EP1050575B1 - Alkaline detergent compositions comprising alkylbenzene sulfonates and alkanolamines - Google Patents

Abstract

Alkaline (laundry) detergent contains: (a) alkylbenzenesulfonic acid(s) or salt(s) with a linear or branched 8-24 carbon (C) alkyl group, (b) alkanolamine(s) and/or their ammonium salt(s) (I) and (c) 0-10 wt.% builder(s), the (a):(b) weight ratio being (7-1):1. Alkaline (laundry) detergent contains: (a) alkylbenzenesulfonic acid(s) or salt(s) with a linear or branched 8-24 carbon (C) alkyl group, (b) alkanolamine(s) and/or their ammonium salt(s) of formula (I) and (c) 0-10 wt.% builder(s), the (a):(b) weight ratio being (7-1):1; (H+)nN(RaO)kH(RbO)lH(RcO)mH (I) k, l, m = 0-3; k+l+m = over 1; n = 0 or 1; Ra, Rb, Rc = linear or branched hydrocarbyl with 2-6 C and, in at least case, 3-6 C.

Description

The invention relates to alkaline washing and cleaning compositions containing alkylbenzenesulfonates and alkanolamines and to a process for washing or cleaning using such compositions and using calcium ions-rich washing water. In particular, the invention relates to the use of alkanolamines to improve the hardness stability of alkylbenzenesulfonates in alkaline detergents and cleaners and to delay the precipitation of calcium carbonate from such detergent and cleaner compositions.

Sodium alkylbenzenesulfonates, in particular those containing linear alkyl radicals (LAS), are surfactants which are widely used because of their detergency, biodegradability and cost-effective production in detergents and cleaners. These detergents and cleaners contain e.g. LAS typically in amounts of from 3 to 30% by weight in addition to generally other known components such as builders, bleaches, perfumes, foam inhibitors, etc.

The use of alkanolamines in detergents and cleaners is also known. These are used, inter alia, for the neutralization of anionic surfactants. It is known that the neutralization products of anionic surfactants with alkanolamines, unlike, and in preference to, the use of alkali metal salts, prevent the formation of liquid crystalline surfactant phases in formulation. WO 96/07724 describes, for example, monophasic soap gels and viscous soap formulations in which the neutralization products of fatty acids with the alkanolamines, such as triethanolamines, are used to prepare homogeneous formulations.

US 4,105,592 describes a liquid detergent containing nonionic and anionic surfactants in addition to alkanolamines and minor amounts of additives such as fatty acid-based corrosion inhibitors and alkali metal salts. The alkanolamines are used to neutralize the alkylbenzenesulfonic acids and other acidic components, with the alkanolamines preferably being used in excess to act simultaneously as a buffer in the formulation and to provide a pH of from 7 to 9. As alkanolamines only C1 or C2 alkanolamines are mentioned.

US 4,476,045 describes highly concentrated surfactant compositions for use as a washstock which contain organic sulfates or sulfonates in the acid form which are neutralized with a secondary or tertiary amine having at least three carbon atoms on the nitrogen atom and further a hydroxy group in the 2 or 3 position ,

As a washing and cleaning solvent tap water is often used, which u. a. Contains calcium and magnesium ions (hard tap water). Anionic surfactants, e.g. Alkylbenzenesulfonates or fatty alcohol sulfates form sparingly soluble salts with the hardness ions. If the anionic surfactant fails as a sparingly soluble precipitate, this has the consequence that part of the surfactant is no longer available for cleaning, so that the concentration of washing-active substance in the liquor is reduced and results in a reduced washing result. Furthermore, the sparingly soluble precipitate has the property of settling on the substrate to be cleaned. In textile washing, therefore, an increase in the textile shrinkage is observed. When cleaning hard surfaces, precipitates are formed on the surface, e.g. lead to a decrease in gloss.

In order to prevent the precipitation of the sparingly soluble precipitates of anionic surfactants with calcium or magnesium, one sets the detergent or detergency builder, which have the task of binding the calcium and magnesium ions and to prevent the precipitation of anionic surfactants. As builders, for example, zeolites or silicates are used. But also soluble phosphates or hydroxy acids, e.g. Citrates are widely used because of their ability to form soluble complexes with the hardness ions.

The hardness ions not only reach the wash liquor through the water used, but are also often part of the dirt. Occasionally, the detergents themselves contain calcium or magnesium ions in order to obtain special benefits in terms of cleaning performance, builder action or detergent formulation. In this case, the use of co-builders, chelating agents or the like must prevent the deposition of poorly soluble calcium or magnesium deposits on the substrate to be cleaned.

There has therefore been no lack of attempts to develop additives that are used in the washing and cleaning process, inhibiting the precipitation of calcium precipitates of anionic surfactants and the formation of calcium carbonate. DE 43 109 95-A1 describes, for example, the use of polyaspartic acids in detergent formulations. In WO 96/19445 diaminoalkyl disulphosucciates are used as builder substances in detergent formulations described for applications where the sequestration of water hardness is required.

The processes known in the prior art for inhibiting the precipitation of calcium salts in the washing and cleaning process have the disadvantage that they require the use of expensive additives such as builders or cobuilders.

