EP0906394B1 - Improved detergent and tableware cleaner - Google Patents

Description

The invention relates to mixtures containing at least one polycarboxylate, at least one amine and at least one acid, detergents containing them and their use as incrustation inhibitors in detergents and as incrustation inhibitors and deposit inhibitors in dishwashers.

BE 773 260 describes detergents which, in addition to LAS and Contain tripolyphosphate as fabric softener component N-alkyl propane diamines, in particular N-dodecylpropane-1,3-diamine, N-cocopropane-1,3-diamine, or N-tallow fat propane-1,3-diamine.

EP-A-0 173 398 describes detergent compositions which a mixture of long chain primary or secondary amines and cellulase as the essential fabric softening ingredients. As an amine tallow fatty amine can be used. The compositions can Alkali metal phosphates and polycarboxylates in addition to LAS and sodium triphosphate contain.

WO 86/07603 contains detergents for low washing temperatures described the ether amines, amido amines, glucamine or morpholine derivatives, and may contain polycarboxylic acids.

GB-A-2 172 910 describes detergent compositions which Have fabric softening properties. Certain are used for this primary, secondary or tertiary amines with a long chain hydrocarbyl radical used, in particular N, N-dimethyllaurylamine or N-dimethylcocoamine, which can be mixed with a Brönstedt acid as a dispersant. Inorganic acids, as well as organic acids, such as polymeric carboxylic acids. Monocarboxylic acids are preferred. The compositions contain LAS and sodium tripolyphosphate.

DE-A-195 32 717 describes detergents which are modified polyaspartic acids included as incrustation inhibitors. The polyaspartic acids are polycondensates of aspartic acid, certain amines and phosphorus containing acids.

WO 95/33035 describes detergent compositions which are particularly effective for removing grease / oil-like dirt from substrates such as textile products or dishes. A detergent composition contains 0.5% by weight of 1-hexylamine, 9.0% by weight of C _12-16 fatty acid and 6.0% by weight of anhydrous citric acid and 10.0% by weight of oleoyl sarcosinate.

US 4,687,592 relates to builder systems for detergents. The in Examples 1 to 4 The compositions listed contain polycarboxylates and amines, but none Mineral acids and organic acids with one or two carboxyl groups and maximum 15 carbon atoms. The formulation according to Example 1 contains, for example, 3-oxa-1,2,4,5-pentantetracarboxylic acid sodium salt and sodium polyacrylate. In addition, the Formulations of TAED-related compounds, i.e. Nitrogen-containing Have polycarboxylic acids. In Example III is a combination of Trenntanolamin, 3-oxa-1,2,4,5-pentantetracarboxylic acid and polyacrylic acid.

EP-A-0 233 010 also relates to detergent builder systems. In Examples 2, 4 and 5 are sodium polyacrylate and sodium carbonate or polyacrylic acid and triethanolamine or carboxyl-containing polymers.

An object of the present invention is to provide incrustation inhibitors for Provide detergents and dishwashers.

Another task is to use incrustation inhibitors for reduced phosphates or to provide phosphate-free detergents and dish detergents.

Another object is detergent containing incrustation inhibitors and to provide dishwashers.

Another object of the present invention is to provide Incrustation inhibitors for detergents and dishwashers that are opposite the aspartic acid polycondensates are easier to produce and a have better effect.

Another job is to have scale inhibitors for dishwashing detergents provide

Another object is to use dishwashing detergents containing scale inhibitors provide.

Another task is to provide scale inhibitors for dishwashing detergents, compared to conventional polycarboxylates have better effect.

(a) 0,1 bis 99 Gew.-% mindestens eines Polycarboxylats mit mindestens 3 Carboxylgruppen, wobei das Polycarboxylat mindestens einen der Grundbausteine Acrylsäure, Maleinsäure, Maleinsäureanhydrid, Asparaginsäure enthält, gegebenenfalls in Form eines Alkalimetallsalzes

(b) 0,1 bis 99 Gew.-% mindestens eines Amins mit einem pK_s-Wert größer 9, und

(c) 0,1 bis 99 Gew.-% mindestens einer Säure, ausgewählt aus Mineralsäuren und organischen Säuren mit einer oder zwei Carboxylgruppen und maximal 15 C-Atomen,

mit der Maßgabe, daß das Gemisch weniger als 24 Gew.-% Triphosphate enthält und die Gesamtmenge der Inhaltsstoffe 100 Gew.-% ergibt, und die Verwendung dieses Gemisches in Waschmittel- oder Geschirreinigerformulierungen. These problems are solved by a mixture containing

(a) 0.1 to 99% by weight of at least one polycarboxylate with at least 3 carboxyl groups, the polycarboxylate containing at least one of the basic building blocks acrylic acid, maleic acid, maleic anhydride, aspartic acid, optionally in the form of an alkali metal salt

(b) 0.1 to 99 wt .-% of at least one amine with a _pK a value greater than 9, and

(c) 0.1 to 99% by weight of at least one acid, selected from mineral acids and organic acids with one or two carboxyl groups and a maximum of 15 carbon atoms,

with the proviso that the mixture contains less than 24% by weight triphosphates and the total amount of the ingredients gives 100% by weight, and the use of this mixture in detergent or dishwashing detergent formulations.

Compared to pure polycarboxylates like the one they have For example, described in DE-A-195 32 717, the mixtures have improved incrustation-inhibiting and deposit-inhibiting properties.

First, components (a), (b) and (c) of the invention Mixtures described.

Component (a)

Polycarboxylates which can be used according to the invention have at least three carboxyl groups in the molecule. These polycarboxylates according to the invention can be monomeric compounds or polymeric compounds which are a Have molecular weight distribution. It can be both naturally occurring as well as synthetically produced polycarboxylates. According to a preferred embodiment, such polycarboxylates used that are biodegradable or can be eliminated in sewage treatment plants are. According to one embodiment of the invention, the weight average is the molecular weights of the polycarboxylates 100 to 300,000, preferably 800 to 500,000, especially 800 to 200,000.

Polycarboxylates which can be used according to one embodiment of the invention are, for example, proteins that contain aspartic acid, such as casein, gelatin, wheat proteins, soy proteins, pea proteins, Polyaspartic acid, polycocondensates of aspartic acid and / or carboxylic acids. According to one embodiment of the invention it is advantageous to lower the molecular weight of the proteins, preferably to a weight average molecular weight of 800 to 200,000 by it is treated, for example, oxidatively, reductively or hydrolytically. The hydrolytic Treatment can be done with the help of enzymes, acids or bases respectively.

Synthetic polycarboxylates which can be used according to one embodiment of the invention are advantageously prepared by radical polymerization of unsaturated monomers. At least one of the basic building blocks, acrylic acid, maleic acid, maleic anhydride, and, if appropriate, methacrylic acid, itaconic acid, aconitic acid, vinylsulfonic acid, methallylsulfonic acid, cinnamic acid, acrylic acid esters, such as methacrylate, butyl acrylate, ethylhexyl acrylate, olefin acrylate, stearyl acrylate acrylate, tallow acrylate acrylate, tallow acrylate acrylate, tallow acrylate, tallow acrylate, tallow acrylate, tallow acrylate, tallow acrylate, such as maleic acid mono- and dimethyl ester, maleic acid mono- and diethyl ester, maleic acid mono- and diisopropyl ester, maleic acid mono- and di-butyl ester, maleic acid mono- and distearyl ester. In addition to the unsaturated carboxylic acids, up to 90% other monomers such as vinyl acetate, vinyl propionate, vinyl sulfonic acid, vinyl stearate, styrene, olefins such as ethylene, propylene, butene, isobutene, diisobutene, hexene, octene, octadecene, C ₂₀ / C ₂₄ olefin, cyclopentene , Cyclopentadiene, cyclohexene, butadiene, vinyl ethers, such as methyl vinyl ether, isobutyl ether, butanediol monovinyl ether ethoxylates, allyl alcohol ethoxylates or furan. The polycarboxylates are prepared by known free-radical polymerization methods in the form of solution polymerization or precipitation polymerization in water, polyalkylene glycols, nonionic surfactants, acetone, toluene, o-xylene, isopropanol or other organic solvents. All initiators commonly used are used as radical initiators. If low molecular weight polymers are desired, polymerization can also be carried out in the presence of regulators. According to one embodiment of the invention, the polycarboxylates are used in the sodium or potassium salt form. This applies in particular to copolymers of maleic anhydride, which are mostly insoluble in water and other solvents. In the hydrolyzed alkali metal salt form, they are then usually soluble or at least dispersible in water.

