WO2001014507A1 - Composition de tensides - Google Patents

Composition de tensides Download PDF

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Publication number
WO2001014507A1
WO2001014507A1 PCT/EP2000/007885 EP0007885W WO0114507A1 WO 2001014507 A1 WO2001014507 A1 WO 2001014507A1 EP 0007885 W EP0007885 W EP 0007885W WO 0114507 A1 WO0114507 A1 WO 0114507A1
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weight
surfactant
acid
composition according
agents
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PCT/EP2000/007885
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German (de)
English (en)
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Georg Meine
Hans-Christian Raths
Thomas Müller-Kirschbaum
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Henkel Kommanditgesellschaft Auf Aktien
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    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters

Definitions

  • the present invention relates to a surfactant composition containing a combination of anionic surfactants based on Guerbet alkyl sulfates and other surfactants, and a detergent for textiles which contains this surfactant combination.
  • the surfactants contained in the detergents are most effective when they are completely dissolved.
  • a physical parameter for the dissolving behavior of surfactants is the so-called Krafft point, which is a term for the temperature at which the solubility of ionic surfactants increases sharply due to the formation of micelles.
  • Detergents preferably contain surfactants whose Krafft point is above the washing temperature.
  • JP08188793 A and JP08188794 A describe surfactant compositions which contain a combination of primary alkyl sulfates and Guerbet alkyl sulfate. Good biodegradability and a good cleaning effect against lipid-containing soiling are advertised.
  • the present invention was accordingly based on the object of providing a surfactant composition which shows outstanding effectiveness even at wash temperatures up to 40 ° C. and which can be used in detergents for textile household laundry.
  • a combination of special anionic surfactants based on Guerbet alkyl sulfates and at least one further surfactant shows great washing activity even at washing temperatures up to 40 ° C. and is suitable for being incorporated into detergents for household laundry.
  • the present invention accordingly relates to a surfactant composition which contains a combination of Guerbet alkyl sulfates with 12 to 22 carbon atoms and at least one further surfactant.
  • the Guerbet alkyl sulfates used according to the invention are obtained by sulfonating the Guerbet alcohols.
  • Guerbet alcohols are well-known compounds that are used as raw materials for the cosmetic industry. They result from the condensation of primary and secondary alcohols in the presence of strong alkali bases according to the reaction scheme
  • the starting compounds for the sulfonation are usually prepared from alcohols having 6 to 9 carbon atoms.
  • the Guerbet alkyl sulfates used according to the invention are generally used in the form of their sodium, potassium or ammonium salts. They show better solubility and thus also improved washing performance compared to the corresponding linear fatty talc sulfates.
  • the content of Guerbet alkyl sulfates in the composition according to the invention is preferably 1 to 40% by weight, particularly preferably 5 to 35% by weight and in particular 6 to 28% by weight, in each case based on the overall composition.
  • Nonionic, anionic, amphoteric and / or cationic surfactants can be contained as further surfactants.
  • the total content of other surfactants is on average preferably 1 to 40% by weight, particularly preferably 5 to 35% by weight and in particular 12 to 28% by weight, in each case based on the total composition.
  • the Guerbet alkyl sulfates and the other surfactants are preferably present in the composition according to the invention in a weight ratio of 10: 1 to 1:10, in particular 5: 1 to 1: 5 and particularly preferably 2: 1 to 1: 2.
  • the composition according to the invention preferably contains nonionic surfactants as further surfactants, in particular those selected from the alkoxylated alcohols, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, polyhydroxy fatty acid amides or any mixtures thereof.
  • the nonionic surfactants are preferably used in an amount of 1 to 25% by weight, in particular 1 to 15% by weight, based on the total composition.
  • the alkoxylated, advantageously ethoxylated, especially primary alcohols used are preferably those having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C 12- ⁇ 4 alcohols containing 3 EO, 7 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13-15 - alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 . 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • Mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • Alkyl glycosides have the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • amine oxides are N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide.
  • the amount of the amine oxides and the fatty acid alcoholamides is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Polyhydroxy fatty acid amides have the formula III,
  • RCO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for one linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula IV,
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylene derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • anionic surfactants that can be used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 . 13 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, as they ⁇ for example, C 12 8 - onoolefinen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products , into consideration.
  • alkanesulfonates which are composed of C 12 .
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing, the C 12 -C 16 alkyl sulfates and C 12 are - C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates of preferably.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, paimitic acid, stearic acid or behenic acid.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue that differs from ethoxylated fat derives alcohols, which are non-ionic surfactants (see description below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps can also be considered as further anionic surfactants.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the surfactant composition according to the invention can be used in all conventional detergents and cleaning agents, such as textile detergents, manual and machine dishwashing detergents, household cleaners and cleaning agents for the commercial sector. They can be assembled as desired, i.e. in liquid to gel and also in solid media.
  • the solid agents include the powders and extrudates, granules and moldings (tablets).
