ES2259954T3 - COMPOSITION OF WASHING AGENT AND CLEANING ALKALINE CONTAINING SULPHONATES OF ALKYLBENZENE AND ALCANOLAMINES. - 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

Composition of washing and cleaning agent alkaline containing alkylbenzene sulfonates and alkanolamines

The invention relates to compositions of alkaline washing and cleaning agents containing sulphonates of alkylbenzene and alkanolamines, as well as a procedure for washing or cleaning under use of such compositions and under use of wash water rich in calcium ions. The invention is referred to in special to the use of alkanolamines for the improvement of hardening stability of alkylbenzene sulphonates in alkaline washing and cleaning agents, and the delay of precipitation of calcium carbonate from such compositions of washing and cleaning agents.

Sodium alkylbenzene sulphonates, in especially those with linear alkyl residues (LAS), are agents surfactants that, due to their washing power, biodegradability and economical obtaining, they are frequently used in washing agents and cleaning. These washing and cleaning agents contain, by example, LAS typically in amounts of 3 to 30% by weight, in addition to other components generally known as adjuvants, bleaching agents, perfuming substances, foam inhibitors, etc.

The use of alkanolamines is also known. in washing and cleaning agents. These are used, among others things, for the neutralization of anionic surfactants. Is known that the surfactant neutralization products anionic with alkanolamines, unlike the use of salts alkaline metals, and preferably against these, prevent formation of crystalline fluid surfactant phases in the formulation. WO 96/07724 describes, by way of example, gels of single-phase soap and viscous soap formulations, in which they use the neutralization products of fatty acids with the alkanolamines, such as triethanolamines, to obtain homogeneous formulations.

US 4,105,592 describes a washing agent liquid containing nonionic and anionic surfactants, in addition to alkanolamines and smaller fractions of additives, such as corrosion inhibitors based on fatty acids and salts alkaline The alkanolamines are used for the neutralization of alkylbenzenesulfonic acids and other acidic components, using the alkanolamines preferably in excess, to act simultaneously as a buffer in the formulation, and guarantee a pH from 7 to 9. Alkanolamines are referred to exclusively as alkanolamines with 1 or 2 carbon atoms.

US 4,476,045 describes compositions of highly concentrated surfactants for use as raw material for washing, containing sulfates or sulphonates organic in the acid form, which are neutralized with an amine secondary or tertiary with at least 3 carbon atoms in the atom of nitrogen, and also a hydroxy group in position 2 or 3.

The washing and cleaning solvent is used frequently running water, which contains, among others, ions calcium and magnesium (hard running water). Surfactants anionics, such as alkylbenzene sulphonates or sulfates of fatty alcohol, form poorly soluble salts with ions hardeners. If the anionic surfactant precipitates as poorly soluble deposit, this results in a portion of Surfactant is no longer available for cleaning, so that the concentration in substance with washing activity in the bathroom it is reduced, and it results in a reduced washing result. In addition, the poorly soluble precipitate has the property of fixing to the substrate to be cleaned. In the washing of textile materials observe, therefore, an increase in material embedding textiles In cleaning hard surfaces, on the surface precipitates, or impurities, are formed that lead to a decrease of brightness

To prevent precipitation of deposits little soluble anionic surfactants with calcium or magnesium adjuvants that have the committed to bind calcium and magnesium ions, and prevent precipitation of anionic surfactants. As adjuvants are they use, by way of example, zeolites or silicates. However, due to its property of forming soluble complexes with ions hardeners, large-scale soluble phosphates are also used or hydroxy acids, such as citrates.

Hardener ions not only reach the bathroom washing through the water used, but frequently They are also components of dirt. Occasionally, also in the washing agents themselves are contained calcium ions or magnesium to obtain special advantages in the performance of cleaning, adjuvant action or the preparation of washing agent. In this case, through the use of adjuvants, complexing agents or similar, the deposit of calcium precipitates or Slightly soluble magnesium on the substrate to be cleaned.

Therefore, there have been no attempts to develop additives that are used in the washing process and cleaning, which inhibit the precipitation of calcium deposits from anionic surfactants and carbonate formation of calcium. DE 43 109 95-A1 describes, by way of for example, the use of polyaspartic acids in formulations of cleaning agents WO 96/19445 describes diaminoalkyldisulfosuccinates as adjuvant substances in washing agent formulations for applications where it is the abduction of water hardness is necessary.

The procedures for the inhibition of precipitation of calcium salts in the washing and cleaning process,  known for the state of the art, they have the disadvantage of that make the use of expensive additives necessary, such as adjuvants, or adjuvants.

In addition, to avoid the formation of precipitates poorly soluble calcium or magnesium salts of surfactants  Anionic attempts have been made to formulate washing and cleaning agents mainly based on surfactants insensitive to hardness, such as alcoholic ethoxylates, to be able to dispense with water thinning in this way. Due to the good washing performance of anionic surfactants, in especially for soils that contain pigments, or mud type, together with economic productivity and good workability, however, in most cases you cannot do without of the use of anionic surfactants.