According to one embodiment of the invention, graft polymers are also suitable from acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, methallylsulfonic acid, Methacrylic acid and glucose, polysaccharides such as starch or Starch hydrolyzates, proteins, protein hydrolyzates or polyalkylene glycols. Examples are graft polymers of acrylic acid and maleic acid on matrodextrins, Graft polymers from maleic acid and starch, graft polymers from Acrylic acid and casein, graft polymers from acrylic acid, methyl methacrylate and gelatin.

Typical polycarboxylates which can be used according to the invention are polyacrylic acids with molecular weights between 1,000 and 250,000, copolymers of acrylic acid and maleic acid in a ratio of 70/30 with a molecular weight of 70,000, copolymers of acrylic acid and maleic acid in a ratio of 40/60 with a molecular weight of 40,000, copolymers of maleic acid and isobutene with a molecular weight of 4,000, Copolymers of maleic acid and diisobutene with a molecular weight of 12,000, copolymers of maleic acid and styrene with a molecular weight of 20,000, copolymers of maleic acid and C ₂₀ / C ₂₄ olefin with a molecular weight of 15,000, polymaleic acid with a molecular weight of 1,000, polyaspartic acids with a molecular weight of between 1,000 and 50,000, terpolymers made of acrylic acid Maleic acid and vinyl acetate with a molecular weight of 40,000, graft polymers of acrylic acid and maleic acid on matrodextrins with a molecular weight of 40,000, graft polymers of acrylic acid and polyethylene glycols with a molecular weight of 60,000, graft polymers of acrylic acid and maleic acid and polyethylene glycols with a mole important 20,000.

According to one embodiment, the polycarboxylates contain no aromatic Residues.

Component (b)

As component (b) of the mixtures of the invention an amine is at least, preferably used with a _pK a value greater than 9 9.5 to 12.

According to one embodiment, the amines contain only aliphatic, cycloaliphatic and / or araliphatic residues. Among araliphatic residues are understand those in which aromatic radicals have alkylene groups are connected to the amine nitrogen atom.

According to one embodiment of the invention, the amines which can be used have the general formula (II) R ⁵ NR ⁹ - [(CR ⁷ R ⁸ ) _m ―NH] _n ―R ⁶ where n has an integer value from 0 to 20 and m has an integer value from 1 to 4, the radical R ^{5 is} a C _1-30 , preferably C _1-20 , in particular C _1-10 alkyl radical, C _2-30 -, preferably C _2-20 -, in particular C _2-10 alkenyl radical and each of the radicals R ⁶ , R ⁷ , R ⁸ and R ^{9 is} independently a hydrogen atom or as defined for the radical R ⁵ .

According to one embodiment of the invention, n has the value zero, the radical R ⁵¹ is a C _6-20 alkyl or alkenyl radical, the radical R ^{6 is} a C _1-4 alkyl radical or C _2-4 alkenyl radical and the radical R ⁹ a hydrogen atom or a C _1-4 alkyl radical or C _2-4 alkenyl radical.

According to one embodiment of the invention, the amine for use in a detergent a _pK a value, which is greater than the reduced by 1 pH is preferably greater than the pH, more preferably at least 0.5 greater is as the pH of the 1 wt .-% wash liquor of the detergent. The pK _S value means the value of the corresponding acid of the amine, ie the protonated amine, and is equal to 14-pK _{B of} the amine.

Monovalent or polyvalent amines, preferably having at least 4 carbon atoms, are preferably used as component (b). The amines can be primary, secondary or tertiary. The amines can be hydrophilic or hydrophobic.
According to one embodiment of the invention, component (b) are primary amines with preferably 3 to 20, in particular 4 to 10, carbon atoms, such as butylamine, tert-butylamine, sec-butylamine, ethylhexylamine, 2-methylheptylamine, octylamine, 2-ethylhexylamine , Nonylamine, decylamine, 2-propylheptylamine, undecylamine, cetylamine, tridecylamine, isotridecylamine, fatty amines, such as oleylamine, stearylamine, octadecylamine, tallow fatty amine, hydrogenated tallow fatty amine, amines based on coconut fatty acids, polyisobutenamine, alkylpolyphenol amines, alkyl amine, by polypropylene amines, alkylpolyylenes, polyphenylene amines, alkyl amines, by polypropylene amine, alkyl can. Polyvalent primary amines are, for example, 1,6-diaminohexane, 1,8-diaminooctane, 1,3-diaminopropane, isophorone diamine, polyoxyalkylene diamines, such as polyethylene oxide diamine, polypropylene oxide diamine, polybutylene oxide diamine, polytetrahydrofuran diamine, co (polyethylene oxide / propylene oxide) amines, which are produced by amination of polyoxides can be, as well as aminated alkoxylated fatty alcohols and oxo alcohols, such as aminated reaction products from a C ₁₆ / C ₁₈ oxo alcohol and 7 mol of ethylene oxide, which has subsequently been aminated. These types of amines can be referred to as ether amines.

According to one embodiment of the invention, component (b) are secondary dialkylamines having preferably 5 to 40, in particular 8 to 36, carbon atoms, such as N, N-dibutylamine, N, N-dihexylamine, N, N-diisopentylamine, N, N-dipentylamine , N, N-diethylhexylamine, N, N-ditallow fatty amine, hydrogenated N, N-ditallow fatty amine, N, N-distearylamine, N, N-dioleylamine, mixed secondary amines such as N-methyl-N-octylamine, N-methyl-N- stearylamine, N-methyl-N-tallow fatty amine, hydrogenated N-methyl-N-tallow fatty amine, N-methyl-N-decylamine, N-methyl-N-octylamine, N-methyl-N-ethylhexylamine, alkanolamines, or reaction products of primary and secondary amines with 1 to 100 mol, preferably 1 to 20 mol, in particular 1 to 15 mol ethylene oxide and / or propylene oxide, such as reaction products of isotridecylamine with 7 mol ethylene oxide, reaction products from N-methyl-N-tallow fatty amine with 10 mol ethylene oxide and 3 mol Propylene oxide, from tallow fatty amine with 1 mol ethylene oxide, oleylamine with 3 mol ethylene oxide, from tallow fatty amine with 3 mol ethylene oxide and 1 mol propylene oxide, from hydrogenated tallow fatty amine with 2 mol ethylene oxide, from stearylamine with 1 mol ethylene oxide. According to one embodiment of the invention, reaction products of primary and secondary amines with other epoxides, such as mono- and polyvalent glycidyl ethers, such as butyl glycidyl ether, ethylhexyl glycidyl ether, C ₁₂ / C ₁₄ alcohol glycidyl ether, C ₁₃ / C ₁₅ - Alcohol-glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, polypropylene glycidyl ether can be used. According to the invention, long-chain epoxides can also be used as epoxides, for example epoxidized castor oil, or alkyloxiranes which can be prepared by epoxidizing olefins, such as propyloxirane, decyloxirane, dodecyloxirane, octadecyloxirane.

According to one embodiment of the invention, tertiary amines can also be used, preferably having 6 to 60, in particular 9 to 54, carbon atoms. Examples are tributylamine, trioctylamine, tridecylamine, tridodecylamine, dimethyldodecylamine, dimethyllaurylamine, Dimethylkokosfettamin, dimethylcetylamine, dimethylstearylamine, dimethyloctadecylamine, methyldioctylamine, methyldidecylamine, Methyldikokosölamin, Methylditalgfettamin, hydrogenated Methylditalgfettamin, Methyldioctadecylamin, dimethyl-C ₁₂ / C ₁₄ amine, N, N-dimethylcyclohexylamine.