  • a further area of application of the surfactant composition according to the invention is cosmetic products.
  • the surfactant composition according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder and further conventional ingredients, in particular organic and / or in particular inorganic bleaching agents, Enzymes, complexing agents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, bitterns, color transfer inhibitors, foam regulators, additional bleach activators, dyes and fragrances.
  • Organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight.
  • Particularly suitable water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of this are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight. used.
  • the detergent-grade crystalline sodium aluminosilicates in particular zeolite A, P and / or X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m. Your calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12 and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Crystalline sheet silicates of the general formula Na 2 Si x 0 2x + 1 y H 2 O are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates, in which x, the so-called named module, a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 y H 2 O
  • ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as is described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the zeolite used can be, for example, finely crystalline, synthetic and bound water-containing zeolite, such as zeolite A, zeolite P or mixtures of A and P.
  • Zeolite MAP® commercial product from Crosfield
  • Zeolites of the faujasite type may be mentioned as further preferred and particularly suitable zeolites.
  • the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double six-ring subunit D6R (compare Donald W.
  • the zeolite structure group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.
  • Faujasite-type zeolites are made up of ß-cages, which are linked tetrahedrally via D6R subunits, the ß-cages being arranged in a diamond similar to the carbon atoms.
  • the three-dimensional network of the zeolites of the faujasite type used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities with a diameter of approximately 13 ⁇ and can be calculated using the formula Na 86 [(AIO 2 ) 86 (SiO 2 ) 106 ] • 264 H 2 O.
  • the network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume).
  • zeolite Y approx. 48% void volume
  • faujasite approx. 47% void volume.
  • zeolite of the faujasite type denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention, pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can also be used according to the invention, the advantages of the process according to the invention being particularly evident when at least 50 % By weight of the zeolites are faujasite-type zeolites.
  • the aluminum silicates which are used in the process according to the invention are commercially available and the methods for their preparation are described in standard monographs.
  • x can have values between 0 and 276 and the pore sizes range from 8.0 to 8.4 ⁇ .
  • zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ® and through the formula
  • Y-type zeolites are also commercially available and can be expressed, for example, by the formulas
  • the particle sizes of the zeolites of the Fauja-sit type used in the process according to the invention are in the range from 0.1 to 100 ⁇ m, preferably between 0.5 and 50 ⁇ m and in particular between 1 and 30 ⁇ m, in each case using standard particle size determination methods measured.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which a distinction can be made between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91, preferably “3 , melting point 60 °) and as a monohydrate (density 2.04, preferably " 3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 '3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) J and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 like 3 , water loss at 95 °), 7 mol. (Density 1, 68 like 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol.
  • Water (density 1 , 52 like “3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more.
  • Disodium hydrogenphosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals, which like dodecahydrate have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5) 5) a density of 2.536 have like 3 has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O.
  • trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of Disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is in water with an alkaline reaction easily soluble. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534, preferably 3 , melting point 988 °, also given as 880 °) and as decahydrate (density 1, 815-1, 836, gladly "3 , melting point 94 ° Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 O 7 is formed when disodium phosphate is heated to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying Decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4. Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher moles.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Organic cobuilders which can be used in the washing and cleaning agents according to the invention are, in particular, polycarboxylates, polymeric polycarboxylates, aspartic acid, polyacetal, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • pole are particularly preferred lyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • Oxydisuccinates and other derivatives of disuccinates preferably ethylenediaminisisuccinate, are further suitable cobuilders.
  • Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Builder substances are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide can also be used, which can be described by the formula H 2 N-CO-NH 2 ⁇ 2 0 2 .
  • the agents for cleaning hard surfaces when using the agents for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is in principle also possible for agents for textile washing.
  • Typical organic bleaching agents are the diacyiperoxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxyidoproic acid, phthalimide, phthalimide o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydiperbutyldiacid, diperoxybriperoxydiacid, diperoxybrassoxydiacid, diperoxybras
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in surfactant mixtures for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibronoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin, are also suitable.
  • a surfactant mixture according to the invention contains bleaching agents, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, while in the disinfectants according to the invention Bleaching agents are preferably contained from 0.5 wt .-% to 40 wt .-%, in particular from 5 wt .-% to 20 wt .-%.
  • bleach activators can be incorporated as the sole component or as an ingredient of component b).