Furthermore, attempts have been made to avoid the formation of sparingly soluble precipitates of calcium or magnesium salts of anionic surfactants to formulate detergents and cleaning agents mainly based on hardness-insensitive surfactants, such as the Akoholethoxylaten to waive water softening in this way can. Due to the good washing performance of anionic surfactants, especially for pigment-containing or clay-like soils, coupled with the cost-effective manufacturability and the good processability, however, the use of anionic surfactants can not be dispensed with in most cases.

It was therefore an object to find a cost-effective and ecotoxicologically acceptable alternative to the known co-builders or to reduce the use of builders, which inhibits or delays the precipitation of calcium salts in the relevant temperature ranges in alkylbenzenesulfonate-containing detergents and cleaning agents during the cleaning process can be.

It has surprisingly been found that both the precipitation of the calcium salts of the alkylbenzenesulfonate and the precipitation of coarse-disperse calcium carbonate is inhibited by the simultaneous presence of specific alkanolamines in combination with alkylbenzenesulfonic acids or their salts in the wash liquor.

• (A) zumindest eine Alkylbenzolsulfonsäure bzw. deren Salz, die einen linearen oder verzweigten Alkylrest mit 8 bis 24 C-Atomen aufweist,
• (B) zumindest ein Alkanolamin, bzw. dessen Ammoniumsalz, der allgemeinen Strukturformel I,
  
  worin, jeweils unabhängig voneinander,

  k, l, oder m

  0, 1, 2 oder 3 ist, wobei k + l + m > l ist

  n

  0 oder 1 ist und

  R^a, R^b oder R^c

  ein linearer oder verzweigter Kohlenwasserstoff mit 2 bis 6 Kohlenstoffatomen ist, wobei zumindest ein R 3 bis 6 Kohlenstoffatome aufweist, und

• (C) zu 0 bis 10 Gew.%, bezogen auf die Gesamtzusammensetzung, einen oder mehrere Builder, und
  weiterhin zu 0.001 bis ca. 5 Gew %, bezogen auf die Gesamtzusammensetzung, Enzyme, wobei die Komponenten (A) und (B) im Gewichtsverhältnis 7:1 bis 1:1 eingesetzt

The invention thus alkaline washing and cleaning compositions containing as components

• (A) at least one alkylbenzenesulfonic acid or its salt, which has a linear or branched alkyl radical having 8 to 24 C atoms,
• (B) at least one alkanolamine, or its ammonium salt, of the general structural formula I,
  
  wherein, independently of one another,

  k, l, or m

  0, 1, 2 or 3, where k + l + m> l

  n

  0 or 1 is and

  R ^a , R ^b or R ^c

  a linear or branched hydrocarbon having 2 to 6 carbon atoms, wherein at least one R has 3 to 6 carbon atoms, and

• (C) from 0 to 10% by weight, based on the total composition, of one or more builders, and
  further to 0.001 to about 5% by weight, based on the total composition, of enzymes, wherein components (A) and (B) are used in a weight ratio of 7: 1 to 1: 1

become. Another object of the invention is a method according to claim 14.

The ammonium salts of the alkanolamines used according to the invention are protonated alkanolamines (n = 1). R ^a , R ^b or R ^c are divalent linear or branched hydrocarbons, which are preferably linear and are substituted in the 1,2-position oxygen or nitrogen. The hydrocarbons R ^a , R ^b or R ^c in the sum preferably at least 5 and at most 15 carbon atoms, more preferably at least 6, more preferably at least 7 and at most 12 carbon atoms. The alkanolamines used according to the invention preferably have at least two isopropanol radicals.

beschreiben, worin die Reste bzw. Indizes jeweils unabhängig voneinander sind:

k, l, m

0, 1, 2 oder 3, wobei k + l + m > 1 ist

n

0 oder 1 und

R¹, R² oder R³

voneinander unabhängig H oder lineare oder verzweigte C₁- bis C₄- Alkylreste sind, wobei zumindest ein R für eine CH_3-Gruppe steht.

Preferred alkanolamines, or their ammonium salts, can also be represented by the general structural formula II

in which the radicals or indices are each independent of one another:

k, l, m

0, 1, 2 or 3, where k + l + m> 1

n

0 or 1 and

R ¹ , R ² or R ³

independently of one another are H or linear or branched C ₁ - to C ₄ -alkyl radicals, at least one R being a CH ₃ group.

According to a further embodiment of the invention, the alkylbenzenesulfonic acids or salts thereof have a linear alkyl radical having 8 to 24 carbon atoms.

The components (A) and (B) can also be used in a ratio of 2: 1 to 1: 2, preferably 1.2: 1 to 1: 0.8, based on the molar concentration.

In a further embodiment of the invention, the builder fraction (C) of the detergent composition is preferably from 0.1 to 5% by weight, based on the total composition. In a particularly preferred embodiment, the presence of insoluble builder is completely dispensed with.

Solid formulations may e.g. at least about 0.5% by weight, liquid formulations and granulated formulations of from 5 to 50% by weight of builder. Both inorganic and organic systems can be used. They are used in detergent formulations to aid particulate soil removal and control water hardness.

