8 18th Tower powder component Amount [% by weight] Zeolite A 46.25 Sokalan CP 5 ³ 8.75 Phosponate 0.5 C _9-13 alkyl benzene sulfonate 31.25 Soap 2.5 water 10.75

L test

To determine the residue behavior or the solubility behavior, in a 2 l beaker 8 g of the agent to be tested with stirring (800 rpm with laboratory stirrer / propeller stirring head Centered 1.5 cm from the bottom of the beaker) and stirred at 30 ° C for 1.5 minutes. The test was carried out with water with a hardness of 16 ° d carried out. The wash liquor was then poured off through a sieve (80 μm). The beaker was rinsed over the sieve with very little cold water. It was done a double determination. The screens were in the drying cabinet at 40 ° C ± 2 ° C to dried to constant weight and the detergent residue weighed out. The residue is given as the average of the two individual determinations in percent. At Deviations of the individual results by more than 20% from each other usually carried out further tests; this was the case with the present Examinations are not necessary. All of the examples examined showed in the frame the error results consistent with the comparative example.

The test results show that the agent according to the invention is significantly better Has solubility as the agent from the comparative example.

Claims (9)

Solid or liquid to gel-form detergents and cleaning agents containing surfactants and other detergent components, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols is} contained. Agent according to claim 1, characterized in that di-, tri- and polycarboxylic acid esters are selected from malic acid, tartaric acid, citric acid, propane tricarboxylic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, mellitic acid or mixtures thereof. _Agent according to claim 1 or 2, characterized in that the alkoxylated C _{8-22 alcohols} are ethoxylated and / or propoxylated C _{8-22 alcohols} . Agent according to one of claims 1 to 3, characterized in that further surfactants, in particular anionic surfactants, and builder substances, inorganic salts, bleaching agents, bleach activators, enzymes, enzyme stabilizers, graying inhibitors, foam inhibitors, silicone oils, soil release compounds, color transfer inhibitors, salts of polyphosphonic acids, optical brighteners, fluorescent agents, fragrances, dyes, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, UV absorbers or mixtures thereof are contained. Agent for cleaning hard surfaces, containing surfactants and other detergent components, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols is} contained. Agent according to Claim 5, characterized in that it contains 0.5 to 15% by weight of the surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} , from 0.5 to 10% by weight. % of further surfactants, up to 10% by weight of organic solvent (hydrophilizing agent), optionally complexing agent and water. Textile detergent containing surfactants and other detergent ingredients, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols is} contained. Agent according to Claim 7, characterized in that it is in solid form and 3 to 15% by weight of a surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} , 2.5% by weight. % to 20% by weight of anionic surfactant, 1% by weight to 20% by weight of further nonionic surfactant, 30% by weight to 55% by weight of water-insoluble inorganic builder, up to 25% by weight, in particular 1 % By weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight. % to 15% by weight of inorganic salts, in particular alkali carbonate, sulfate and / or silicate, and up to 2% by weight, in particular 0.4% by weight to 1.2% by weight of enzyme are. Agent according to claim 7, characterized in that it is in liquid to gel form and 3 to 60 wt .-% of a surfactant from the group of di-, tri- and polycarboxylic _{acid esters} with alkoxylated C _{8-22 alcohols} , up to 15 wt %, in particular 3% by weight to 10% by weight of anionic surfactants, up to 15% by weight, in particular 3% by weight to 10% by weight of further nonionic surfactants, up to 18% by weight , in particular 4% by weight to 16% by weight of soap, 0.5% by weight, up to 20% by weight of water-soluble organic builder, up to 20% by weight, in particular 0.1% by weight to 5% by weight of water-insoluble inorganic builders, and up to 60% by weight, in particular 10% by weight to 50% by weight of water and / or water-miscible solvent, enzyme and up to 10% by weight, in particular 0, 01 wt .-% to 7.5 wt .-% enzyme stabilizer system are included.