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacet
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are also used as bleaching catalysts
  • Enzymes which can be used in the agents are those from the class of oxidases, proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean® , Maxacal®, Maxapem®, Alcalase®, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and or Carezame®.
  • proteases such as BLAP®, Optimase®, Opticlean® , Maxacal®, Maxapem®, Alca
  • Fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomo- nas cepacia obtained enzymatic agents.
  • the enzymes which may be used, as described for example in European patent EP 0 564 476 or in international patent applications WO 94/23005, can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation.
  • surfactant mixtures according to the invention are contained in the surfactant mixtures according to the invention preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to enzymes stabilized against oxidative degradation, for example from international ones Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.
  • the color transfer inhibitors that are suitable for use in agents according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular from the textile fiber suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used ,
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted type can also be used Diphenylstyryl be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) - 4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned optical brighteners can also be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
  • washing or cleaning agents can contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate.
  • antimicrobial action and antimicrobial active substance have the customary meaning, as used, for example, by KH Wallberger in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th ed.
  • suitable antimicrobial active substances are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives , Diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, anti- microbial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above.
  • the antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N- Methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan) , 2,4,4'-trichloro-2 , -hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1, 10-decanediyldi-1-pyridinyl
  • Halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial active ingredients of vegetable origin (for example from spices or herbs), animal and microbial origin are also suitable.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline, and essential oils such as Eugeneol , Thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium , iodonium or arsonium group, peroxo compounds and chlorine compounds.
  • Substances of microbial origin so-called bacteriocins, can also be used.
  • the quaternary ammonium compounds (QAV) suitable as antimicrobial active substances have the general formula (R 1 ) (R 2 ) (R 3 ) (R 4 ) N + X ⁇ , in which R to R 4 are identical or different C 7 -C 28 aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X "represent halide ions, sulfate ions , Hydroxide ions or similar anions
  • at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QAV can be prepared by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with a long alkyl residue and two methyl groups succeeds particularly easily, also the quaternization of tertiary amines with two long residues and a methyl group can be carried out with the help of methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyldimethyl-C12-alkylammonium chloride, CAS No. 58390- 78-6), benzoxonium chloride (benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No.
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1, 1, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • Dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridinium chloride ( CAS No.
  • QAV Benzalkonium chlorides with C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethyl-ammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are commercially available, for example, as Barquat® ex Lonza, Marquat® ex Mason, Variquat® ex Witco / Sherex and Hyamine® ex Lonza, and Bardac® ex Lonza.
  • Other commercially available antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide® and Dowicil® ex Dow, benzethonium chloride such as Hyamine® 1622 ex Rohm & Haas, methylbenzethonium chloride such as Hyamine® 10X ex Rohm & Haas, cetylpyridinium chloride such as cepacol chloride ex Merrell Labs.
  • the antimicrobial active ingredients are used in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3% by weight .-% and in particular from 0.01 to 0.2 wt .-% used.
  • the agents can contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of the other formulation components. UV absorbers are understood to mean organic substances (light protection filters) which are able to absorb ultraviolet rays and which taken energy in the form of longer-wave radiation, for example to release heat again.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
  • Biphenyl and especially stilbene derivatives as described, for example, in EP 0728749 A and which are commercially available as Tinosorb® FD or Tinosorb® FR ex Ciba are of particular importance.
  • 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as described in EP 0693471 B1, are to be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenz
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their salts
  • Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2-oxo-3-bomylidene-methyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
  • benzoylmethane such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-, are particularly suitable as typical UV-A filters.
  • Butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
  • the UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.
  • the composition contains common solvents, which include water-soluble or water-miscible organic solvents.
  • Solvents that can be used in the liquid to gel compositions come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, or methoxy, ethoxy Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutan
  • one or more thickeners or thickening systems can be added to the composition according to the invention.
  • the viscosity of the compositions according to the invention can be measured using customary standard methods (for example Brookfield RVD-VII viscometer at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 100 to 5000 mPas.
  • Preferred compositions have viscosities of 200 to 4000 mPas, values between 400 and 2000 mPas being particularly preferred.
  • Suitable thickeners are usually polymeric compounds. These swelling agents are mostly organic, high-molecular substances that absorb liquids, swell and eventually convert into viscous real or colloidal solutions, come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