Multi-valued ones can also be used according to one embodiment of the invention Amines are used which, in addition to primary amino groups, also secondary or have tertiary amino groups, preferably with 3 to 60, in particular 4 to 40 carbon atoms, for example alkylaminoalkylamines such as 2-ethylaminoethylamine, Tallow fat amino propylamine, hydrogenated tallow fat amino propylamine, Coconut oil aminopropylamine, oleylamino propylamine (e.g. commercially available as Duomeen® from Akzo), 3-isopropylaminopropylamine, or dialkylaminoalkylamines such as 3-methyl tallow fatty aminopropylamine, 3-ditallow fatty aminopropylamine, 2-dimethylaminoethylamine, 1-diethylamino-4-aminopentane, Dimethylaminopropylamine.

According to one embodiment of the invention, oligomeric or polymeric amines are used, for example secondary amino groups have, preferably with a weight average molecular weight from 100 to 250,000, especially from 200 to 100,000. Examples are diethylenetriamine, triethylenetetramine, polyethyleneimine, polyvinylamine, Copolymers of vinylamine and vinylformamide, alkylaminopolyalkyleneamines, such as N-tallow fat tripropylenetetramine, or dialkylaminopolyalkylene amines, such as N, N-Ditalgfett dipropylenetriamine.

Furthermore, according to one embodiment of the invention, amidoamines can be used, preferably with a weight average molecular weight of 200 to 100,000, in particular 250 to 80,000, which can be prepared by condensing mono- and polyvalent carboxylic acids and at least divalent amines and contain at least one basic amino group, for example, a condensation product from 1 mol stearic acid and 1 mol hexamethylenediamine, a condensation product from 1 mol oleic acid and 1 mol ethylenediamine, a condensation product from 1 mol C ₁₀ / C ₁₂ fatty acid and 1 mol isophoronediamine, a condensation product from 1 mol adipic acid and 2 mol hexamethylenediamine , a condensation product from 1 mol phthalic acid and 2 mol ethylenediamine, a condensation product from 1 mol oleic acid and 1 mol ethylenediamine, a condensation product from 2 mol adipic acid and 3 mol hexamethylenediamine, a condensation product from 3 mol terephthalic acid and 2 mol butylenediamine min, a condensation product of 4 mol adipic acid and 3 mol hexamethylenediamine.

According to one embodiment of the invention, ester amines can also be used as amines are used, preferably with a weight average molecular weight from 200 to 100,000, especially 300 to 10,000, by Esterification of alkanolamines with carboxylic acids can be prepared for example esters from stearic acid and ethanolamine, esters from oleic acid and N, N-dimethylethanolamine, esters of tallow fatty acid and diethanolamine, Esters of coconut fatty acid and triethanolamine, esters of phthalic acid and Ethanolamine.

According to one embodiment of the invention, N-alkyl, N-alkenyl or N-hydroxyalkyl glucamines or morpholines with up to 30 Carbon atoms are used.

The amine is preferably at least one of amines having at least four carbon atoms, preferably tallow fatty amine, hydrogenated tallow fatty amine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, 2-propylheptylamine, undecylamine, dodecylamine, tridecylamine, cetylamine, stearylamine, palmitylamine, oleylamine, cocylamine, cocylamine, cocylamine, mono-α-branched secondary amines, bis-α-branched secondary amines of the general formula (I) R ⁴ R ³ HC ― HN ― CHR ¹ R ² wherein the radicals R ¹ , R ² , R ³ and R ^{4 are,} independently of one another, optionally substituted C _1-20 alkyl radicals.

Component (c)

Component (c) of the mixture according to the invention is at least one acid, selected from mineral acids and organic acids with one or two Carboxyl groups, which according to one embodiment have no aromatic radicals contain.

Acids containing phosphorus are preferred.

Saturated or unsaturated organic acids can be used as component (c) with one or two carboxylic acid groups and up to 15 C atoms, in particular up to 10 carbon atoms, such as formic acid, acetic acid, Propionic acid, capric acid, oxalic acid, succinic acid, adipic acid, maleic acid, Fumaric acid, sebacic acid, malic acid, lactic acid, glycolic acid, Tartaric acid, glyoxylic acid, and mineral acids are used.

Examples of acids according to the invention are hydrochloric acid, sulfuric acid, Sulphurous acid, meta-silica, boric acid, heteropolyacids of tungsten or molybdenum, acidic ion exchangers, acidic silicates or aluminosilicates, Benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid. Prefers acids containing phosphorus are used. Examples are phosphoric acid, Diphosphoric acid, triphosphoric acid, polyphosphoric acid, phosphorous acid, Hypophosphorous acid, phosphonic acids, primary and secondary phosphoric acid esters, primary and secondary phosphoric acid amides, such as phosphoric acid 2-ethyl-hexyl, oleyl or ditallow fatty amide and phosphonic acids such as diethylenetriaminepentamethylenephosphonic acid.

The mixtures according to the invention which contain components (a), (b) and (c) contain, according to the invention, less than 24% by weight, preferably at most 20% by weight of triphosphate, preferably at most 10% by weight, in particular at most 5 % By weight triphosphate. According to one embodiment of the invention, the mixtures are essentially or completely free from triphosphate.
According to one embodiment of the invention, the mixtures according to the invention which contain components (a), (b) and (c) contain a maximum of 20% by weight of LAS, preferably a maximum of 10% by weight, in particular a maximum of 5% by weight of LAS , According to one embodiment of the invention, the mixtures are essentially or completely free of LAS.

Preparation of the mixtures

b + c → bc   (Salzbildung)

bc → d   (Tempern des Salzes)

a + bc → abc   (Abmischen von Polycarboxylat mit Salz)

a + d → ad

a + b → ab

ab + c → abc

a + c → ac

ac + b → abc

To produce the mixtures, components (a), (b) and (c) can be mixed in any order. The mixtures (abc) of polycarboxylate (a), amine (b) and acid (c) can be prepared according to the following general scheme:

b + c → bc (salt formation)

bc → d (annealing the salt)

a + bc → abc (mixing polycarboxylate with salt)

a + d → ad

a + b → ab

from + c → abc

a + c → ac

ac + b → abc

The mixtures can be prepared according to one embodiment of the Invention are made by amine (b) and acid (c) first at 10 to 150 ° C. be neutralized and the neutralization product (e.g. alkylammonium phosphate) is added to the polycarboxylate. The neutralization of Amines and acids can be in bulk or in a diluent respectively. The process in bulk is carried out, for example, in an extruder carried out at 20 to 150 ° C, for example according to a Embodiment of the invention phosphoric acid and molten tallow fatty amine be dosed. The alkyl ammonium phosphate is used as a melt discharged and can be made up in the form of strands or granules become. As a diluent for neutralization according to one Embodiment of the invention water, acetone, methanol, ethanol, glycerol, Surfactants, nonionic surfactants, such as alkoxylation products from Oxooder Fatty alcohols, ethylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols, Propylene glycol, dipropylene glycol, polypropylene glycol, copolymers from ethylene oxide and propylene oxide, block-linked polyethylene glycols and polypropylene glycols can be used.

If phosphoric acid is used as component (c), the preparation can the mixtures according to an embodiment of the invention advantageously are done by first adding alkylamines and phosphoric acids 10 to 150 ° C are brought to the neutralization reaction and the salt-like Neutralization products are then heated up to 250 ° C. The tempered Alkylammonium phosphates are subject to temperatures between 150 and 250 ° C at least partially with elimination of water from a conversion in alkyl ammonium polyphosphates and alkyl amine phosphoric acid amides (Component (d)). The condensation can be in a diluent or preferably be carried out in bulk. Suitable as a diluent high-boiling diluents such as glycerin, surfactants, nonionic Surfactants, ethylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols, Propylene glycol, dipropylene glycol, polypropylene glycol, copolymers Ethylene glycol and propylene glycol, block-linked polyethylene glycols and polypropylene glycols. An extruder or kneader can be used as the reaction apparatus or paddle dryer can be used. The annealed adducts Alkylamine and phosphoric acids are then mixed into the polycarboxylate.