The inorganic builders include, without limiting the formulations of the invention thereto, alkali metal, ammonium and alkanolammonium salts of polyphosphates (eg tripolyphosphates, pyrophosphates and polymeric metaphosphates), phosphonates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates ,

Examples of silicate builders are alkali metal silicates, especially those with a SiO ₂ to Na ₂ O in the ratio 1.6 to 1 to 3.2 to 1 and sheet silicates such as sodium silicates of the type NaMSi _x O _{2x + 1} yH ₂ O (M is Na or H, x = 1.9 -4, y = 0-20), particularly preferred is the type designated SKS-6. Magnesium silicates can also be used here. Aluminosilicates are also useful in the formulations of the present invention and especially important in granular detergent formulations. The aluminosilicate builders useful can be described by the empirical formula [M _z (z AlO ₂ ) y] x H ₂ O, where z and y are at least 6, and the molar ratio of z to y is in the range of 1.0 is up to 0.5, x can take values of about 0 to 30. It can be both crystalline and amorphous, synthetic or naturally occurring aluminosilicates.

Organic builders also belong to the builders which can be used in the formulations according to the invention. These include polycarboxylates such as ether carboxylates, cyclic or acyclic, hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, all in the form of the acid or its alkali, Ammonium or Organoammoniumsalze can be used. Alkyl, ammonium or organoammonium salts of polyacetic acid are suitable as well as salts of citric acid or combinations of different builders. Alkenylsuccinic acids and salts are particularly preferred organic builders. Monocarboxylic acid salts can also be incorporated into the formulations of the invention either alone or in combination with one of the aforementioned builders.

• (D) zu 0,001 bis 8 Gew.%, vorzugsweise 0,5 bis 5 Gew.%, bezogen auf das Gewichtsverhältnis Metallion zur Gesamtzusammensetzung, 2-wertige Metallionen bzw. deren Salze, insbesondere Calcium- oder Magnesium-Ionen.

Another component of the compositions according to the invention are:

• (D) to 0.001 to 8 wt.%, Preferably 0.5 to 5 wt.%, Based on the weight ratio of metal ion to the total composition, 2-valent metal ions or their salts, in particular calcium or magnesium ions.

The composition according to the invention is advantageously used for washing and / or cleaning using additives containing 2-valent metal salts, in particular calcium, e.g. in compositions containing water and calcium ions in a concentration of 0.2 to 6 mmol / l in the washing composition.

The subject matter of the composition according to the invention is also a product which is obtained by neutralization of the alkylbenzenesulfonic acids used according to the invention with the alkanolamine used according to the invention.

Examples of alkanolamines used in accordance with the invention are triisopropanolamine, diethanolmonoisopropanolamine, monoethanolamine diisopropanolamine, butanol isopropanolamine, hexanolisopropanolamine, etc., or mixtures thereof, for example a mixture of mono-, di- and triisopropanolamine. The alkonolamine used according to the invention are also those by alkoxylation, eg are accessible with propylene oxide, such as ammonia, alkanolamines or alkylamines.

It has surprisingly been found that the presence of the alkanolamines according to the invention in formulations comprising alkylbenzenesulfonic acids or salts thereof reduces the tendency of the alkylbenzenesulfonic acids to precipitate in the form of their calcium alkylbenzenesulfonates.

• durch Bestimmung des Rückstandes nach Filtration einer Alkylbenzolsulfonatlösung (ca. 1 g/l), welcher steigende Mengen an Calciumhärte zugesetzt werden,
• durch Verfolgen der Trübung einer verdünnten Lösung (ca. 1g/l) von Alkylbenzolsulfonat bei Zugabe von Calciumhärte oder
• durch die Bestimmung der dynamischen Oberflächenspannung der Lösung kann die Menge an freiem Alkylbenzolsulfonat bestimmt werden, aus der die Menge an ausgefallenem Calciumalkylbenzolsulfonat ermittelt werden kann.

The tendency to precipitate calcium salts, for example calcium alkylbenzenesulfonates or calcium carbonate, can be determined in a simple manner, for example by the following methods:

• by the determination of the residue after filtration of an alkylbenzenesulphonate solution (about 1 g / l) to which increasing amounts of calcium hardness are added,
• by monitoring the turbidity of a dilute solution (about 1 g / l) of alkylbenzenesulfonate with the addition of calcium hardness or
• By determining the dynamic surface tension of the solution, the amount of free alkylbenzenesulfonate from which the amount of precipitated calcium alkylbenzenesulfonate can be determined can be determined.

The alkanolamines according to the invention surprisingly reduce the amount of calcium carbonate in the precipitate. The inhibition of the precipitation of calcium carbonate in the presence of alkylbenzenesulfonates and alkonolamines used in the invention can also be determined by qualitative and quantitative determination of the residue after filtration of a solution. As a simple method of measurement, it is also possible to track the turbidity and the surface tension.

Inhibition in the sense of the invention does not necessarily mean the complete suppression of sparingly soluble calcium precipitates, but according to the invention may also be a delay of calcium precipitation under conditions close to the application.

