EP1106675B1 - Verwendung von Partialglyceridpolyglycolethern - Google Patents
Verwendung von Partialglyceridpolyglycolethern Download PDFInfo
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- EP1106675B1 EP1106675B1 EP00125727A EP00125727A EP1106675B1 EP 1106675 B1 EP1106675 B1 EP 1106675B1 EP 00125727 A EP00125727 A EP 00125727A EP 00125727 A EP00125727 A EP 00125727A EP 1106675 B1 EP1106675 B1 EP 1106675B1
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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
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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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
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
Definitions
- the invention is in the field of surface active preparations and relates to the use of selected mixtures of ethoxylated partial glycerides and glycerol ethoxylates for the production of washing, rinsing and cleaning agents.
- Nonionic surfactants are of particular importance for the production of washing, rinsing and Detergents, as they have a special cleaning ability against fatty soiling have. They prove to be complementary in their properties to anionic surfactants, with however, they are commonly used together but have the advantage over them inverse solubility, i. Nonionic surfactants dissolve at low temperatures while they are in the heat by breaking polar polar hydrogen bonds and therefore are suitable especially for the production of liquid detergents.
- ethoxylated fatty alcohols are used for the production of detergents, however in a series of particularly stubborn stains, such as Make Up or Lipstick Have weaknesses.
- the incorporation into solid detergents, in particular detergent tablets, is associated with problems because the fatty alcohol ethoxylates show a tendency to bleed, i.e. Separate from the homogeneous preparation, resulting in a whole series of unwanted side effects causes: the washing power is reduced, the cardboard is softened and not uncommon partially deactivated with defoamer used.
- EP-A-1 045 021 shows a composition containing mixtures of ethoxylation products of mono-, di- and tri-glycerides and glycerols, in the weight ratio 85/15 to 40/60; This composition is used as a surfactant or co-surfactant in detergents and cleaners used. This patent application falls under Art. 54 (3) EPC.
- the complex object of the present invention has been to provide new nonionic Surfactants for the preparation of solid or liquid washing, rinsing and cleaning agents, preferably to provide those in tablet form, which reliably the above-mentioned disadvantages avoid.
- the invention relates to the use of ethoxylation of Partialglyceriden for the production of detergents, dishwashing detergents and cleaning agents, which are characterized in that they from mixtures of Partialglyceridethoxylaten and Glycerinethoxylaten in the weight ratio 3.3: 1 to 6: 1 and preferably 3.5 : 1 to 4.5: 1 using partial glycerides of formula (I) in which R 1 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms and R 2 and R 3 are independently of each other R 1 CO or hydrogen, with the proviso that either R 2 or R 3 is hydrogen, wherein adducts of average 5 to 20 moles of ethylene oxide to 1 mole of partial glyceride is used.
- R 1 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms
- R 2 and R 3 are independently of each other R 1
- the ethoxylation products are particularly critical Stains such as make-up or lipstick even at low temperatures have a particularly high cleaning power. This was not to be expected, since the The prior art teaches that mixtures of ethoxylated partial glycerides and glycerol ethoxylates only up to a weight ratio of 3: 1 maximum have a sufficient detergency.
- the invention also includes the recognition that the mixtures are stable in solid preparations, especially in detergent tablets, i. it does not bleed or bleed a deactivation of the defoamer instead.
- the ethoxylation products of partial glycerides are known substances, as described, for example, in BE 866868 (Ashland Oil, cited by Derwent Abstract 82097A / 46) and German Patent DE-C3 2024051 (Henkel). These are therefore technical mono- and diglyceride mixtures, which are usually obtained by alkali-catalyzed transesterification of corresponding triglycerides with glycerol and optionally subsequent purification by molecular distillation. Such products are for example under the brand Monomuis® (Cognis Germany GmbH / DE) in the trade. Usually the Monoglyceridanteil in these starting materials in the range of 65 to 90 Gew.
- the difference consists essentially of Diglycerid;
- small quantities of the starting triglyceride may be contained due to the production.
- the Partialglyceride are then subjected to ethoxylation, which can be done in a conventional manner.
- the starting materials are usually introduced in a pressure reactor, the alkaline catalyst is added, for example sodium methylate or calcined hydrotalcite, and the desired amount of ethylene oxide is pressed on.
- the temperature is usually in the range of 110 to 180 ° C, the autogenous pressure can rise to 5 bar. After the required amount of ethylene oxide has been added and the pressure has reached a constant value, it is allowed to react for about 30 minutes before cooling the autoclave, depressurized and neutralized or filtered off the alkaline catalyst, for example by adding lactic acid.