You can also insulation according to one embodiment of the invention Avoid the reaction product of amine and acid by the Polycarboxylate (a) in the form of an aqueous solution or, if the polycarboxylates (a) are not completely soluble in water, even in the form of a First suspension with acids (c) and then with amines (b). The With this procedure, polycarboxylates can be in the form of anhydrides, Acid forms or alkali salt forms are used. Will the polycarboxylates used in the form of anhydrides or acids, so after Addition of the amines (b) and acids (c) neutralization with alkalis be performed.

The mixtures can be produced according to an embodiment of the Invention are made by the polycarboxylates (a) in the form of an aqueous Solution or suspension first with amines (b) and then with acids (c) be transferred. The further neutralization can be as described above respectively.

If anhydrides of the polycarboxylates arise during the polymerization, then according to an embodiment of the invention, these anhydrides with the Components (b) and (c) are mixed. Then the hydrolysis with alkalis and transfer to an aqueous solution or suspension respectively.

The polycarboxylates are usually in the form of detergents Alkali salts used. The polycarboxylates can be neutralized before or after the addition of alkylamine and phosphoric acid. Most of time the mixtures are then neutralized to a pH that is between 6 and 10.

If the polycarboxylates are available in solid form, so can the polycarboxylate powder or granules with the salts from (b) and (c) be mixed. Solid polycarboxylates can be in the form of powders or Granules accumulate. For example, a solution of a copolymer Acrylic acid and maleic acid or its salt by spray drying or Spray granulation can be converted into a solid powder. In precipitation polymerization of maleic anhydride and isobutene in organic solvents creates a solid polycarboxylate powder that the polycarboxylate in contains the anhydride form. Solid or similarly produced solid polycarboxylates can then with solid adducts of the amines (b) and acids (c) be mixed. The solid adducts from (b) and (c) are obtained, for example by converting tallow fatty amine and phosphoric acid in the extruder and subsequent shaping of the melt, or by the amines (b) and neutralizing the acids (c) in a diluent in which the adduct from (b) and (c) is insoluble and precipitates. For example, you can use 2-ethylhexylamine or tallow fatty amine and phosphoric acid or react polyphosphoric acid in acetone or toluene, so that the adduct is obtained in the form of a powder.

The possible procedures are exemplified below: Maleic anhydride and isobutene are according to one embodiment of the Invention in an organic solvent radical in the form of a precipitation polymerization polymerized and the resulting polymer in the anhydride form isolated by filtration. The polymer is in the anhydride form as a slurry in water, first mixed with alkyl ammonium phosphate and then neutralized with sodium hydroxide solution.

The polymer can also be used according to one embodiment of the invention from MSA with isobutene first with sodium hydroxide solution to an aqueous sodium salt solution hydrolyze and then add alkyl ammonium phosphate. One can use the aqueous sodium salt solution of the maleic acid / isobutene copolymer also add first with alkylamine and then with phosphoric acid. But you can also first phosphoric acid and then tallow fatty amine to admit. You can also start with a condensation product from tallow fatty amine and produce phosphoric acid at 200 ° C and then this to the aqueous Give sodium salt solution of the copolymer.

According to one embodiment of the invention, an aqueous can be used Solution of polyacrylic acid in the acid form first with alkylamine and then add phosphoric acid.

According to one embodiment of the invention, a solution can be found Neutralize polyacrylic acids first with sodium hydroxide solution and then with tallow fatty amine phosphoric acid salt offset.

The mixtures (abc) according to the invention can be clearly soluble in water. However, suspensions can also result if one or more Components of the mixture (ABC) is not soluble in water. In these Cases, it may be helpful to stir one by vigorous stirring or shearing to produce the finest possible suspension. This can be done with the help of a Dispersing and homogenizing machine, an intensive mixer, with cutting blades equipped fast rotating agitator, calender or under Exposure to ultrasound can be achieved.

The mixtures according to the invention can be used in detergents especially as an incrustation inhibitor or scale inhibitor. You can also used in dishwashing detergent formulations, particularly as an incrustation inhibitor or scale inhibitor.

detergent formulations

(a) mindestens einem Polycarboxylat mit mindestens drei Carboxylgruppen, wie in Anspruch 6 definiert,

(b) mindestens einem Amin, dessen pK_s-Wert größer ist als der um 1 verminderte pH-Wert einer 1 gew.-%igen Waschflotte des Waschmittels,

(c) mindestens einer Säure, ausgewählt aus Mineralsäuren und organischen Säuren mit einer oder zwei Carboxylgruppen und maximal 10 C-Atomen,

und gegebenenfalls sonstige übliche Bestandteile, mit der Maßgabe, daß das Waschmittel weniger als 24 Gew.-% Triphosphat enthält.The invention also relates to detergent formulations containing at least one surfactant and a mixture of

(a) at least one polycarboxylate with at least three carboxyl groups as defined in claim 6,

(b) at least one amine whose _pK a value is greater than the value decreased by 1 pH of a 1 wt .-% aqueous wash liquor of the detergent,

(c) at least one acid selected from mineral acids and organic acids with one or two carboxyl groups and a maximum of 10 carbon atoms,

and optionally other conventional ingredients, with the proviso that the detergent contains less than 24% by weight of triphosphate.

The invention further relates to detergents containing at least one Surfactant and a mixture according to the invention and optionally other usual components.

According to one embodiment, the detergents contain 0.01 to 40, preferably 0.1 to 30, in particular 0.5 to 20% by weight of the component (a), 0.01 to 20, preferably 0.03 to 10, in particular 0.05 to 5% by weight component (b), and 0.01 to 20, preferably 0.02 to 10, in particular 0.03 to 8% by weight of component (c).

The mixtures of (a), (b) and (c) are in one embodiment in an amount of 0.1 to 20, preferably 1 to 15 wt .-% in detergent formulations used.

The detergents can be in powder form or in liquid form available. The composition of detergents and cleaning agents can be very be different. Detergent and cleaning agent formulations included usually 2 to 50 wt .-% surfactants and optionally builders. This Information applies to both liquid and powder detergents. Detergent and cleaner formulations sold in Europe, the U.S.A. and are common in Japan can be found, for example, in Chemical and Engn. News, volume 67, 35 (1989). More information about the composition of detergents and cleaning agents Ullmann's Encyclopedia of Technical Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160.

Such formulations are to be understood as low-phosphate detergents which contain at most 25% by weight of phosphate, calculated as Pentasodium. The detergents can be heavy duty detergents or special detergents. Both come as surfactants anionic as well as nonionic or mixtures of anionic and nonionic surfactants. The surfactant content of the detergent is preferably 8 to 30% by weight.

surfactants

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, such as C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₃ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated, ethoxylated C ₈ to C ₂₂ alcohols or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, mol of ethylene oxide being used per mol of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Such alkoxylated C ₈ are suitable also - to C ₂₂ alcohols, the ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylated C ₈ to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

Further suitable anionic surfactants are alkyl sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ -C ₁₈ alkane sulfonates and soaps, such as the salts of C ₈ to C ₂₄ carboxylic acids.

Further suitable anionic surfactants are N-acyl sarcosinates with aliphatic saturated or unsaturated C ₈ to C ₂₅ acyl radicals, preferably C ₁₀ to C ₂₀ acyl radicals, such as N-oleoylsarcosinate.

Further suitable anionic surfactants are C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS). The polymers according to the invention are preferably used in low-LAS detergent formulations with less than 4%, particularly preferably in LAS-free formulations.