The reduction in the tendency to precipitate sparingly soluble calcium or magnesium salts, for example, reduces the formation of textile incrustations in textile laundering. The encrustations formed after repeated washing lead to a deterioration of the wearing properties of textiles and to an increase in graying. Textile upholstery, which after several times Laundry on the textile can be determined, for example gravimetrisch, by ashing of the fabric and annealing of the residue in the porcelain crucible.

New textiles have e.g. an ash content of less than 0.5% by weight. As the number of washes increases, depending on the detergent used, water hardness, washing temperature, tissue, etc., the ash content increases. After 25 washings ash contents of 3 wt.% And higher are quite common with commercial detergents and an average water hardness.

The washing and cleaning solutions may contain other ingredients in addition to the alkanolamines used in the invention. The detergents and cleaners according to the invention may contain anionic (a), nonionic (b) or cationic surfactants (c). In Central Europe, mixtures of anionic and nonionic products are typically used which exhibit synergistic washing effects and are often combined with soaps.

The amount of surfactant in the detergent and cleaner composition according to the invention, as far as these are present as powder detergents, is preferably from 3 to 70% by weight, for liquid formulations preferably from 15 to 80% by weight. However, the washing and cleaning agent according to the invention can also be present as anhydrous liquid formulations. These have an advantageously low viscosity compared to conventional liquid formulations.

Furthermore, the compositions of the invention contain from 0.001 to about wt .-% based on the total composition, enzymes.

A whole range of enzymes can be present in the formulations according to the invention, for example proteases, amylases, lipases, cellulases and peroxidases and mixtures of the respective enzymes. Other enzymes can be incorporated into detergent formulations, where they, like the aforementioned, from various sources of bacteria, fungi, z. As yeasts and other plants, but may also be of animal origin.

Different factors determine the selection of individual enzymes, such as the pH activity and / or stability optima, the thermostability, the stability to various surfactants, builders, etc. Enzymes can be up to 5 mg, preferably 0.01 mg to 3 mg active in weight percent Enzyme can be used on one gram of detergent formulation. For proteases, a use concentration of an activity of 0.005 to 0.1 Anson units (Anson Units = AU) per gram of formulation according to the invention applies.

The enzymes may be adsorbed in a manner known per se to excipients, embedded in encapsulants and / or granulated with the aid of excipients in order to make them easier to handle and protect against premature inactivation when they are to be incorporated into particulate detergents or cleaners ,

In the following, the optional constituents (a) to (l) of the detergent and cleaner composition according to the invention are explained:

(a) anionic surfactants (in addition to the alkylbenzenesulfonic acids or salts thereof used according to the invention). Examples of anionic, surface-active substances which may be part of the compositions according to the invention are ether carboxylic acids and their salts, alkyl sulfonates, alpha-olefinsulfonates, alpha-sulfofatty acid derivatives, sulfonates higher Fatty acid esters, higher alcohol sulfates (primary and secondary), alcohol ether sulfates, hydroxy mixed ether sulfates, alkoxylated carboxylic acid alkanolamide sulfates, salts of phosphate esters, taurides, isethionates, linear alkylbenzenesulfonates, bridged alkylbenzenesulfonates (such as DOWFAX types from Dow), alkylarylsulfonates, sulfates of polyoxyethylene fatty acid amides, and derivatives of Acylamino acids, alkylethercarboxylic acids, alkyl and dialkylsulphosuccinates, alkenylsulphosuccinates, Alkyl- or alkenyl-sarcosinates and sulfated glycerol-alkyl ethers.

As further anionic surfactants, especially soaps are contemplated, wherein saturated fatty acid soaps, such as the alkali and alkanolamine soaps of lauric acid, myristic acid, palmitic acid or stearic acid, as well as from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures, are suitable.

(b) nonionic surfactants: Further constituents of the compositions according to the invention may be compounds from the group of nonionic surfactants. As nonionic surfactants, the washing and cleaning agent according to the invention may contain in particular lower and higher ethoxylated alcohols. The ethoxylated alcohols are derived in particular from primary alcohols having preferably 6 to 18 carbon atoms. The low ethoxylated fatty alcohols have on average 1 to 8 moles and the higher ethoxylated alcohols have an average of 9 to 22 moles of ethylene oxide units. The stated degrees of ethoxylation represent statistical mean values which may be an integer or a fractional number for a specific product. The alcohol radical can be methyl-branched linearly or in the 2-position, or contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms are preferred, for example from coconut, tallow or oleyl alcohol. In addition to ethoxylated alcohols, it is of course also possible to use propoxylated or mixtures of ethoxylated / propoxylated alcohols. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Another class of nonionic surfactants which may also be used in combination with the above-mentioned nonionic surfactants are alkoxylated fatty acid methyl esters, e.g. are prepared according to the method described in WO 90/13533.

Without limiting the formulations thereto, as further examples of nonionic surfactants, fatty acid glycerides, fatty acid polyglycerides, fatty acid esters, alkoxylated fatty acid glycerides, polyoxyethylene oxypropylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, Polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, alkylamine oxides, derivatives of protein hydrolysates, hydroxy mixed ethers, alkylpolyglycosides and alkylglucamides (eg N-methyl-alkylglucamides).