- heterogeneous catalysts such as, for example, calcined hydrotalcite, which is hydrophobized with fatty acids
- calcined hydrotalcite which is hydrophobized with fatty acids
- appreciable amounts of insertion products can be formed.
- further transesterification takes place during the ethoxylation, in the course of which free glycerol is also formed.
- This competes with the partial glycerides in the addition of the ethylene oxide, whereby by the greater number of free, preferably primary hydroxyl groups naturally there is even a preference for the formation of glycerol ethoxylates.
- Corresponding products are incidentally, for example, under the brand Cetiol® HE (Cognis Germany GmbH) in the trade.
- the mixtures can also be prepared by reacting triglycerides with ethylene oxide in a first step - thus enforcing an insertion into the ester group - and carrying out the transesterification with fatty acids or fatty acid alkyl esters in the second step.
- a description of such a method can be found for example by Ropuszynski in IV International Conference on Interfacial Active Materials, Berlin, 1974, treatises of the Academy of Sciences of the GDR, born 1976, No.1N, Akademieverlag Berlin, 1977, p.119-121.
- the ethoxylation products can be used both for the production of liquid and serve solid preparations and are usually in quantities of 1 to 30, preferably 2 to 15 and in particular 5 to 10 wt .-% - based on the means - used.
- the preparations can also contain a variety of other conventional auxiliaries and additives.
- Primary constituents of the solid and liquid washing, rinsing, cleaning and softening compositions that can be prepared using the ethoxylated partial glycerides are anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants, but are preferably anionic surfactants or combinations of anionic and nonionic surfactants.
- anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates , Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl
- Preferred alkylbenzenesulfonates preferably follow the formula (I) R 4 -Ph-SO 3 X 1 (II) in which R 4 is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X 1 is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- R 4 is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms
- Ph is a phenyl radical
- X 1 is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary and / or secondary alcohols which preferably follow the formula (III) , R 5 O-SO 3 X 2 (III) in which R 5 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X 2 is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxo synthesis.
- the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
- alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
- branched primary alcohols are oxo alcohols, as they are accessible, for example, by reacting carbon monoxide and hydrogen to alpha-olefins by the shop process.
- Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
- oxo alcohols as obtained by the classical oxo process of Enichema or the Condea by addition of carbon monoxide and hydrogen to olefins.
- These alcohol mixtures are a mixture of highly branched alcohols.
- Such alcohol mixtures are commercially available under the trade name Lial®.
- Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
- R 6 CO-OX 3 (IV) in which R 6 CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X 3 is alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
- Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
- coconut or palm kernel fatty acids are used in the form of their sodium or potassium salts.
- nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides.
- the preferred fatty alcohol polyglycol ethers follow the formula (V) , R 7 O (CH 2 CHR 8 O) n 1 H (V) in which R 7 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 8 is hydrogen or methyl and n 1 is a number from 1 to 20.
- Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.
- Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) , R 9 CO- (OCH 2 CHR 10) n 2 OR 11 (VI) in the R 9 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 10 is hydrogen or methyl, R 11 is linear or branched alkyl radicals having 1 to 4 carbon atoms and n 2 is a number from 1 to 20 stands.
- Typical examples are the formal charge products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and technical mixtures thereof.
- the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite.
- catalysts such as, for example, calcined hydrotalcite.
- Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettklamethylestern.
- Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VII) , R 12 O- [G] p (VII) in which R 12 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature reference is made here to the documents EP-A1 0301298 and WO 90/03977 .
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
- the index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10.
- the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
- the alkyl or alkenyl radical R 12 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
- the alkyl or alkenyl radical R 12 can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
- Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above.
- Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
- cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyl distearyl ammonium chloride or hydroxyethyl hydroxycetyl dimmonium chloride (Dehyquart E) or esterquats .
- R 14 and R 15 are each independently hydrogen or R 13 CO
- R 16 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H Group
- m1, m2 and m3 are in total 0 or numbers from 1 to 12
- m4 is numbers from 1 to 12
- Y is halide, alkylsulfate or alkyl phosphate.
- esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. It is preferred to use technical C 12/18 coconut fatty acids and, in particular, partially hydrogenated C 16/18 tallow or palm oil fatty acids and also high-acid C 16/18 fatty acid cuts having high elaidic acid content.
- the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used.
- an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
- the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 . Tallow or palm fatty acid (iodine number 0 to 40) from.
- quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be particularly advantageous in which R 13 CO is an acyl radical having 16 to 18 carbon atoms, R 14 is R 13 CO, R 15 is hydrogen, R 16 is a methyl group, m1 , m2 and m3 are 0 and Y is methylsulfate.
- suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) , in the R 17 CO for an acyl radical having 6 to 22 carbon atoms, R 18 is hydrogen or R 17 CO, R 19 and R 20 are independently alkyl radicals having 1 to 4 carbon atoms, m1 and m2 in total for 0 or numbers from 1 to 12 and Y is halide, alkyl sulfate or alkyl phosphate.
- R 21 CO for an acyl radical having 6 to 22 carbon atoms
- R 22 is hydrogen or R 21 CO
- R 23 , R 24 and R 25 are independently alkyl radicals having 1 to 4 carbon atoms
- Y is halide, alkyl sulfate or alkyl phosphate.
- esterquats are substances in which the ester is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine, in which R 26 is CO for an acyl radical having 6 to 22 carbon atoms, R 27 is hydrogen or R 26 CO, R 28 and R 29 are independently alkyl radicals having 1 to 4 carbon atoms and Y is halide, alkyl sulfate or alkyl phosphate.
- Such Amidesterquats are available for example under the name Incroquat® (Croda) in the market.
- alkylbetaines examples include alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
- suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII) , R 30 is alkyl and / or alkenyl radicals having from 6 to 22 carbon atoms, R 31 is hydrogen or alkyl radicals having from 1 to 4 carbon atoms, R 32 is alkyl radicals having from 1 to 4 carbon atoms, q 1 is from 1 to 6, and Z is from 1 to 6 Alkali and / or alkaline earth metal or ammonium.
- Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C 16/18 tallowalkyldimethylamine, and technical mixtures thereof.
- carboxyalkylation products of amidoamines which follow the formula (XIII) , in the R 33 CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 34 for hydrogen or alkyl radicals having 1 to 4 carbon atoms, R 35 for alkyl radicals having 1 to 4 carbon atoms, q 2 for numbers from 1 to 3, q3 represents numbers from 1 to 6 and Z represents an alkali and / or alkaline earth metal or ammonium.
- Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethyl-aminopropylamine, which are condensed with sodium chloroacetate.
- the use of a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
- imidazolinium betaines are also suitable .
- These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
- AEEA aminoethylethanolamine
- the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
- Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
- the washing, rinsing, cleaning and softening compositions according to the invention may additionally be additional inorganic and organic builders, wherein as inorganic builders mainly zeolites crystalline phyllosilicates, amorphous silicates and - as far as permissible - also Phosphates, e.g. Tripolyphosphate be used.
- the amount of co-builder is on the to include preferred amounts of phosphates.
- the finely crystalline, synthetic and bound water-containing zeolite frequently used as detergent builder is preferably zeolite A and / or P.
- zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P as well as Y are also suitable.
- VEGOBOND AX® commercial product from Condea Augusta SpA
- the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Suitable substitutes or sub-substituents for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 ⁇ yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European Patent Application EP 0164514 A1 .
- Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171 .
- Further suitable phyllosilicates are known, for example, from the patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here.
- small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas.
- the phyllosilicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na + and Ca 2+ , due to their ion-exchanging properties.
- the amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing.
- Useful layered silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647, EP 0026529 A1 and EP 0028432 A1 .
- phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment
- the preferred builder substances also include amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties.
- the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
- Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- phosphates as builders possible, unless such use should be avoided for environmental reasons.
- Suitable the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates.
- Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10 wt .-%, based on the finished agents, in combination with other builders to a synergistic improvement of secondary washing power.
- Useful organic builders are, for example, usable in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and mixtures thereof.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
- 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 cleaners.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- 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. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100.
- 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.
- Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 and 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 .
- Also suitable is an oxidized oligosaccharide according to the German patent application DE 19600018 A1.
- a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
- Suitable co-builders are oxydisuccinates and other derivatives of disuccinates , preferably ethylenediamine disuccinate .
- glycerol disuccinates and glycerol trisuccinates are also particularly preferred in this connection, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0150930 A1 and Japanese Patent Application JP 931339896.
- Suitable amounts are in zeolith lotteryn and / or silicate-containing formulations at 3 to 15 wt .-%.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders are described, for example, in International Patent Application WO 95/20029 .
- Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrenesulfonic acid).