The anionic surfactants are preferably in the form of Added salts. Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and ammonium salts, such as hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Examples of suitable nonionic surfactants are alkoxylated C ₈ -C ₂₂ -alcohols. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 5, preferably 3 to 20, mol of at least one alkylene oxide are used per mole of alcohol. Preferably used as the alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. This Compounds contain on average 1 to 20, preferably 1.1 to 5 Glucoside.

wobei A ein C₆- bis C₂₂-Alkyl-, B ein H oder C₁- bis C₄-Alkyl- und C ein Polyhydroxyalkanyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise steht A für C₁₀- bis C₁₈-Alkyl-, B für CH₃- und C für einen C₅- oder C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀-C₁₈-Carbonsäuren. Die Waschmittelformulierungen enthalten vorzugsweise mit 3 bis 12 mol Ethylenoxid ethoxylierte C₁₀-C₁₆-Alkohole, besonders bevorzugt ethoxylierte Fettalkohole als nichtionische Tenside.Another class of nonionic surfactants are N-alkylglucamides of the general structures (III) and (IV)

where A is a C ₆ to C ₂₂ alkyl, B is an H or C ₁ to C ₄ alkyl and C is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups. A is preferably C ₁₀ to C ₁₈ alkyl, B is CH ₃ and C is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ -C ₁₈ carboxylic acids. The detergent formulations preferably contain C ₁₀ -C ₁₆ alcohols ethoxylated with 3 to 12 mol of ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.

R¹

einen C₅- bis C₂₁-Alkyl- oder -Alkenylrest bezeichnet,

R²

eine C₁- bis C₄-Alkylgruppe bedeutet,

A

für C₂- bis C₄-Alkylen steht,

n

die Zahl 2 oder 3 bezeichnet und

x

einen Wert von 1 bis 6 hat.

Further preferred surfactants are the end group-capped fatty acid amide alkoxylates of the general formula (V) known from WO 95/11225 R ¹ -CO-NH- (CH ₂ ) _n -O- (AO) _x -R ² in the

R ¹

denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,

R ²

represents a C ₁ to C ₄ alkyl group,

A

represents C ₂ -C ₄ -alkylene,

n

denotes the number 2 or 3 and

x

has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

Builder

The powdery or granular detergents and, if appropriate, also Structured liquid detergents also contain one or more inorganic builder. All are suitable as inorganic builder substances usual inorganic builders such as aluminosilicates, silicates, carbonates and Phosphates.

Suitable inorganic builders are, for example, aluminosilicates with ion-exchanging Properties, like zeolites. Different types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na partly against other cations like Li, K, Ca, Mg or ammonium are exchanged. Suitable zeolites are described for example in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US 4 604 224, GB-A-2 013 259, EP-A-0 522 726, EP-A-0 384 070 and WO 94/24251.

Other suitable inorganic builders are, for example, amorphous or crystalline silicates, such as amorphous disilicates, crystalline disilicates, such as that Layered silicate SKS-6 (manufacturer Hoechst AG). The silicates can be in shape their alkali, alkaline earth or ammonium salts are used. Preferably Na, Li and Mg silicates are used.

Other suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be in the form of their alkali, alkaline earth or ammonium salts be used. Na, Li and Mg carbonates are preferred or hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate used.

The inorganic builders can be present in detergents in amounts of 0 up to 60 wt .-% together with any organic to be used Cobuilders may be included. The inorganic builders can either alone or incorporated into the detergent in any combination become. They are used in powder or granular detergents in amounts of 10 to 60% by weight, preferably in amounts of 20 to 50 % By weight used. In structured (multi-phase) liquid detergents are inorganic builders in amounts of up to 40 wt .-%, preferably up to 20 wt .-% used. They are in the liquid formulation ingredients suspended.

In powder or granular as well as in liquid detergent formulations are organic cobuilders in amounts of 0.1 to 20% by weight, preferably in amounts of 1 to 15 wt .-% together with inorganic Builders included. The powder or granular detergent can a bleaching system consisting of at least one bleach, optionally in combination with one Bleach activator and / or contain a bleach catalyst.

bleach

Suitable bleaching agents are perborates and percarbonate in the form of their alkali, especially their Na salts. They are in amounts of 5 to 30% by weight, preferably 10 to 25 wt .-% contained in the formulations. Further Suitable bleaching agents are inorganic and organic peracids in the form their alkali or magnesium salts or partly in the form of the free Acids. Examples of suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and dodecane-1,10-diper acid. An example of an inorganic peracid salt is potassium peroxomonosulfate (Oxon).

• Acylamine, wie Tetraacetylethylendiamin, Tetraacetylglycoluril, N,N'-Diacetyl-N,N'-dimethylharnstoff und 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin
• acylierte Lactame, wie Acetylcaprolactam, Octanoylcaprolactam und Benzoylcaprolactam
• substituierte Phenolester von Carbonsäuren, wie Na-acetoxybenzolsulfonat, Na-octanoyloxybenzolsulfonat und Na-nonanoyloxybenzolsulfonat
• acylierte Zucker, wie Pentaacetylglucose
• Anthranilderivate, wie 2-Methylanthranil oder 2-Phenylanthranil
• Enolester, wie Isopropenylacetat
• Oximester, wie O-Acetylacetonoxim
• Carbonsäureanhydride, wie Phthalsäureanhydrid oder Essigsäureanhydrid.

Suitable bleach activators are, for example

• Acylamines such as tetraacetylethylenediamine, tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
• acylated lactams such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam
• substituted phenol esters of carboxylic acids such as Na-acetoxybenzenesulfonate, Na-octanoyloxybenzenesulfonate and Na-nonanoyloxybenzenesulfonate
• acylated sugars such as pentaacetyl glucose
• Anthranil derivatives, such as 2-methylanthranil or 2-phenylanthranil
• Enol esters such as isopropenyl acetate
• Oxime esters such as O-acetylacetone oxime
• Carboxylic anhydrides such as phthalic anhydride or acetic anhydride.

Tetraacetylethylenediamine and Na-nonanoyloxy-benzenesulfonates are preferred used as bleach activators. The bleach activators become heavy-duty detergents in amounts of 0.1 to 15% by weight, preferably in amounts from 1.0 to 8.0% by weight, particularly preferably in amounts from 1.5 to 6.0 % By weight added.

Suitable bleaching catalysts are quaternized imines and sulfonimines, such as they are described in US 5 360 568, US 5 360 569 and EP-A-0 453 003 and Mn complexes, see WO 94/21777. If bleaching catalysts in The detergent formulations are used in quantities up to 1.5% by weight, preferably up to 0.5% by weight, in the case of very active manganese complexes in amounts up to 0.1% by weight.

enzymes

The detergents preferably contain an enzyme system. This is what it is about proteases, lipases commonly used in detergents, Amylases and cellulases. The enzyme system can work on a single one of the Enzymes may be restricted or a combination of different enzymes include. Of the commercial enzymes, the detergents are in usually amounts of 0.1 to 1.5 wt .-%, preferably 0.2 to 1.0 % By weight of the compounded enzyme was added. Suitable proteases are for example Savinase and Esperase (manufacturer Novo Nordisk). A suitable one Lipase is, for example, Lipolase (manufacturer Novo Nordisk). A suitable cellulase is, for example, Celluzym (manufacturer Novo Nordisk).

Other common ingredients

The detergents preferably contain soil as other conventional ingredients release polymers and / or graying inhibitors. This is for example to polyester from polyethylene oxides with ethylene glycol and / or Propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids, or polyester from end groups capped on one side Polyethylene oxides with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, see US 3,557,039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US 5 142 020.

Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, see US 4 746 456, US 4,846,995, DE-A-3,711,299, US 4,904,408, US 4,846,994 and US 4,849,126 or modified celluloses, such as methyl cellulose, Hydroxypropyl cellulose or carboxymethyl cellulose.

Graying inhibitors and soil release polymers are in the detergent formulations 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably contain 0.3 to 1.2% by weight. Preferred used Soil release polymers are the graft polymers known from US Pat. No. 4,746,456 of vinyl acetate on polyethylene oxide with a molecular weight of 2,500 - 8,000 im Weight ratio 1.2: 1 to 3.0: 1, and commercially available polyethylene terephthalate / polyoxyethylene terephthalate with a molecular weight of 3,000 to 25,000 made of polyethylene oxides the molecular weight 750 to 5,000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and those known from DE-A-44 03 866 Block polycondensates, the blocks of ester units from polyalkylene glycols a molecular weight of 500 to 7,500 and aliphatic dicarboxylic acids and / or Monohydroxymonocarboxylic acids and blocks made from ester units aromatic dicarboxylic acids and polyhydric alcohols. This Amphiphilic block copolymers have molecular weights of 1,500 to 25,000.