Therefore, there was the task of finding a economic and harmless alternative from the point of view toxicological to the known adjuvants, or to the reduction of use of adjuvants, by which it could be inhibited, or delay the precipitation of calcium salts in the intervals of relevant temperature in washing and cleaning agents that contain alkylbenzene sulphonate during the process of cleaning.

Surprisingly, it was discovered that, by simultaneous presence of special alkanolamines in combination with alkylbenzenesulfonic acids, or their salts in the wash bath, both the precipitation of calcium salts of alkylbenzene sulphonate, as well as the precipitation of calcium carbonate are grossly inhibited.
dispersed.

Accordingly, they are the subject of the invention. alkaline washing and cleaning agent compositions that contain as components

(TO)

    at least one alkylbenzenesulfonic acid, or its salt, which it has a linear or branched alkyl moiety with 8 to 24 atoms of carbon,

(B)

     at least one alkanolamine, or its ammonium salt, which has the general structural formula I,

one

where respectively so independent between yes,

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

n

is 0 or 1, and

R a, R b or R c    it is a linear or branched hydrocarbon with 2 to 6 atoms of carbon, presenting at least one R 3 to 6 carbon atoms, Y

(C)

     at 0 to 10% by weight, based on the total composition, one or several adjuvants, and

also in a 0.001 a approximately 5% by weight, based on the total composition, enzymes, using components (A) and (B) in proportion weight 7: 1 a 1: 1.

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

The ammonium salts of alkanolamines used according to the invention are protonated alkanolamines (n = 1), R a, R b or R c are linear or branched hydrocarbons divalents, which are preferably linear, and are substituted with oxygen, or nitrogen in position 1,2. Hydrocarbons R a, R b or R c preferably present in sum minus 5, and at most 15 carbon atoms, especially preferably at least 6, better still at least 7, and at most 12 carbon atoms The alkanolamines used according to the invention They preferably have at least two isopropanol residues.

Preferred alkanolamines, or their salts ammonia, can also be described by the formula general structural II

2

where the remains, or indexes, respectively independently of each other, They are:

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

n

0 or 1, and

R 1, R 2 or R 3    independently of each other, H or linear alkyl moieties or branched with 1 to 4 carbon atoms, representing at least one R a group SCH_ {3}.

According to another conditioning of the invention, alkylbenzenesulfonic acids, or their salts, have a linear alkyl moiety with 8 to 24 carbon atoms.

Components (A) and (B) can be used also in a ratio of 2 to 1 to 1 to 2, preferably 1.2 1 to 1 to 0.8, referred to the molar concentration.

In another embodiment of the invention, the adjuvant fraction (C) of the washing agent composition and cleaning preferably amounts to 0.1 to 5% by weight, referred to the total composition. In a form of execution especially preferred, the presence is completely dispensed with of insoluble adjuvant.

Solid formulations may contain, by example, at least about 0.5% by weight of formulations liquid and granulated formulations of 5 to 50% by weight of adjuvants In this case, both systems can be used inorganic as well as organic. These are used in washing agent formulations to promote the elimination of particle dirt, and control water hardness.

Among inorganic adjuvants, not limited to the formulations according to the invention, there are alkaline salts, ammonium and alkanolammonium polyphosphates (for example tripolyphosphates, pyrophosphates and polymeric metaphosphates), phosphonates, silicates, carbonates (also bicarbonates and sesquicarbonates), sulfates and alumosilicates.

Examples of silicate adjuvants especially those with a SiO2 ratio with respect to Na 2 O 1.6 to 1 to 3.2 to 1, and stratified silicates, such as sodium silicates of the NaMSi x O 2x + 1 and H 2 O type (M represents Na or H, x = 1.9 -4, y = 0-20), is the type designated with SKS-6 In this case they can also be used magnesium silicates The alumosilicates are equally useful in the formulations according to the invention, and especially important in formulations of granulated washing agents. The adjuvants of employable alumosilicate can be described by the formula empirical [M_ {z} (zAlO2) y} xH2 O, adopting z e and values of at least 6, placing the proportion molar of z with respect to y in the range of 1.0 to 0.5, being able to adopt x values of approximately 0 to 30. You can try both crystalline and amorphous, synthetic or synthetic alumosilicates present in nature.

Also the organic adjuvants belong to the adjuvants employable in the formulations according to the invention. These include polycarboxylates, such as ether, cyclic or acyclic carboxylates, hydroxypolycarboxylates, copolymers of maleic acid anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, which can all be used in the form of acid or its alkaline ammonium or organoamonic salts. The alkyl, ammonium or organoammonium salts of polyacetic acid are equally suitable as citric acid salts, or combinations of various adjuvants. Especially preferred adjuvants are alkenyl succinic acids and salts. The monocarboxylic acid salts may also be incorporated separately, or in combination with one of the adjuvants mentioned above in the formulations according to the
invention.