  • the thickeners can be present in an amount of up to 5% by weight, preferably from 0.01 to 3% by weight, based on the finished composition.
  • Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob flour, starch, dextrins, gelatin and casein.
  • Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
  • a large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickeners from the substance classes mentioned are commercially available and are sold, for example, under the trade names Acusol ® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% strength in water, Rohm & Haas), Dapral ® -GT -282-S (alkyl polyglycol ether, Akzo), DeuteroP polymer 11
  • Preferred aqueous compositions contain 0.05 to 3% by weight, preferably 0.1 to 2% by weight and in particular 0.2 to 1.0% by weight, of a polysaccharide as thickener.
  • xanthan a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million daltons.
  • Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
  • Xanthan can be described by the following formula:
  • Examples of other preferred synthetic thickeners are polyurethanes and modified (meth) acrylates.
  • Polyurethanes are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula I.
  • R 1 is a low molecular weight or polymeric diol radical
  • R 2 is an aliphatic or aromatic group
  • n is a natural number.
  • R 1 is preferably a linear or branched C 2 . 12 -alk (en) yl group, but can also be a radical of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from formula I given above in that the radical R 1 contains further -O-CO-NH groups are bound.
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • HMDI, R 2 (CH 2 ) 6 ].
  • polyurethane-based thickeners are, for example, under the names AcrysoPPM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ® L75-N (nonionic PU dispersion, 50% ig in water, Borchers), Coatex ® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco ® DSX-1514 (PUR dispersion, 40% in water / butyltrigylcol.Henkel- Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit ® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.
  • AcrysoPPM 12 V mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas
  • Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula II
  • R 3 is H or a branched or unbranched C 1-4 alk (en) yl radical
  • X is NR 5 or O
  • R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8 . 22 -alk (en) yl radical
  • R 5 is H or R 4 and n is a natural number.
  • modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 represents H or a methyl group.
  • the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation.
  • Formula II only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO " groups.
  • Modified polyacrylates to be used with preference in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula IIa
  • R 4 represents a preferably unbranched, saturated or unsaturated C 8-22 alk (en) yl radical
  • R 6 and R 7 independently of one another are H or CH 3
  • the degree of polymerization n is a natural number
  • the degree of alkoxylation a is a natural number is between 2 and 30, preferably between 10 and 20.
  • Products of the formula IIa are commercially strength, for example, under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available.
  • R 4 is a stearyl radical
  • R 6 is a hydrogen atom
  • R 7 is H or CH 3
  • the degree of ethoxylation a is 20.
  • Modified polyacrylates of the formula II can be used in the compositions according to the invention in an amount of 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight, based on the entire composition.
  • complexing agents can be used to stabilize the viscosity.
  • complexing agents are low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof, citric acid or sodium citrate being particularly preferred.
  • the complexing agents can be present in an amount of 1 to 8% by weight, preferably 3.0 to 6.0% by weight and in particular 4.0 to 5.0% by weight, based on the finished composition ,
  • Another object of the present invention is an agent for washing textiles, which contains the surfactant combination according to the invention.
  • This textile detergent can be in liquid or solid, i.e. present in powder or granular form or as a so-called shaped body and also represent a so-called compound which is further processed as a preliminary product together with other preliminary products and starting materials to give the finished product.
  • such a detergent is in solid to granular form or as a shaped body and contains 1 to 10% by weight of Guerbet alkyl sulfate, 1 to 30% by weight of further surfactants, 1 to 25% by weight of builder substances, to up to 20% by weight of bleach, up to 10% by weight of bleach activator and possibly enzymes, complexing agents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, colorants and fragrances.
  • such an agent is in the form of a liquid detergent and contains 1 to 10% by weight of Guerbet alkyl sulfate and 1 to 30% by weight of further re surfactants, 1 to 25% by weight of builder substances, up to 20% by weight of bleach, up to 10% by weight of bleach activator, solvent and optionally enzymes, complexing agents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, colorants and fragrances.
  • an anionic detergent compound contains 5 to 30% by weight of Guerbet alkyl sulfate, 50 to 70% by weight of anionic surfactant, 5 to 20% by weight of nonionic surfactant, optionally cationic surfactant and detergency booster, as well as water and salts
  • a preferred nonionic detergent compound contains 5 to 20% by weight of Guerbet alkyl sulfate, up to 10% by weight of anionic surfactant, 5 to 30% by weight of nonionic surfactant, carrier material for the nonionic surfactant, optionally cationic surfactant and detergency booster, and Water and salts.
  • Yet another object of the present invention is an agent for cleaning hard surfaces.
  • Such an agent contains 1 to 10% by weight of Guerbet alkyl sulfate, 1 to 10% by weight of further surfactants, 1 to 20% by weight of builder substances, solvents and optionally enzymes, complexing agents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as dyes and fragrances.
  • Another object of the present invention is a means for manual cleaning of dishes.
  • Such an agent contains 1 to 10% by weight of Guerbet alkyl sulfate, 1 to 40% by weight of further surfactants, 1 to 20% by weight of builder substances, solvents and optionally enzymes, complexing agents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as dyes and fragrances.
  • the composition in wt .-%) is shown in Table 1, at 40 ° C and 60 ° C.
  • the reflectance values of the textiles were determined after washing (5-fold determination).
  • the dosage was 3.8 g / l, the water hardness 16 ° d.
  • Polymeric polycarboxylate manufactured by BASF AG
  • BASF AG Polymeric polycarboxylate

