Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/40—Monoamines or polyamines; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/08—Acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines

Definitions

• 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.
• 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.
• 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 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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
• the polycarboxylates contain no aromatic Residues.
• an amine is at least, preferably used with a pK a value greater than 9 9.5 to 12.
• the amines contain only aliphatic, cycloaliphatic and / or araliphatic residues.
• araliphatic residues are understand those in which aromatic radicals have alkylene groups are connected to the amine nitrogen atom.
• 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 .
• 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
• the radical R 9 a hydrogen atom or a C 1-4 alkyl radical or C 2-4 alkenyl radical.
• 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 are preferably used as component (b).
• the amines can be primary, secondary or tertiary.
• the amines can be hydrophilic or hydrophobic.
• 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
• 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.
• 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-ethylhexylamine, alkanolamines
• 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.
• mono- and polyvalent glycidyl ethers such as butyl glycidyl ether, ethylhexyl glycidyl ether, C 12 / C 14 alcohol glycidyl ether, C 13 / C 15 -
• 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.
• epoxidized castor oil or alkyloxiranes which can be prepared by epoxidizing olefins, such as propyloxirane, decyloxirane, dodecyloxirane, octadecyloxirane.
• 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.
• 3-isopropylaminopropylamine or dialkylaminoalkylamines such as 3-methyl tallow fatty aminopropylamine, 3-ditallow fatty aminopropylamine, 2-dimethylaminoethylamine, 1-diethylamino-4-aminopentane, Dimethylaminopropylamine.
• 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.
• 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,
• 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.
• 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, cocylamine, mono- ⁇ -branched secondary amines, bis- ⁇ -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) 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• Solid polycarboxylates can be in the form of powders or Granules accumulate.
• 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.
• 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.
• 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.
• an aqueous can be used Solution of polyacrylic acid in the acid form first with alkylamine and then add phosphoric acid.
• 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.
• the invention further relates to detergents containing at least one Surfactant and a mixture according to the invention and optionally other usual components.
• 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.
• 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.
• 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.
• the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
• 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.
• 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.
• 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.
• LAS linear alkylbenzenesulfonates
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• zeolites Different types 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.
• 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.
• 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.
• 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.
• 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.
• 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).
• 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.
• 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.
• 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).
• 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.
• 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.
• 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.
• 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.
• 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.
• the detergents can optionally contain other customary additives.
• additional additives for example, complexing agents, Phosphonates, optical brighteners, dyes, perfume oils, foam attenuators and Corrosion inhibitors may be included.
• the preferred embodiments of the agents and Quantities also apply to the dishwasher detergent formulations.
• the dishwashing detergents can be in powder form or can also be in liquid form.
• Example 2 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.
• 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.
• 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%.
• 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.
• 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%
• Table 3 contains the results obtained when testing the incrustation-inhibiting effect.
• 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%
• 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.
• 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.

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• 1997
  • 1997-03-25 US US09/155,410 patent/US6172028B1/en not_active Expired - Lifetime
  • 1997-03-25 BR BR9708274A patent/BR9708274A/pt not_active Application Discontinuation
  • 1997-03-25 ES ES97914304T patent/ES2201281T3/es not_active Expired - Lifetime
  • 1997-03-25 DE DE59710275T patent/DE59710275D1/de not_active Expired - Lifetime
  • 1997-03-25 JP JP53403497A patent/JP4240535B2/ja not_active Expired - Fee Related
  • 1997-03-25 BR BRPI9701467-2A patent/BR9701467B1/pt not_active IP Right Cessation
  • 1997-03-25 EP EP97914304A patent/EP0906394B1/de not_active Expired - Lifetime
  • 1997-03-25 AU AU21600/97A patent/AU2160097A/en not_active Abandoned
  • 1997-03-25 WO PCT/EP1997/001511 patent/WO1997035949A1/de not_active Ceased

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