Another component of the compositions according to the invention are:

(D)

     in 0.001 to 8% in, preferably 0.5 to 5% by weight, referred to the weight ratio of metal ion to total composition of divalent metal ions, or their salts, especially calcium or magnesium ions.

The composition according to the invention is used advantageously for washing and / or cleaning under the use of additives containing divalent metal salts, especially calcium, by example in compositions containing water and calcium ions in a concentration of 0.2 to 6 mmol / l in the wash composition.

It is also the subject of the composition according to invention a product that is obtained by neutralizing alkylbenzenesulfonic acids used according to the invention with the alkanolamine used according to the invention.

Examples of alkanolamines used according to invention triisopropanolamine, dietanolmonoisopropanolamine, monoethanolamindiisopropanolamine, butanolisopropanolamine, hexanolisopropanolamine, etc., or mixtures thereof, for example, with a mixture of mono-, di- and triisopropanolamine. Alkanolamines used according to the invention are also those that are accessible by alkoxylated, for example, with propylene oxide, for example ammonia, alkanolamines or alkylamines.

       \ newpage
    

Surprisingly it was discovered that the presence of alkanolamines according to the invention in formulations containing alkylbenzenesulfonic acids, or their salts, reduce the tendency of precipitation of alkylbenzenesulfonic acids in the form of its calcium alkylbenzenesulfonates.

The tendency to precipitation of salts from calcium, for example calcium alkylbenzenesulfonates, or Calcium carbonate, can be determined simply, by example, according to the following methods:

-

         by determining the residue after filtration of a alkylbenzene sulfonate solution (approximately 1 g / l), at which add increasing amounts of calcium hardness,

-

         by monitoring the turbidity of a diluted solution (approximately 1 g / l) of alkylbenzene sulphonate in the case of addition of calcium hardness, or

-

         by determining the dynamic surface tension of the solution you can determine the amount of sulfonate of free alkylbenzene, from which the amount of precipitated calcium alkylbenzenesulfonate.

The alkanolamines according to the invention reduce surprisingly the amount of calcium carbonate in the precipitate. The carbonate precipitation inhibition of calcium in the presence of alkylbenzene sulphonates and alkanolamines used according to the invention can be calculated also by qualitative and quantitative determination of residue after filtration of a solution. As a measurement method simple also offers opacity monitoring and surface tension

Inhibit within the meaning of the invention no necessarily means the complete suppression of precipitates from Slightly soluble calcium, but also within the meaning of the invention may be a delay in calcium precipitation under conditions next to application.

The reduction of the tendency to precipitation of poorly soluble calcium or magnesium salts reduces, by way of example in the washing of textile materials, the formation of inlays in textile materials. The inlays formed in repeated washing lead to a reduction in properties of use of textile materials and an increase in gray. The textile inlays, which have been formed on the textile material  after repeated washing, they can be determined, by way of example, by gravimetry, by incineration of the tissue and calcined of the residue in porcelain crucible.

The new textile materials present, by For example, an ash content of less than 0.5% by weight. With increasing number of washes, depending on washing agent used, hardness of water, washing temperature, fabric, etc., the content in Ashes increases. After 25 washes with boiling water, with Commercial washing agents and an average water hardness are Absolutely common ash content of 3% by weight.

Washing and cleaning solutions can contain other components, in addition to the alkanolamines used according to the invention. Washing and cleaning agents according to the invention may contain anionic surfactants (a), not ionic (b) or cationic (c). In central Europe they are used typically mixtures of anionic and nonionic products, which show synergistic wash effects and combine frequently with soaps.

The amount of surfactants in the composition of washing and cleaning agents according to the invention, in both this is present as a powder washing agent, ascends preferably at 3 to 70% by weight, for formulations liquid, preferably 15 to 80% by weight, the agents of washing and cleaning according to the invention can also be presented as water-free liquid formulations. These present a advantageously reduced viscosity against liquid formulations conventional.

The compositions according to the invention contain also 0.001 to 5% by weight of enzymes, referred to the total composition

In the formulations according to the invention they can be contained a whole series of enzymes, for example proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures of respective enzymes. Other enzymes can also be incorporated into washing agent formulations, which can proceed as those cited above, of the most diverse origins from bacteria, fungi, for example yeasts, and other plants, but It can also be of animal origin.

Different factors determine the selection of isolated enzymes, such as pH activity optimal and / or stability, thermostability, stability against various surfactants, adjuvants, etc. Enzymes are can be used in weighing up to 5 mg, preferably 0.01 mg to 3 mg of active enzyme with respect to one gram of agent formulation washed. An employment concentration of one is valid for proteases 0.005 to 0.1 Anson activity (Anson Units = AU) per gram of formulation according to the invention.