• 3 bis 50, vorzugsweise 8 bis 30 Gew.-% mindestens eines anionischen und/oder nichtionischen Tensids,
• 5 bis 50, vorzugsweise 15 bis 42,5 Gew.-% mindestens eines anorganischen Builders,
• 5 bis 30, vorzugsweise 10 bis 25 Gew.-% eines anorganischen Bleichmittels,
• 0,1 bis 15, vorzugsweise 1 bis 8 Gew.-% eines Bleichaktivators,
• 0 bis 1, vorzugsweise bis höchstens 0,5 Gew.-% eines Bleichkatalysators,
• 0,05 bis 5 Gew.-%, vorzugsweise 0,2 bis 2,5 Gew.-% eines Farbübertragungsinhibitors auf Basis von wasserlöslichen Homopolymerisaten von N-Vinylpyrrolidon oder N-Vinylimidazol, wasserlöslichen Copolymerisaten aus N-Vinylimidazol und N-Vinylpyrrolidon, vernetzten Copolymerisaten aus N-Vinylimidazol und N-Vinylpyrrolidon mit einer Teilchengröße von 0,1 bis 500, vorzugsweise bis zu 250 µm, wobei diese Copolymerisate 0,01 bis 5, vorzugsweise 0,1 bis 2 Gew.-% N,N'-Divinylethylenharnstoff als Vernetzer enthalten. Weitere Farbübertragungsinhibitoren sind wasserlösliche und auch vernetzte Polymerisate von 4-Vinylpyridin-N-oxid, die durch Polymerisieren von 4-Vinylpyridin und anschließende Oxidation der Polymeren erhältlich sind,
• 0,1 bis 20, vorzugsweise 1 bis 15 Gew.-% mindestens eines erfindungsgemäßen Gemisches aus Komponenten (a), (b) und (c),
• 0,2 bis 1,0 Gew.-% Protease,
• 0,2 bis 1,0 Gew.-% Lipase,
• 0,3 bis 1,5 Gew.-% eines Soil release Polymers,
• weniger als 24 Gew.-%, bevorzugt maximal 20 Gew.-%, vorzugsweise maximal 10 Gew.-%, insbesondere kein Triphosphat,
• gemäß einer Ausführungsform maximal 20 Gew.-%, vorzugsweise maximal 10 Gew.-%, insbesondere kein LAS,

   wobei die Gesamtmenge der Inhaltsstoffe 100 Gew.-% ergibt.A typical powder or granular heavy-duty detergent can have the following composition, for example:

• 3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,
• 5 to 50, preferably 15 to 42.5% by weight of at least one inorganic builder,
• 5 to 30, preferably 10 to 25% by weight of an inorganic bleaching agent,
• 0.1 to 15, preferably 1 to 8% by weight of a bleach activator,
• 0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst,
• 0.05 to 5 wt .-%, preferably 0.2 to 2.5 wt .-% of a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and N-vinylpyrrolidone, crosslinked Copolymers of N-vinylimidazole and N-vinylpyrrolidone with a particle size of 0.1 to 500, preferably up to 250 microns, these copolymers 0.01 to 5, preferably 0.1 to 2 wt .-% N, N'-divinylethylene urea included as crosslinker. Further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers,
• 0.1 to 20, preferably 1 to 15% by weight of at least one mixture according to the invention of components (a), (b) and (c),
• 0.2 to 1.0% by weight of protease,
• 0.2 to 1.0% by weight lipase,
• 0.3 to 1.5% by weight of a soil release polymer,
• less than 24% by weight, preferably at most 20% by weight, preferably at most 10% by weight, in particular no triphosphate,
• According to one embodiment, a maximum of 20 wt.%, preferably a maximum of 10 wt.

the total amount of the ingredients being 100% by weight.

• 3 bis 50, vorzugsweise 8 bis 30 Gew.-% mindestens eines anionischen und/oder nichtionischen Tensids,
• 10 bis 60, vorzugsweise 20 bis 55 Gew.-% mindestens eines anorganischen Builders,
• 0 bis 15, vorzugsweise 0 bis 5 Gew.-% eines anorganischen Bleichmittels,
• 0,05 bis 5 Gew.-%, vorzugsweise 0,2 bis 2,5 Gew.-% eines Farbübertragungsinhibitors, siehe oben,
• 0,1 bis 20, vorzugsweise 1 bis 15 Gew.-% mindestens eines erfindungsgemäßen Gemisches aus den Komponenten (a), (b) und (c),
• 0,2 bis 1,0 Gew.-% Protease,
• 0,2 bis 1,0 Gew.-% Cellulase,
• 0,2 bis 1,5 Gew.-% eines Soil release Polymers, z.B. einem Pfropfpolymerisats von Vinylacetat auf Polyethylenglykol,
• weniger als 24 Gew.-%, vorzugsweise maximal 10 Gew.-%, insbesondere kein Triphosphat,
• gemäß einer Ausführungsform maximal 20 Gew.-%, vorzugsweise maximal 10 Gew.-%, insbesondere kein LAS,

   wobei die Gesamtmenge der Inhaltsstoffe 100 Gew.-% ergibt.A bleaching system is often completely or partially dispensed with in color-preserving special detergents (for example in so-called color detergents). A typical powder or granular color detergent can have the following composition, for example:

• 3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,
• 10 to 60, preferably 20 to 55% by weight of at least one inorganic builder,
• 0 to 15, preferably 0 to 5% by weight of an inorganic bleaching agent,
• 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor, see above,
• 0.1 to 20, preferably 1 to 15% by weight of at least one mixture according to the invention of components (a), (b) and (c),
• 0.2 to 1.0% by weight of protease,
• 0.2 to 1.0% by weight cellulase,
• 0.2 to 1.5% by weight of a soil release polymer, for example a graft polymer of vinyl acetate on polyethylene glycol,
• less than 24% by weight, preferably at most 10% by weight, in particular no triphosphate,
• According to one embodiment, a maximum of 20 wt.%, preferably a maximum of 10 wt.

the total amount of the ingredients being 100% by weight.

The powdered or granular detergents can be used as other usual Contain components up to 60 wt .-% of inorganic adjusting agents. Sodium sulfate is usually used for this. Preferably, the detergents according to the invention but low in adjusting agents and contain up 20% by weight, particularly preferably up to 8% by weight, of adjusting agents.

The detergents according to the invention can have different bulk densities Have a range from 300 to 950 g / l. Have modern compact detergents usually high bulk densities, such as 550 to 950 g / l, and show one Granular structure.

• 5 bis 60, vorzugsweise 10 bis 40 Gew.-% mindestens eines anionischen und/oder nichtionischen Tensids,
• 0,05 bis 5 Gew.-%, vorzugsweise 0,2 bis 2,5 Gew.-% eines Farbübertragungsinhibitors (siehe oben),
• 0,1 bis 20, vorzugsweise 1 bis 15 Gew.-% mindestens eines oben beschriebenen erfindungsgemäßen Gemisches,
• 0 bis 1,0 Gew.-% Protease,
• 0 bis 1,0 Gew.-% Cellulase,
• 0 bis 1,5 Gew.-% eines Soil release Polymers und/oder Vergrauungsinhibitors,
• 0 bis 60 Gew.-% Wasser,
• 0 bis 10 Gew.-% Alkohole, Glykole wie Ethylenglykol, Diethylenglykol oder Propylenglykol oder Glycerin,

   wobei die Gesamtmenge der Inhaltsstoffe 100 Gew.-% ergibt.The liquid detergents according to the invention contain, for example

• 5 to 60, preferably 10 to 40% by weight of at least one anionic and / or nonionic surfactant,
• 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor (see above),
• 0.1 to 20, preferably 1 to 15% by weight of at least one mixture according to the invention described above,
• 0 to 1.0% by weight of protease,
• 0 to 1.0% by weight cellulase,
• 0 to 1.5% by weight of a soil release polymer and / or graying inhibitor,
• 0 to 60% by weight of water,
• 0 to 10% by weight of alcohols, glycols such as ethylene glycol, diethylene glycol or propylene glycol or glycerin,

the total amount of the ingredients being 100% by weight.