(c) Cationic Surfactants: As examples of common cationic surface-active substances which can be used for combinations are alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, quaternized fatty acid esters of alkanolamines, alkylisoquinolinium salts, benzethonium chlorides and cationic acylamino acid derivatives. As examples of surfactants, ampholytes and betaines that can be used for combinations, be Carbobetaine such. Cocoacylamidopropyldimethylbetaine, acylamidopentanediethylbetaine, dimethylammoniohexanoate, acylamidopropane (or ethane) dimethyl (or diethyl) betaine - all with C chain lengths between 10 and 18, sulfobetaines, imidazoline derivatives, soybean oil lipids and lecithin. The above-mentioned amine N-oxides may also be present in polymeric form, wherein a ratio of amine to amine N-oxide of 10: 1 to 1: 1,000,000 must be present. The average molecular weight is 500 to 1,000,000, more preferably 5,000 to 100,000.

(d) Enzyme stabilizers: These include water-soluble sources of calcium and / or magnesium ions, which must be added frequently so that the builder system does not also remove and thus deactivate these central atoms of the enzymes. Calcium ions are generally more effective than magnesium ions here. Additional stabilization can be achieved by the addition of borates, for example in US Pat. No. 4,537,706. Typically, the formulations according to the invention contain 1 to 30, preferably 2 to 20, more preferably 5 to 15, and most preferably 8 to 12 millimoles of calcium ions per liter of final formulation.

Although the concentration in different formulations may vary depending on the enzymes used, there should always be enough calcium ions available after complexation by the builder system and soaps to keep the enzymes activated. Any water-soluble calcium or magnesium salt may be used, but the following examples, without limiting the formulations of the invention thereto, are mentioned: calcium chloride, formate, sulfate, hydroxide, malate, maleate, acetate, and the corresponding magnesium salts. Depending on the amount and type of enzymes used, the detergent formulations according to the invention contain from 0.05 to 2% by weight of water-soluble calcium and / or magnesium salts.

Borate stabilizers are present at 0.25 to 10% by weight, preferably 0.5 to 5% by weight and more preferably 0.75 to 3% by weight, calculated as boric acid, in the formulations according to the invention. The added borate stabilizers must be able to form boric acid, here the direct use of boric acid is preferred, but can also, without limiting, boron oxide, borax, other alkali metal borates and substituted boric acids such. As phenyl, butyl and p-Bromphenylboräure be used.

(e) Bleaching Systems - Bleaching Agents and Bleach Activators: For the formulations of the invention, the use of a bleach system, whether bleach and activator or only a bleach, is optional. If used, the bleaching agents are used in amounts of from 0.5 to 30% by weight, preferably from 5 to 20% by weight, and the bleach activators in amounts of from 0.1 to 60% by weight of the bleaching agent. Thus, from 0.5 to 40% by weight of bleach system, based on the formulation according to the invention, are preferably used. Any bleaching agent suitable for cleaning textiles, hard surfaces or other cleaning tasks may be used. These include, for example, oxygen-based bleaching agents. Perborates, e.g. As sodium perborates, whether as mono- or tetrahydrate, can be used, as well as percarboxylic acid bleach and salts thereof. Suitable representatives of this class include magnesium peroxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutanoic acid, diperoxydodecanedioic acid and, most preferably, 6-nonylamino-6-oxoperoxycapric acid. Peroxygen bleaching agents can also be used. Suitable representatives of this class include sodium carbonate peroxohydrate and comparable percarbonates, sodium pyrophosphate peroxohydrate, urea peroxohydrate, sodium peroxide and persulfate bleach. Mixtures of bleaching agents can also be used in the washing and cleaning agent formulations according to the invention.

Peroxygen bleaching agents are preferably combined with bleach activators, including without limitation the formulations of the invention, nonanoyloxy-phenylsulfonate, tetraacetylethylenediamine and mixtures thereof, and others described in U.S. Pat. 4,634,551 mentioned combinations of bleaching agents and activators.

Very particularly preferred as bleach activators are amide derivatives of the formulas R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L, where R ¹ an alkyl group having 6 to 12 carbon atoms, R ^{2 is} an alkylene group having 1 to 6 carbon atoms, R ^{5 is} a hydrogen atom or alkyl, aryl or alkylaryl having 1 to 10 carbon atoms and L is any nucleophilic leaving group (eg phenylsulfonate) , Examples which may be mentioned here are the following compounds: (6-octanamido-caproyl) oxyphenylsulfonate, (6-nonanamido-ca-proyl) oxyphenylsulfonate, (6-decanamido-caproyl) oxyphenylsulfonate and mixtures thereof.

Acyl lactam activators belong to a different class of preferred bleach activators. Particular mention may be made here of acylcaprolactam and acylvalerolactam having alkyl, aryl, alkoxyaryl and alkylaryl acyl groups containing from 1 to 16 carbon atoms. Included among the non-oxygen based bleaching agents sulfonated zinc and / or aluminum phthalocyanines to the preferred systems.

(f) Chelating Agents / Complexing Agents: In the formulation according to the invention, iron and manganese ions are also optionally included as chelating agents which belong to the group of aminocarboxylates, aminophosphonates, polyfunctionalized aromatics (eg dihydroxybenzenesulfonic acid derivatives). Also, mixtures of the various chelating agents are effective. A preferred biodegradable chelating agent is ethylenediamine disuccinate. The abovementioned agents are used in proportions of from 0.1 to 10% by weight, particularly preferably from 0.1 to 3.0% by weight, in the detergent formulation.