Enzymes may have been adsorbed on supporting substances, housed in enveloping substances and / or granulated with the help of supporting substances, to make them more easily manageable and protect against a deactivated premature, if these should be incorporated into washing agents or cleaning in the form of particles.

The components are explained below. optional (a) to (l) of the washing agent composition and cleaning according to the invention:

(to)

Anionic surfactants (in addition to the alkylbenzenesulfonic acids used according to the invention, or their salts). As examples of anionic surfactants, which may be a component of the compositions according to the invention, ether carboxylic acids and their salts, alkyl sulphonates, α-olefin sulfonates, α-sulfograse acid derivatives, ester sulphonates of higher fatty acids, higher alcoholic sulfates (primary and secondary), alcoholic ether sulfates, mixed hydroxyether sulfates, alkoxylated carboxylic acid alkanolamide sulfates, phosphate ester salts, taurides, isethionates, linear alkylbenzene sulphonates, bridged alkylbenzene sulphonates (as Dowfax types from Dow), alkylaryl sulphonates, sulfates of polyoxyethylene fatty acid amides, and derivatives of acylamino acids, alkylethercarboxylic acids, alkyl and dialkyl sulfosuccinates, alkenyl sulphosuccinates, alkyl or alkenyl sarcosinates and sulfated glycerine alkyl ethers.

As agents additional anionic surfactants come into consideration in special soaps, fatty acid soaps being appropriate saturated, such as alkaline acid alkanolamine soaps lauric, myristic acid, palmitic acid or stearic acid as well as mixtures of soaps derived from natural fatty acids, by example coconut, palm kernel or tallow fatty acids.

(b)

Non-ionic surfactants : Other components of the compositions according to the invention may be compounds of the group of non-ionic surfactants. As non-ionic surfactants, the washing and cleaning agent according to the invention may contain, in particular, alcohols of reduced and high degree of ethoxylate. Ethoxylated alcohols are derived in particular from primary alcohols, preferably with 6 to 18 carbon atoms. Fatty alcohols of reduced ethoxylate grade have an average of 1 to 8 moles, and higher ethoxylate grade alcohols average 9 to 22 moles of ethylene oxide. In this case, the degrees of ethoxylate indicated represent statistical mean values, which can be an integer or fractional number for a special product. The alcoholic moiety can be linear, or be branched with methyl in position 2, or contain linear and branched moieties with methyl in mixture, as well as usually present in oxoalcohol moieties. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example coconut alcohol, tallow or oleic alcohol, are especially preferred. In addition to ethoxylated alcohols, of course, propoxylated alcohols, or mixtures of ethoxylated / propoxylated alcohols, can also be used. Preferred alcoholic ethoxylates have a limited homolog distribution (narrow range ethoxylates, NRE).

Other class of non-ionic surfactants, which can also be used in combination with the agents nonionic surfactants mentioned above are esters methyls of alkoxylated fatty acids, which are obtained by example, according to the procedure described in WO 90/13533.

Without limiting the formulations to these, cite as additional examples of non-ionic surfactants fatty acid glycerides, fatty acid polyglycerides, fatty acid esters, alkoxylated fatty acid glycerides, polyoxyethylene oxypropylene glycol fatty acid esters, esters of polyoxyethylene sorbitan fatty acids, derived from polyoxyethylene-castor oil or castor oil hardened, polyoxyethylenelanoline derivatives, acid amides polyoxyethylene grease, polyoxyethylene alkylamines, oxides of alkylamine, derivatives of protein hydrolysates, hydroxyethers mixed, alkyl polyglycosides and alkylglucamides (for example N-methyl alkylglucamides).

(C)

Cationic surfactants : as examples of cationic surfactants in common use, which can be used for combinations, mention alkyltrimethylammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethylbenzylammonium salts, alkyl dimethylbenzylammonium salts, alkylpyridinium salts, quaternum fatty acid esters, salts of alkyl isoquinolinium, benzethonium chlorides and cationic acylamino acid derivatives. As examples of surfactants, ampholytes and betaines, which can be used for combinations, cite carbobetaines, such as coco-acylamidopropyl dimethylbetaine, acylamidopentanedimethylbetaine, dimethylammonium-hexanoate-acylamidopropan- (o-ethan-) dimethyl- (o-diethyl -) all with carbon chain lengths between 10 and 18, sulfobetaines, imidazolinium derivatives, soybean oil and lecithin lipids. The mentioned amine N-oxides can also be presented in polymeric form, having an amine ratio with respect to amine N-oxide of 10: 1 to 1: 1,000,000, the average molecular weight amounts to 500 to 1,000,000 , but especially preferably 5,000 to 100,000.