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une combinaison de tensides réalisée à partir de tensides anioniques sur la base d'alkylsulfates Guerbet et d'autres tensides. Cette combinaison de tensides atteint une bonne efficacité de lavage dès 40 DEG C.
PCT/EP2000/007885 1999-08-24 2000-08-12 Composition de tensides WO2001014507A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19939991.3 1999-08-24
DE1999139991 DE19939991A1 (de) 1999-08-24 1999-08-24 Tensidzusammensetzung

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115664A3 (fr) * 2009-03-30 2010-12-29 Unilever Nv Composition de conditionnement de tissus
WO2015191434A2 (fr) 2014-06-09 2015-12-17 Stepan Company Détergents pour nettoyage à l'eau froide
WO2016111884A2 (fr) 2015-01-08 2016-07-14 Stepan Company Détergents textiles à l'eau froide
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same

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US3480556A (en) * 1966-09-29 1969-11-25 Atlantic Richfield Co Primary alcohol sulfate detergent compositions
GB1257679A (fr) * 1969-02-20 1971-12-22
EP0439316A2 (fr) * 1990-01-22 1991-07-31 Unilever Plc Composition détergente
WO1991016409A1 (fr) * 1990-04-25 1991-10-31 Unilever N.V. Compositions pour detergents liquides
WO1995000117A1 (fr) * 1993-06-28 1995-01-05 The Procter & Gamble Company Compositions detergentes liquides a faible pouvoir moussant
JPH08188793A (ja) * 1995-01-12 1996-07-23 Kao Corp 洗浄剤組成物

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Publication number Priority date Publication date Assignee Title
US3480556A (en) * 1966-09-29 1969-11-25 Atlantic Richfield Co Primary alcohol sulfate detergent compositions
GB1257679A (fr) * 1969-02-20 1971-12-22
EP0439316A2 (fr) * 1990-01-22 1991-07-31 Unilever Plc Composition détergente
WO1991016409A1 (fr) * 1990-04-25 1991-10-31 Unilever N.V. Compositions pour detergents liquides
WO1995000117A1 (fr) * 1993-06-28 1995-01-05 The Procter & Gamble Company Compositions detergentes liquides a faible pouvoir moussant
JPH08188793A (ja) * 1995-01-12 1996-07-23 Kao Corp 洗浄剤組成物

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DATABASE WPI Week 199639, Derwent World Patents Index; AN 1996-388757, XP002154741 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115664A3 (fr) * 2009-03-30 2010-12-29 Unilever Nv Composition de conditionnement de tissus
WO2015191434A2 (fr) 2014-06-09 2015-12-17 Stepan Company Détergents pour nettoyage à l'eau froide
WO2015191434A3 (fr) * 2014-06-09 2016-04-21 Stepan Company Détergents pour nettoyage à l'eau froide
CN106574209A (zh) * 2014-06-09 2017-04-19 斯泰潘公司 用于冷水清洗的洗涤剂
US10421930B2 (en) 2014-06-09 2019-09-24 Stephan Company Detergents for cold-water cleaning
CN106574209B (zh) * 2014-06-09 2020-02-14 斯泰潘公司 用于冷水清洗的洗涤剂
WO2016111884A2 (fr) 2015-01-08 2016-07-14 Stepan Company Détergents textiles à l'eau froide
WO2016111884A3 (fr) * 2015-01-08 2016-11-24 Stepan Company Détergents textiles à l'eau froide
US10570352B2 (en) 2015-01-08 2020-02-25 Stepan Company Cold-water laundry detergents
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
US11891586B2 (en) 2019-04-12 2024-02-06 Ecolab Usa Inc. Highly acidic antimicrobial multi-purpose cleaner and methods of making and using the same

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