(g) Components for Removing Clay or Clay Dirt and Preventing Resoiling: The formulations according to the invention may contain for this purpose alkoxylated, preferably ethoxylated, amines, irrespective of whether these are mono-, oligo- or polymeric amines. For solid formulations, the amount used is 0.01 to 10 wt.%, In liquid formulations at 0.01 to 5 wt.% Of the total formulation. Other groups of compounds having these properties are cationic compounds (as in EP 0 111 984-A1), zwitterionic polymers (as in EP 0 112 592) or carboxymethyl cellulose, which also can enhance the soil-carrying capacity of a wash liquor. As additional graying inhibitors, water-soluble colloids are mostly of an organic nature, for example soluble starch preparations and degraded starch, aldehyde starches, etc. Preferred uses include polyvinylpyrrolidone.

(h) Polymeric dispersion aids (cobuilders): These additives are used in amounts of from 0.1 to 7.0% by weight of the overall formulation according to the invention, which are polycarboxylates or polyethylene glycols which enhance both the action of the builder used and also Prevent encrustations and re-soiling and play a role in the removal of particle dirt. The compounds which can be used here are obtained by polymerization or copolymerization of suitable unsaturated carboxylic acid or carboxylic acid anhydride monomers. Here, polyacrylates but also maleic anhydride / acrylic acid copolymers are preferred. The molecular weights of the former are in a range of 2,000 to 10,000 g / mol, preferably 4,000 to 7,000 g / mol, and more preferably in the range of 4,000 up to 5,000 g / mol. Suitable copolymers have molecular weights of 2,000 to 100,000 g / mol, preferably 5,000 to 75,000 g / mol and more preferably 7,000 to 65,000 g / mol. Useful polyethylene glycols have molecular weights in the range 500 to 100: 000, particularly preferably 1,500 to 10,000. Also polyasparagates and glutamates can be used together with zeolite builders, wherein the usable polyasparagates have average molecular weights of about 10,000.

(i) Optical brighteners: All optical brighteners known from the prior art can be used in the formulations according to the invention. They are incorporated to 0.05 to 1.2 wt.%, Based on the total formulation. Some non-limiting examples of suitable linking groups are: stilbene derivatives, pyrazolines, coumarin, carboxylic acids, methine cyanines, dibenzotholine-5,5-dioxide, azoles, 5- and 6-membered heterocycles.

(j) Foam inhibitors: Depending on the exact composition (ie foaming power of the surfactants used) and type of foam inhibitor, according to a further embodiment of the invention, from 0 to 5% by weight (based on total formulation) of foam inhibitor is used. Monofatty acid salts are used in an amount of 0 to 5% by weight, but preferably 0.5 to 3% by weight. Silicones are used in an amount of up to 2% by weight, but preferably 0.01 to 1% by weight, and especially preferably used from 0.25 to 0.5 wt.%. The compounds which can be used as foam inhibitor in the formulations according to the invention also include monofatty acids and their salts with C chain lengths of 10 to 24, but preferably 12 to 18 carbon atoms. Also high molecular weight non-surface active compounds, such as paraffins, fatty acid esters (eg triglycerides), aliphatic ketones, N-alkylated aminotriazines or di- to tetraalkyldiaminochlorotriazines, monostearyl phosphates and monostearyl alcohol phosphate esters. Silicones can also be used as foam inhibitors in the present formulation, as can mixtures of silicones and silane-modified silicates, in which case polyalkylene glycols can be used as the solvent. .

(k) Fabric softening agents : Various fabric softening agents useful in the washing process can be used herein, but especially smectite clays as well as other softening clays in amounts between 0.5 and 10 wt% (based on the total formulation). The aforementioned plasticizers can be used in Combination with other plasticizers such as amines and the common cationic plasticizers used.

(l) Further components: Further components can be incorporated into the detergent formulations: Further carriers, hydrotropes, processing aids, dyes or pigments, perfumes, preservatives, buffering systems, etc. To increase the foaming power and the fat-dissolving power, water-soluble alkaline earth salts in amounts from 0.001 to 3% by weight.

If necessary, some of the above-mentioned surfactant components can also be stabilized by adsorption on porous hydrophobic substances and incorporated into the formulation in a sealed manner with a further hydrophobic layer. Liquid detergents may also contain water, alcohols or other solubilizing agents. The water content of liquid detergents is for example between 40 and 80 wt .-%. Furthermore, anhydrous liquid detergents are the subject of the invention. The detergent formulations according to the invention may also be powdered types and granules or pasty or liquid products.

The detergents according to the invention can be prepared in a manner known per se, e.g. by mixing, granulating, extruding and / or by spray-drying. The builders zeolite and alkali silicate can be incorporated individually in a conventional manner and any order in the agent. The preparation of the liquid detergent products can be carried out by mixing the components.

The formulations may be detergents or cleaning agents. The detergent formulations show very good effectiveness both in laundry detergents for domestic use as well as in detergents for the commercial sector. For detergents, the fields of use of the formulations are e.g. Universal cleaner, cleaner for glass, cleaner for metal, plastic cleaner, floor cleaner and bath and toilet cleaner.