(d)

Enzymatic stabilizers : to these belong water-soluble sources of calcium and / or magnesium ions, which must be added frequently so that the adjuvant system does not also remove these central atoms from enzymes, and deactivate them in this way. In this case, calcium ions are generally more effective than magnesium ions. Additional stabilization can be performed by adding borane, as is done, for example, in US 4,537,706. Typically, the formulations according to the invention contain 1 to 30, preferably 2 to 20, especially preferably 5 to 15, and most particularly preferably 8 to 12 millimoles of calcium ions per liter of final formulation.

Although the concentration in various Formulations may vary depending on the enzymes employed, sufficient calcium ions should always be available after complexed through the adjuvant system and through soaps, to keep enzymes activated. Any salt can be used water soluble calcium or magnesium, in this case mention the following examples, without limiting the formulations to them according to the invention: chloride, formate, sulfate, hydroxide, malate, maleate, calcium acetate, and the corresponding salts of magnesium. Depending on the amount and type of enzymes employees, washing agent formulations according to the invention contain 0.05 to 2% by weight of calcium salts and / or Water soluble magnesium.

Borate stabilizers are contained in the formulations according to the invention by 0.25 to 10% by weight, preferably 0.5 to 5% by weight, and especially preferably 0.75 to 3% by weight, calculated as boric acid. Borate stabilizers added must be fit to form boric acid, in this case the direct use of acid is preferred boric, but can also be used, but not limited to them, boron oxide, borax, other alkali borates and boric acids substituted, such as phenyl-, butyl- and acid p-bromophenylboric.

(and)

Bleaching systems - bleaching agents and bleaching activators : for formulations according to the invention, the use of a bleaching system, either bleaching agent and activator, or only a bleaching agent, is optional. As long as they are used, bleaching agents are applied in amounts of 0.5 to 30% by weight, preferably 5 to 20% by weight, and bleaching activators are applied in amounts of 0.1 to 60% by weight of the bleaching agent. Therefore, preferably 0.5 to 40% by weight of bleaching system is used, based on the formulation according to the invention. All appropriate bleaching agents can be used for cleaning textile materials, hard surfaces, or other cleaning tasks. These include, for example, bleaching agents that work with oxygen. Perborates, for example sodium perborates, either as mono- or tetrahydrate, can be used, as well as percarboxylic acid bleaching agents and their salts. Appropriate representatives of this class include magnesium peroxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxyperoxybutanoic acid, diperoxidedecanoic diacid and, especially preferably, 6-nonylamino-6-oxoperoxicaprinic acid. Peroxide bleaching agents can be used in the same way. Appropriate representatives of this class include sodium carbonate peroxohydrate and comparable percarbonates, sodium pyrophosphate peroxohydrate, urea peroxohydrate, sodium peroxide and persulfate bleaching agents. Mixtures of bleaching agents can also be used in the formulations of washing and cleaning agents according to the invention.

\hbox{otras
combinaciones de agentes y activadores de blanqueo mencionadas en la
U.S. 4,634,551.}

Peroxide bleaching agents are preferably combined with bleaching activators to which, without limiting the formulations according to the invention, belong nonanoyloxy-phenyl sulfonate, tetraacetylethylenediamine and mixtures thereof, as well as

 \ hbox {others
bleaching agent and activator combinations mentioned in the
US 4,634,551.} 

As bleach activators they are very especially preferred 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, R 1 meaning an alkyl group with 6 to 12 carbon atoms, R 2 an alkylene group with 1 to 6 carbon atoms, R 5 a hydrogen atom or alkyl-aryl- or alkylaryl with 1 to 10 carbon atoms, and L any leaving group appropriate nucleophile (eg phenyl sulfonate). In this cite the following compounds as examples: (6-octanamido-caproyl) oxyphenyl,  sulfonate of (6-nonanamido-caproyl) oxyphenyl, sulfonate of (6-decanamido-caproyl) oxyphenyl, and their mixtures.

Acillactam activators belong to another class of preferred bleach activators. In this case mention especially acilcaprolactam and acilvalerolactam with alkyl, aryl, alkoxyaryl and alkylaryl groups, containing 1 to 16 carbon atoms Among bleaching agents not based on oxygen, sulfonated zinc and / or aluminum phthalocyanines They belong to the preferred systems.

(F)

Chelating / complexing agents : in the formulation according to the invention, iron and manganese ion complexing agents are optionally also contained under the formation of chelates, which belong to the group of aminocarboxylates, aminophosphonates, polyfunctionalized aromatic compounds (for example dihydroxybenzenesulfonic acid derivatives). Mixtures of various chelating agents are also effective. A preferred biodegradable chelating agent is ethylenediamine disuccinate. The agents mentioned above are used in fractions of 0.1 to 10% by weight, particularly preferably 0.1 to 3.0% by weight, in the washing agent formulation.