The detergents can optionally contain other customary additives. As additional additives, for example, complexing agents, Phosphonates, optical brighteners, dyes, perfume oils, foam attenuators and Corrosion inhibitors may be included.

TAED:

Tetraacetylethylendiamin

Soil release Additiv 1:

Polyethylenterephthalat/Polyoxyethylenterephthalat im Molverhältnis 3:2, Molmasse des einkondensierten Polyethylenglykols 4.000, Molmasse des Polyesters 10.000

Soil release Additiv 2:

Pfropfpolymerisat von Vinylacetat auf Polyethylenglykol der Molmasse 8.000, Molmasse des Pfropfpolymerisats 24.000

EO:

Ethylenoxid

(Fortsetzung der Tabelle) Bestandteile A B C D E F G H I J K L M N O P Perborat-4-H₂O 20 20 24 Perborat-2-H₂O 15 14,5 Percarbonat 15 15 18 20 15 15 15 15 Carboximethylcellulose 1 1 1,5 2,5 0,5 2 1 1,3 1,5 1 1 1 1 1 1 Soil release Additiv 1 0,8 0,8 0,8 0,5 0,5 0,5 0,5 0,5 0,5 Soil release Additiv 2 0,5 0,5 Lipase 0,2 0,5 0,5 0,5 0,5 0,5 0,5 Protease 0,5 0,5 0,5 0,5 0,5 0,5 1 0,5 Cellulase 0,3 0,2 0,2 Natriumsulfat 3 3 3 1,5 3,5 3 3,5 2,4 3 3 2,4 1,3 2 Ethanol Cobuilder 1 5 5 5 5 5 5 8 5 5 5 5 5 5 5 5 15 Phosphonat 0,2 0,2 0,5 opt. Aufheller 0,2 0,2 0,2 0,2 0,2 0,2 0,2 0,2 0,2 Farbübertragungsinhibitor 1,5 1 Wasser 3,5 3,5 0,3 1 1 1 22,5 11 40,6 The detergent formulations below are suitable for using the mixtures according to the invention. Compositions A - M are compact detergents, N and O are examples of color detergents, and formulation P is a structured liquid detergent. The abbreviations have the following meaning:

TAED:

tetraacetylethylenediamine

Soil release additive 1:

Polyethylene terephthalate / polyoxyethylene terephthalate in a molar ratio of 3: 2, molecular weight of the condensed polyethylene glycol 4,000, molecular weight of the polyester 10,000

Soil release additive 2:

Graft polymer of vinyl acetate on polyethylene glycol with a molecular weight of 8,000, molecular weight of the graft polymer 24,000

EO:

ethylene oxide

(Continuation of the table) ingredients A B C D e F G H I J K L M N O P Perborate-4-H ₂ O 20 20 24 Perborate-2-H ₂ O 15 14.5 percarbonate 15 15 18 20 15 15 15 15 carboxymethylcellulose 1 1 1.5 2.5 0.5 2 1 1.3 1.5 1 1 1 1 1 1 Soil release additive 1 0.8 0.8 0.8 0.5 0.5 0.5 0.5 0.5 0.5 Soil release additive 2 0.5 0.5 lipase 0.2 0.5 0.5 0.5 0.5 0.5 0.5 protease 0.5 0.5 0.5 0.5 0.5 0.5 1 0.5 cellulase 0.3 0.2 0.2 sodium sulphate 3 3 3 1.5 3.5 3 3.5 2.4 3 3 2.4 1.3 2 ethanol Cobuilder 1 5 5 5 5 5 5 8th 5 5 5 5 5 5 5 5 15 phosphonate 0.2 0.2 0.5 opt. brighteners 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Color transfer inhibitor 1.5 1 water 3.5 3.5 0.3 1 1 1 22.5 11 40.6

Dishwashing formulations

The mixtures of (a), (b) and (c) as described above according to one embodiment of the invention in dishwashing detergent formulations used, in particular as incrustation inhibitor and / or deposit inhibitor.

The preferred embodiments of the agents and Quantities also apply to the dishwasher detergent formulations.

Nachstehend werden die erfindungsgemäßen Gemische, Waschmittel und Reinigungsmittel anhand von Beispielen näher erläutert. Sofern nicht anders angegeben, beziehen sich Prozentangaben auf das Gewicht. The dishwashing detergents can be in powder form or can also be in liquid form. The composition of the dishes can vary widely. They usually contain sodium citrate, sodium carbonate and sodium disilicate. Dishwashing detergent formulations are given below as examples. (N = comparison) in which the mixtures according to the invention can be used.

The mixtures, detergents and cleaning agents according to the invention are explained in more detail below with the aid of examples. Unless otherwise stated, percentages relate to the weight.

example 1 Production of tallow fatty amine phosphoric acid salt

535 g of tallow fatty amine are dissolved in 1,500 ml of acetone and stirred with 261 g of 75% phosphoric acid are added. The rainfall is about one Suction filtered and dried. The yield is 720 g. The salt has a waxy consistency.

Example 2 Production of tallow fatty amine phosphoric acid salt

13.5 g of tallow fatty amine are melted in a beaker at 60 ° C and while stirring with a spatula containing 6.5 g of 75% phosphoric acid added. The temperature of the paste rises. After cooling you get a soft wax that is easy to cut.

Example 3

20 g of the salt prepared in Example 1 are placed in a 100 ml round bottom flask, which is purged with nitrogen, poured in and up for 4 hours Heated 200 ° C. After cooling, the wax-like content is crushed and analyzed analytically. It consists of 1/3 tallow fatty amine phosphoric acid salt and 2/3 from a condensation product of tallow fatty amine and Phosphoric acid.

Example 4 Production of tallow fatty amine polyphosphoric acid salt

56 g of tallow fatty amine are dissolved in 150 ml of toluene at 70 ° C and with 16 g of polyphosphoric acid were added within 15 minutes. The resulting precipitation is suctioned off and dried.

Example 5

13.7 g of tallow fatty amine are dissolved in 40 g of glycerol at 60 ° C and with 6.5 g 75% phosphoric acid added. A viscous paste is obtained.

Example 6-8

In a beaker, taig fatty amine, a reaction product of a C ₁₆ / C ₁₈ oxo alcohol with 7 mol ethylene oxide (nonionic surfactant) and water according to Table 1, is prepared at 60 ° C. and 75% phosphoric acid is added. Viscous pastes are obtained, which solidify softly like a wax upon cooling.

Production of the blends Example 9

Polymer Nr. 1:

Copolymer aus Maleinsäure und Acrylsäure im Verhältnis 70:30 in Form des Natriumsalzes, 40%ig, Molgewicht 70.000

Polymer Nr. 2:

Copolymer aus Maleinsäure und Diisobuten in Form des Natriumsalzes, 44%ig, Molgewicht 4.000

Polymer Nr. 3:

Polyacrylsäure in Form des Natriumsalzes, 45%ig, Molgewicht 8.000

Polymer Nr. 4:

Polyasparaginsäure, Natriumsalz, 42%ig, Mol-gewicht 30.000

S:

trübe Lösung

L:

klare Lösung

Aqueous solutions of polycarboxylates in the sodium form are mixed with tallow fatty amine phosphoric acid salt in accordance with Table 2 and dispersed as finely as possible using a dispersing machine (Ultra Turrax). Depending on the polymer, this results in clear solutions to cloudy suspensions.

Polymer No. 1:

Copolymer of maleic acid and acrylic acid in a ratio of 70:30 in the form of the sodium salt, 40%, molecular weight 70,000

Polymer No. 2:

Copolymer of maleic acid and diisobutene in the form of the sodium salt, 44%, molecular weight 4,000

Polymer No. 3:

Polyacrylic acid in the form of the sodium salt, 45%, molecular weight 8,000

Polymer No. 4:

Polyaspartic acid, sodium salt, 42%, molecular weight 30,000

S:

cloudy solution

L:

clear solution

Example 17

40 g of a copolymer of maleic anhydride and isobutene with molecular weight 6,000 (which is in the anhydride form) are in 40 ml of water suspended and mixed with 4 g of tallow fatty amine phosphoric acid salt. The Suspension is neutralized with 50% by weight sodium hydroxide solution until the pH the solution is between 7 and 8 and the polymer is dissolved. The Solids content of the solution is 44%.