Example 1:

Delay the precipitation of poorly soluble calcium salts by addition of alkanolamines to alkylbenzenesulfonate-containing solutions.

The precipitation of poorly soluble calcium salts from solutions with calcium ions and carbonate ions was monitored by turbidity measurement (or transmission measurement). The solutions were mixed with calcium ions and then heated at a heating rate of 2 ° C / min.

Table 1 summarizes the different approaches. <b> Table 1 </ b> product unit 1 2 3 4 5 6 7 8th 9 10 Sodium alkyl benzenesulfonate (Marlon®A 350) mmol / l 2.5 2.5 2.5 2.5 2.5 Sodium lauryl sulfate mmol / l 2.5 2.5 Triisopropanolammoniumalkyl benzenesulfonate mmol / l 2.5 Sokalan® CP5 (BASF) mg / l 150 150 triisopropanolamine mmol / l 2.5 2.5 triethanolamine mmol / l 2.5 diisopropanolamine mmol / l 2.5 sodium g / l each 0.5 calcium chloride mmol / l each 1.78

990 ml of an aqueous solution (demineralized water) containing surfactant, alkanolamine and soda according to Table 1 were stirred at a temperature of 15 ° C under defined conditions. 10 ml of a concentrated calcium chloride solution (19.79 g / l CaCl ₂ ) was added to this solution so that the solution had a calcium ion concentration of 1.78 mmol / l (10 ° dH).

Immediately after adding the calcium chloride solution, the solution was started to be heated at a heating rate of 2 ° C / min. The transmission of the solution and the dynamic surface tension were measured at increasing temperatures. The determination of the dynamic surface tension was carried out with a bubble pressure tensiometer MPT2 Lauda (Königshofen, Germany) at a constant flow rate of 20 mm ³ / s. Table 2 summarizes the transmission and dynamic surface tension values at individual temperatures.

Without the addition of an anionic surfactant (approach 1), CaCO ₃ immediately precipitated as a sparingly soluble precipitate, which can be read off from the drop in transmission from 100% to 31%. With the addition of the commercial co-builder Sokalan® (registered trademark of BASF AG) CP5 (batch 6), the precipitation of calcium salts up to 60 ° C. was prevented.

The inventive approaches 3, 5 and 10 had compared to approach 1 and the approach 2 (LAS only) on a lower tendency to precipitate calcium salts. In these approaches, the interfacial activity of the alkylbenzenesulfonate is maintained, as evidenced by the lowering of the dynamic surface tension compared to the value of pure water (72 mN / m, 25 ° C).

For sodium alkylbenzenesulfonate, the lowering of the surface tension in the simultaneous presence of triisopropanolamine or diisopropanolamine is greater than in the solution without inventive alkanolamines.

The experiments showed that without the addition of surfactant, the formed CaCO ₃ precipitates immediately (approach 1). Also, the triisopropanolamine (TIPA) alone had no positive influence on the delay of CaCO ₃ precipitation. With the sodium salt of the alkylbenzene sulfonic acid LAS, the LAS calcium salt first forms at 15 ° C, before finally calcium carbonate precipitates at approx. 37.5 ° C (LAS-Na). If triisopropanolamine is added to the solution, then the CaCO ₃ precipitation is delayed up to a temperature of about 37.5 ° C. and no precipitation of calcium LAS is observed in the meantime, as shown, for example, by the low dynamic surface tension. Sokalan® CP5 (acrylic acid-maleic acid copolymer, BASF AG), which is used as a co-builder in detergents and cleaners, was measured as a reference. Diisopropanolamine showed similar behavior to triisopropanolamine. Also when Diisopropanolamin (DIPA) falls only a very small proportion of LAS calcium salt precipitates before calcium carbonate precipitates at approx. 37.5 ° C.

Sokalan® CP 5 (acrylic acid-maleic acid copolymer, BASF) used in a concentration of 150 mg / L together with the LAS-Na, inhibits the precipitation of calcium carbonate up to a temperature of about 60 ° C. When using the alkanolamines used in the invention even higher temperatures are reached. <b> Table 2 T. = tranparency in%, O. = surface tension in mN / m </ b> approach T = 20 ° C T = 30 ° C T = 40 ° C T = 50 ° C T = 60 ° C T. O. T. O. T. O. T. O. T. O. 1 31 73 33 71 34 70 31 68 32 67th 2 66 65 65 64 59 60 31 55 24 53 3 99 42 98 38 96 36 54 33 42 33 4 91 61 89 60 85 60 35 59 25 57 5 89 62 84 59 77 54 43 48 35 48 6 100 72 100 70 100 68 100 67 100 66 7 98 60 98 55 97 49 97 46 93 44 8th 34 66 11 64 13 62 53 59 31 59 9 35 69 6 67 7 67 9 64 13 60 10 98 42 98 37 95 36 55 33 41 33

Example 2: Washing tests with formulations containing LAS and triisopropanolamine in the Lini washing machine.