(g)

Components for the removal of dirt from clay or mud and inhibition of the new fouling : the formulations according to the invention may contain for this purpose alkoxylated amines, preferably ethoxylated, regardless of whether in this case it is a question of monomeric, oligomeric or polymeric amines. For solid formulations, the amount of use is 0.01 to 10% by weight, in liquid formulations 0.01 to 5% by weight of total formulation. Other groups of compounds that exhibit these properties are cationic compounds (as in EP 0 111 984-A1, zwitterionic polymers (as in EP 0 112 592) or carboxymethyl cellulose, which can also increase the dirt-holding power of a bath of Washing As additional agrisado inhibitors, water-soluble colloids are suitable, in most cases of an organic nature, for example soluble starch preparations, and for example degraded starch, aldehyde starches, etc. Find preferred employment, among others, polyvinylpyrrolidone.

(h)

Polymer auxiliary dispersion agents (adjuvants) : these additives are used in amounts of 0.1 to 7.0% by weight of the total formulation according to the invention, being polycarboxylates or polyethylene glycols, which both enhance the action of the adjuvant employed, as they also prevent scale and new dirt, and play a role in the release of particulate dirt. The compounds used in this case are obtained by polymerization or copolymerization of appropriate carboxylic acid monomers or unsaturated carboxylic acid anhydride. In this case, polyacrylates are preferred, but also copolymers of maleic acid / acrylic acid anhydride. The molecular weights of the former move in a range of 2,000 to 10,000 g / mol, preferably 4,000 to 7,000 g / mol, and especially preferably in the range of 4,000 to 5,000 g / mol. Appropriate copolymers have molecular weights of 2,000 to 100,000 g / mol, preferably 5,000 to 75,000 g / mol, and especially preferably 7,000 to 65,000 g / mol. The employable polyethylene glycols have molecular weights in the range of 500 to 100,000, particularly preferably 1,500 to 10,000. Polyaspartates and polyglutamates may also be used together with zeolite adjuvants, with the employable polyaspartates having average molecular weights of approximately 10,000.

(i)

Optical clarifiers: in the formulations according to the invention all optical clarifiers known according to the state of the art are employed. These are incorporated in 0.05 to 1.2% by weight, based on the total formulation. Some non-limiting examples of groups of appropriate compounds are cited below: stilbene derivatives, pyrazolines, coumarin, carboxylic acids, methincyanines, 5,5-dibenzothiophene dioxide, azoles, 5 and 6 link heterocycles.

(j)

Foam inhibitors : according to the exact composition (i.e. foaming power) of surfactants used and type of foam inhibitor, according to another conditioning of the invention, 0 to 5% by weight (based on the total formulation) of the inhibitor of foam. Salts of fatty monoacids are used in an amount of 0 to 5% by weight, but preferably 0.5 to 3% by weight. The silicones are used in an amount up to 2% by weight, but preferably 0.01 to 1% by weight, and especially preferably from 0.25 to 0.5% by weight. The compounds that can be used in the formulations according to the invention as a foam inhibitor also include fatty monoacids and their salts, with carbon chain lengths of 10 to 24, but preferably 12 to 18 carbon atoms. Also high molecular weight compounds, non-surfactants, such as paraffins, fatty acid esters (for example triglycerides), aliphatic ketones, N-alkylated aminotriazines or di- to tetraalkyl diamine chlorotriazines, monostearyl phosphates and monostearyl alcohol phosphate esters. In the present formulation silicones can also be used as foam inhibitors, as well as mixtures of silicones and silicates modified with silane, in general, in this case polyalkylene glycols can be used as solvents.

(k)

Textile softeners : in this case, various textile softeners can be used in the washing process, but preferably smectite clays, as well as other softening clays, in amounts between 0.5 and 10% by weight (based on the total formulation ). The softeners mentioned above can be used in combination with other softeners, such as amines, and the extended cationic softeners.

(l)

Other components : in the formulations of washing and cleaning agents, other components can be incorporated: additional supports, hydrotropic agents, auxiliary process agents, dyes or pigments, perfumes, preservatives, buffer systems, etc. In order to increase the foaming power and the fat-dissolving strength, water-soluble alkaline earth salts can also be added in amounts of 0.001 to 3% by weight.

As necessary, some of the surfactant components mentioned above can be also stabilize by adsorption on porous substances hydrophobic, and seal with another hydrophobic layer, and incorporate into the formulation. Liquid washing agents may also contain water, alcohols or other solubilizing agents. The content in water of liquid washing agents is, by way of example, between 40 and 80% by weight, in addition, they are also subject to invention water-free liquid washing agents. In the case of the washing agent formulations according to the invention can be also deal with powdery and granulated types, or products pasty or liquid.

The washing agents according to the invention are they can obtain in a manner known per se, for example by mixing, granulating, extrusion and / or spray drying. In this case, zeolite and alkali silicate adjuvants can be incorporate into agents separately in a manner known per se and in any order. Obtaining liquid washing products is It can be done by mixing the components.