Example 18

40 g of the polymer from Example 17 are suspended in 40 ml Water with 4 g of tallow fatty amine polyphosphoric acid salt and sodium hydroxide solution hydrolyzed. The solids content of the resulting solution is 43%.

Example 19

0.1 kg of the tallow fatty amine phosphoric acid salt from Example 1 are 0.9 kg of a powdery copolymer of 70% acrylic acid and 30% maleic acid in the sodium salt form, which is obtained by spray drying an aqueous Solution was prepared, mixed in a paddle mixer. You get a free-flowing powder.

0.05 kg of the powder mixture becomes 0.95 kg of a powder Detergent mixed in a paddle mixer until even Distribution is reached.

The powder detergent C thus obtained then has the following composition: Zeolite A 36% sodium 12% Dodecylbenzenesulfonate Na salt 6% C ₁₂ / C ₁₈ alkyl sulfate sodium salt 2% Soap 1% Reaction product from C ₁₃ / C ₁₅ oxo alcohol and 7 mol ethylene oxide 7% Na metasilicate x 5H ₂ O 3.5% TAED 3.5% Tylose CR 1500 1.5% sodium sulphate 3% Na perborate monohydrate 15% water 4.5% Mixture of 10% tallow fatty amine phosphoric acid salt and 90% copolymer of 70% acrylic acid and 30% maleic acid in the sodium form 5%

Using the mixtures according to the invention from Examples 1 to 8 the detergent formulations described in Table 3 below Using the powder detergent C.

Table 3 contains the results obtained when testing the incrustation-inhibiting effect. The detergent formulations described in the table were used for washing test fabrics made of cotton. The number of washing cycles was 15. After this type of washing, the ash content of the fabric was determined by ashing the test fabric in each case. washing conditions device Launder-o-meter from Atlas, Chicago Number of wash cycles 15 wash liquor 250 ml liquor washing time 30 min at 60 ° C detergent dosage 4.5 g / l water hardness 22.4 ° dH (4 mmol Ca / l; Ca: Mg = 4: 1) Test fabric 20 g cotton-nettle fabric

From the results given in Table 3 it is clear that when used of the mixtures according to the invention the ash formation of test fabrics is significantly reduced. This corresponds to a much improved one Incrustation inhibition on the tissue.

Dishwashing detergents

Dishwashing detergent E was mixed together and has the following composition: Sodium citrate * 2 H ₂ O 20% Sodium disilicate amorphous 24% sodium 40% Sodium perborate * 1 H ₂ O 7% TAED 2% non-ionic low-foaming surfactant 2% scale inhibitor 5%

a) Gemisch aus 10% Talgfettamin-Phosphorsäuresalz und 90% Copolymer aus 70% Acrylsäure und 30% Maleinsäure in der Natriumform

b) Gemisch aus 10% Talgfettamin-Phosphorsäuresalz und 90% Copolymer aus 50% Maleinsäure und 59% Isobuten in der Natriumform

c) Gemisch aus 10% Talgfettamin-Phosphorsäuresalz und 90% Polyacrylsäure (MW: 8000) in der Natriumform

d) Gemisch aus 10% Talgfettpolyaminphosphorsäurezusatz und 90% Polyacrylsäure

Examples of the deposit inhibitor are:

a) Mixture of 10% tallow fatty amine phosphoric acid salt and 90% copolymer of 70% acrylic acid and 30% maleic acid in the sodium form

b) Mixture of 10% tallow fatty amine phosphoric acid salt and 90% copolymer of 50% maleic acid and 59% isobutene in the sodium form

c) Mixture of 10% tallow fatty amine phosphoric acid salt and 90% polyacrylic acid (MW: 8000) in the sodium form

d) Mixture of 10% tallow fat polyamine phosphoric acid additive and 90% polyacrylic acid

The test for deposit-inhibiting effect is carried out in such a way that 4 g of the dishwashing detergent formulation described above are used per liter of drinking water of 10 ° dH. In a Miele G 590 SC household dishwashing machine, 15 washing cycles are carried out with a set of dishes consisting of black porcelain plates, knives and drinking glasses. After the 15 washing cycles, the dishes were assessed visually. The grade 0 means that even after 15 cycles there is no deposit on the dishes, the grade 9 on the other hand means a very strong deposit. The grades 1-8 are gradations between the grades 0 and 9. The washing results are given in the table. As can be seen from this, the mixtures of amines and phosphoric acid and polycarboxylate are better deposit inhibitors than the polycarboxylates commonly used.

Claims (10)

1. A mixture composed of

   (a) from 0.1 to 99 % by weight of at least one polycarboxylate having at least 3 carboxyls, the polycarboxylate comprising at least one of the structural units acrylic acid, maleic acid, maleic anhydride, aspartic acid, in the form if desired of an alkali metal salt,

   (b) from 0.1 to 99 % by weight of at least one amine having a pK_a value of more than 9, and

   (c) from 0.1 to 99 % by weight of at least one acid selected from the group consisting of mineral acids and organic acids having one or two carboxyls and not more than 15 carbons,

   with the proviso that the mixture contains less than 24 % by weight of triphosphates and the total amount of the ingredients is 100 % by weight.
2. A mixture as claimed in claim 1, wherein the amine (b) is at least one amine having at least four carbons, preferably tallow fatty amine, hydrogenated tallow fatty amine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, 2-propylheptylamine, undecylamine, dodecylamine, tridecylamine, cetylamine, stearylamine, palmitylamine, oleylamine, coconut fatty amine, mono-α-branched secondary amines, bis-α-branched secondary amines of the formula (I) R⁴R³HC-HN-CHR¹R² where R¹, R², R³ and R⁴ independently are substituted or unsubstituted C₁-C₂₀-alkyls, and amines of the formula (II) R⁵NR⁹-[(CR⁷R⁸)_m-NH]_n-R⁶ where n is an integer from 0 to 20 and m is an integer from 1 to 4, R⁵ is a C_1-30, preferably C_1-20, in particular C_1-10 alkyl, or C_2-30, preferably C_2-20, in particular C_2-10 alkenyl and each of R⁶, R⁷, R⁸ and R⁹ independently is hydrogen or is as defined for R⁵.
3. A mixture as claimed in claim 1 or 2, wherein the acid (c) is a phosphorus-containing acid.
4. The use of a mixture as claimed in any of claims 1 to 3 in detergents, especially as an encrustation inhibitor.
5. The use of a mixture as claimed in any of claims 1 to 3 in rinse aid formulations, especially as an encrustation inhibitor or scale inhibitor.
6. A detergent or rinse aid formulation comprising at least one surfactant and a mixture of

   (a) at least one polycarboxylate having at least three carboxyl groups, the polycarboxylate comprising at least one of the structural units acrylic acid, maleic acid, maleic anhydride, aspartic acid, in the form if desired of an alkali metal salt,

   (b) at least one amine whose pK_a value is greater than the pH, reduced by 1, of a 1 % strength liquor of the detergent,

   (c) at least one acid selected from the group consisting of mineral acids and organic acids having one or two carboxyls and not more than 15 carbons,
   and, if desired, other customary constituents, with the proviso that the detergent or the rinse aid contains less than 24 % by weight of triphosphate.
7. A detergent or rinse aid formulation comprising at least one surfactant and a mixture as claimed in any of claims 1 to 3 and, if desired, other customary constituents.
8. A detergent or rinse aid formulation as claimed in claim 6 or 7, composed of

   0.01-40 % by weight of component (a),

   0.01-20 % by weight of component (b), and

   0.01-20 % by weight of component (c),

   the total amount of the ingredients being 100 % by weight.
9. Use of a detergent formulation as claimed in any of claims 6 to 8 for cleaning textiles, especially for inhibiting encrustation.
10. The use of a rinse aid formulation as claimed in any of claims 6 to 8 for cleaning hard surfaces, particularly tableware, especially for inhibiting encrustation and scaling.