Washing tests were carried out in a Lini test machine, using the skin fat pigment soiling on polyester fabric, blended fabric and cotton fabric. As a model formulation, a formulation was selected with 1.72 g / l Marlon® A 350 (sodium alkylbenzenesulfonate, 50%), 0.48 g / l triisopropanolamine and 0.5 g / l sodium carbonate. Water with increasing calcium water hardness was used and the test areas were washed for 1 hour at a temperature of 30 ° C.

Table 3 shows the results at a wash temperature of 30 ° C after averaging across all tissue types. <b> Table 3 </ b> water hardness Washing value [%] Washing value [%] [Ca ²⁺ mmol / l] without triisopropanolamine with triisopropanolamine 0 19.8 21.0 1.78 17.2 16.2 3.56 15.2 15.0 5.34 1.5 13.3

At a water hardness of 5.34 mmol / l Ca ²⁺ almost no washing performance of the solution was observed in the experiment without triisopropanolamine. The washing performance of the alkylbenzenesulfonate solution with triisopropanolamine, however, even at the high water hardness of 5.43 mmol / l Ca ²⁺ still showed about 70% of the washing performance, which is obtained without water hardness.

Claims (14)

1. An alkaline washing and cleaning agent composition comprising as components

   (A) at least one alkyl benzene sulfonic acid or the salt thereof having a linear or branched alkyl residue comprising 8 to 24 carbon atoms,

   (B) at least one alkanolamine or the ammonium salt thereof having the general structural formula I

   

   wherein, each independently of one another,

   k, l, or m is 0, 1, 2, or 3, wherein k + l + m is>1,

   n is 0 or and

   R ^a , R ^b , or R ^c is a linear or branched hydrocarbon having 2 to 6 carbon atoms, wherein at least one R has 3 to 6 carbon atoms and R ^a , R ^b , or R ^c can be different for each k, l, or m, and

   (C) one or more builder(s) in an amount from 0 to 10 % by weight of the total composition, and

   furthermore enzymes in an amount from 0.001 to about 5 % by weight of the total composition, wherein the components (A) and (B) are used at a weight ratio from 7:1 1 to 1:1.
2. Composition of claim 1 comprising as component
   (B) at least one alkanolamine or the ammonium salt thereof having the general structural formula II,

   

   wherein, each independently of one another,

   k, l, m is 0, 1, 2, or 3, wherein k + l + m is >1,

   n is 0 or 1 and

   R ¹ , R ² or R ³ is independently of one another H or linear or branched C₁ to C₄ alkyl residues, wherein at least one R represents a CH₃ group and R ¹ , R ² , or R ³ can be different for each k, l, or m.
3. Composition of claim 1,
   characterized in that the alkanolamine comprises at least two isopropanol residues.
4. Composition according to any one of the preceding claims,
   characterized in that the alkyl benzene sulfonic acid or the salt thereof has a linear alkyl residue comprising 8 to 24 carbon atoms.
5. Composition according to any one of the preceding claims, which comprises the components (A) and (B) at a molar ratio from 2 : 1 to 1 : 2, preferably 1.2 : 1 to 1 : 0.8.
6. Composition according to any one of the preceding claims, which comprises one or several builder(s) in an amount from 0.01 to 5 % by weight of the total composition, preferably no builder.
7. Composition according to any one of the preceding claims, which preferably comprises no insoluble builder.
8. Composition according to any one of the preceding claims, which further comprises as component
   (D) 0.001 to 3 % by weight of divalent metal ions or the salts thereof, particularly calcium or magnesium, based on the ratio of metal ion weight to total composition weight.
9. Composition according to any one of the preceding claims as a liquid formulation comprising 15 to 80 % by weight surfactant.
10. Composition according to any one of the preceding claims as a liquid formulation not comprising any water.
11. Use of a composition according to any one of the preceding claims for washing and/or cleaning with the use of additives comprising divalent metal salts, particularly calcium.
12. Use according to claim 11,
    characterized in that the additive is water comprising calcium ions in a concentration from 0.2 to 6 mmol/l.
13. Use of a composition according to any one of claims 1 to 10 for washing and cleaning textiles.
14. A method of reducing the amount of divalent metal salts, particularly calcium salts, which precipitate in the form of an insoluble deposit when washing and cleaning especially textiles, in comparison with conventional alkyl benzene sulfonate comprising washing and cleaning agents, which comprise no alkanolamines according to any one of claims 1 to 10, by the use of an alkaline washing and cleaning agent composition comprising as components

    (A) at least an alkyl benzene sulfonic acid or the salt thereof having a linear or branched alkyl residue comprising 8 to 24 carbon atoms,

    (B) at least an alkanolamine or the ammonium salt thereof having the general structural formula 1

    

    wherein, each independently of one another,

    k, l, or m is 0, 1, 2, or 3, wherein k + l + m is >1,

    n is 0 or 1 and

    R ^a , R ^b , or R ^c is a linear or branched hydrocarbon having 2 to 6 atoms, wherein at least one R has 3 to 6 carbon atoms and R ^a , R ^b , or R ^c can be different for each k, l, or m, and

    (C) one or several builder(s) in an amount from 0 to 10 % by weight of the total composition, wherein the components (A) and (B) are used at a weight ratio from 7:1 to 1:1.