In the case of formulations it can be treated of washing agents or cleaning agents. The formulations of washing agents show very good efficacy in both agents of washing textile materials for the domestic sector, such as also in washing agents for the industrial sector. If of cleaning agents, the fields of employment of the formulations they are, for example, universal cleaners, glass cleaners, metal cleaners, synthetic materials cleaners, floor cleaners and bathroom and toilet cleaners.

Example 1 Delayed precipitation of poorly soluble calcium salts by adding alkanolamines to solutions containing alkylbenzene sulfonate

The precipitation of calcium salts little soluble from solutions with calcium ions and carbonate ions  it was followed by opacity measurement (or measure of transmission). The solutions were mixed with calcium ions, and at then they were heated with a heating rate of 2ºC / min.

Table 1 shows the different loads

TABLE 1

Product Unity one 2 3 4 5 6 7 8 9 10 alkylbenzenesulfonate sodium mmol / l 2.5 2.5 2.5 2.5 2.5 (Marlon ®A 350) lauryl sulfate sodium mmol / l 2.5 2.5 alkylbenzenesulfonate from mmol / l 2.5 triisopropanolammonium Sokalan® CP5 mg / l 150 150 (BASF) triisopropanolamine mmol / l 2.5 2.5 triethanolamine mmol / l 2.5 diisopropanolamine mmol / l 2.5 sodium carbonate g / l respectively 0.5 calcium chloride mmol / l respectively 1.78

They were stirred at a temperature of 15 ° C under defined conditions 990 ml of an aqueous solution (water demineralized) containing surfactant, alkanolamine and Soda according to Table 1. 10 ml of a solution was added to this solution. concentrated calcium chloride solution (19.79 g / l of CaCl2), so that the solution presented a calcium ion concentration of 1.78 mmol / l (10ºdH).

Directly after adding the solution of calcium chloride began to heat the solution with a heating speed of 2ºC / min. The transmission of the solution and dynamic surface tension were measured at temperatures growing The determination of the dynamic surface tension is performed with a firm MPT2 blow pressure tensiometer Lauda (Königshofen, Germany) at a constant flow rate of 20 mm3 / s. Table 2 shows the transmission values and of dynamic surface tension at isolated temperatures.

No addition of an anionic surfactant (load 1), CaCO 3 immediately precipitated as a little deposit soluble, which can be read in the descent of the transmission of a 100% to 31%. In the case of adding the commercial adjuvant Sokalan® (registered trademark of BASF AG) CP5 (charge 6), the precipitation of calcium salts up to 60 ° C.

Charges 3, 5 and 10 present, in comparison with load 1 and load 2 (LAS only), a smaller trend to the precipitation of calcium salts. In these charges it remains the interfacial activity of alkylbenzene sulfonate, which is known by lowering the dynamic surface tension compared to the value of pure water (72 mN / m, 25 ° C).

For sodium alkylbenzenesulfonate, the decrease of surface tension with simultaneous presence of triisopropanolamine or diisopropanolamine is greater than in the solution without alkanolamines according to the invention.

The tests showed that, without agent addition surfactant, the CaCO3 formed precipitates immediately (charge one). Nor did triisopropanolamine (TIPA) separately have a positive influence on the precipitation delay of CaCO_ {3}. In the case of alkylbenzenesulfonic acid sodium salt LAS, at 15 ° C, the salt of LAS-calcium, before it finally precipitates calcium carbonate at about 37.5 ° C (LAS-Na). Yes at solution is added triisopropanolamine, thus delaying the CaCO 3 precipitation to a temperature of approximately 37.5 ° C, and in the meantime a calcium precipitation-LAS, which is shown, by example, by means of low dynamic surface tension. Sokalan®CP5 (acrylic acid maleic acid copolymer, BASF AG), which is used as an adjuvant in washing and cleaning agents, it measured as a reference. Diisopropanolamine showed a behavior similar to triisopropanolamine. Also in the case of diisopropanolamine (DIPA), precipitates only a very fraction reduced LAS-calcium salt, before precipitate calcium carbonate at approximately 37.5 ° C.

Sokalan® CP 5 (acrylic acid-maleic acid copolymer, BASF), used in a concentration of 150 mg / L together with LAS-Na, inhibits the precipitation of calcium carbonate to a temperature of approximately 60 ° C. Even more temperatures are reached in the case of the use of alkanolamines used according to the invention.
high.

TABLE 2

T. = e n%, O. = surface tension in mN / m. Load T = 20ºC T = 30 ° C T = 40 ° C T = 50 ° C T = 60 ° C T. OR. T. OR. T. OR. T. OR. T. OR. one 31 73 33 71 3. 4 70 31 68 32 67 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 8 3. 4 66 eleven 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 Wash tests with formulations containing LAS and Triisopropanolamine in the Lini washing machine

Wash tests were carried out in a Lini test machine with skin fat pigment dirt on polyester fabric, mixed fabric and cotton fabric. How model recipe a formulation with 1.72 g / l of Marlon® was selected At 350 (50% sodium alkylbenzenesulfonate), 0.48 g / l of triisopropanolamine and 0.5 g / l calcium carbonate. It was used water with increasing calcium water hardnesses, and the 1 hour rags at a temperature of 30 ° C.

Table 3 shows the results at a wash temperature of 30ºC after average of all types of tissue.

TABLE 3

Hardness of Water Washing value [%] Wash 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 of Ca 2+, in the experiment without triisopropanolamine it is no longer observed almost washing performance of the solution. Performance of washing the alkylbenzene sulfonate solution with triisopropanolamine showed, on the contrary, approximately one 70% washing performance, which was preserved without water hardness, even in the case of high water hardness of 5.43 mmol / l Ca 2+.

Claims (14)

1. Composition of washing and cleaning agents alkaline containing as components

(TO)

  to the less an alkylbenzenesulfonic acid, or its salt, which has a linear or branched alkyl moiety with 8 to 24 atoms of carbon,

(B)

   at least one alkanolamine, or its ammonium salt, which has the general structural formula I,

3 where respectively so independent between yes, k, l or m is 0, 1, 2 or 3, where k + 1+ m> one,

n

is 0 or 1, and

R a, R b or R c    it is a linear or branched hydrocarbon with 2 to 6 atoms of carbon, presenting at least one R 3 to 6 carbon atoms, Y

(C)

   at 0 to 10% by weight, based on the total composition, one or several adjuvants, and

also in a 0.001 a approximately 5% by weight, based on the total composition, enzymes, using components (A) and (B) in proportion weight 7: 1 a 1: 1. 2. Composition according to claim 1, which contains as a component

(B)

to the minus an alkanolamine, or its ammonium salt, of the formula general structural II

4 where the remains, or indexes, respectively independently of each other, They are: k, l, m 0, 1, 2 or 3, where k + 1 + m> one,

n

0 or 1, and

R 1, R 2 or R 3    independently of each other, H or linear alkyl moieties or branched with 1 to 4 carbon atoms, representing at least one R a group SCH 3, and may be R 1, R 2 or R 3, in given case, different for each k, l or m. 3. Composition according to claim 1, characterized in that the alkanolamine has at least two isopropanol residues. 4. Composition according to one of the preceding claims, characterized in that the alkylbenzenesulfonic acid, or its salt, has a linear alkyl moiety with 8 to 24 carbon atoms. 5. Composition according to one of the claims above, which contains components (A) and (B) in proportion molar from 2 to 1 to 1 to 2, preferably 1.2 to 1 to 1 to 0.8. 6. Composition according to one of the claims precedents, containing 0.01 to 5% by weight, based on the total composition, one or more adjuvants, preferably not Contains adjuvants. 7. Composition according to one of the claims which preferably does not contain insoluble adjuvants.

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8. Composition according to one of the claims precedents that also contains as a component

(D)

   in 0.001 to 3% by weight divalent metal ions, or their salts, especially calcium or magnesium, referred to the proportion of metal ion weight with respect to total composition weight.

9. Composition according to one of the claims precedents, as a liquid formulation containing 15 to 80% by weight of surfactant. 10. Composition according to one of the preceding claims as a liquid formulation that does not It contains water. 11. Use of the composition according to one of the preceding claims for washing and / or cleaning under use of additives containing divalent metal salts, especially calcium. 12. Use according to claim 11, characterized in that the addition is water, and contains calcium ions in a concentration of 0.2 to 6 mmol / l. 13. Use of the composition according to one of the claims 1 to 10 for washing and cleaning materials textiles 14. Procedure for the reduction of amount of divalent metal salts, especially calcium salts,  that precipitate in the form of an insoluble deposit in processes of washing and cleaning, especially in the washing of textile materials, against conventional washing and cleaning agents that contain alkylbenzene sulphonate, which do not contain alkanolamines according one of claims 1 to 10, using a alkaline cleaning and cleaning agent composition containing as components

(TO)

  to the less an alkylbenzenesulfonic acid, or its salt, which has a linear or branched alkyl moiety with 8 to 24 atoms of carbon,

(B)

   at least one alkanolamine, or its ammonium salt, which has the general structural formula I,

5 where respectively so independent between yes, k, l or m is 0, 1, 2 or 3, where k + 1+ m> one,

n

is 0 or 1, and

R a, R b or R c    it is a linear or branched hydrocarbon with 2 to 6 atoms of carbon, presenting at least one R 3 to 6 carbon atoms, Y

quad

0 to 10% by weight, based on the composition total, one or more adjuvants, using components (A) and (B) in a 7: 1 to 1: 1 weight ratio.