- Suitable copolymeric polycarboxylates are, 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 molecular weight relative to free acids is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (in each case measured against polystyrene sulfonic acid).
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
- Granular polymers are usually added later to one or more basic granules.
- biodegradable polymers of more than two different monomer units for example those according to DE 4300772 A1 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 4221381 C2 as monomers salts of acrylic acid and 2-Alkylallylsulfonklare and sugar derivatives.
- Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids, their salts or their precursors Particular preference is given to polyaspartic acids or their salts and derivatives.
- polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP 0280223 A1 .
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- compositions may also contain components which are oil and grease washout from textiles.
- preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those of the prior Known polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
- compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which do not have outstanding builder properties, or mixtures of these;
- alkali metal carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio of Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
- the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
- the content of sodium silicate (without any special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
- the agents may contain further known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, low Levels of neutral Sleepsalzen and dyes and perfumes and the like included.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
- the content of the bleaching agent is preferably before 5 to 35 wt .-% and in particular to 30 wt .-%, wherein advantageously perborate monohydrate or percarbonate is used.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and the enol esters, acyl
- hydrophilic substituted acyl acetals known from German patent application DE 19616769 A1 and the acyllactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are likewise preferably used.
- the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
- the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleach catalysts.
- Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salene complexes known from German patent application DE 19529905 A1 and their N- analogues known from German patent application DE 19620267 A1, which are known from German Patent Application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German Patent Application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands known from the German patent application DE 19620411 A1 cobalt, iron, copper and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt Complexes containing the cobalt complexes described in European Patent Application EP 0272030 A1 , the manganese known from European Patent Application EP 0693550 A1.
- Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
- Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
- subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
- lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
- the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
- the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
- the agents may contain other enzyme stabilizers .
- enzyme stabilizers 0.5 to 1 wt .-% sodium formate can be used.
- proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
- calcium salts magnesium salts also serve as stabilizers.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
- Graying inhibitors have the task of suspending the fiber-removed dirt in the liquor to keep the dirt from being rebuilt.
- water-soluble Colloids mostly organic nature suitable, for example, the water-soluble salts polymeric Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids or the cellulose or salts of acid sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose.
- Farther soluble starch preparations and other starch products than those mentioned above can be used e.g. degraded starch, aldehyde levels, etc.
- polyvinylpyrrolidone is useful.
- cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of 0.1 to 5 wt .-%, based on the agents used.
- the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
- Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
- brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
- Uniformly white granules are obtained when the means except the usual Aufhellem in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
- a particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).
- Suitable soil repellent polymers are those which are preferred Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, wherein the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate may range from 50:50 to 90:10.
- the molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100.
- the polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure.
- Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers which have linking molecular weight polyethylene glycol units from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers of about 10,000 to about 50,000. Examples of commercially available polymers are the Products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).
- waxy compounds can be used.
- waxy are such Understood compounds having a melting point at atmospheric pressure above 25 ° C (room temperature), preferably above 50 ° C and in particular above 70 ° C.
- the waxy defoamer substances are practically insoluble in water, i. at 20 ° C, they are in 100 g of water a solubility below 0.1 wt .-% on.
- Suitable waxy compounds are, for example Bisamides, fatty alcohols, fatty acids, carboxylic acid esters of monohydric and polyhydric alcohols and paraffin waxes or mixtures thereof.
- the for this Purpose known silicone compounds are used.
- Suitable paraffin waxes are generally a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420 , and / or its solidification point , This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. In this case, at room temperature completely liquid paraffins, that is those with a solidification point below 25 ° C, according to the invention not useful. Soft waxes having a melting point in the range of 35 to 50 ° C preferably include the group of petrolates and their hydrogenation products.
- These petrolatum are mixtures of microcrystalline waxes and refractory n-paraffins.
- the paraffin wax mixtures known from EP 0309931 A1 can be used, for example, from 26% by weight to 49% by weight of microcrystalline paraffin wax having a solidification point of from 62 ° C.
- paraffins or paraffin mixtures are used which solidify in the range of 30 ° C to 90 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin. In the case of the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably completely absent.
- particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10 wt .-%, in particular from 2 wt .-% to 5 wt .-%, at 40 ° C, a liquid content of less than 30 wt .-%, preferably from 5 Wt .-% to 25 wt .-% and in particular from 5 wt .-% to 15 wt .-%, at 60 ° C, a liquid content of 30 wt .-% to 60 wt .-%, in particular of 40 wt .-%.
- the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is, in the case of particularly preferred paraffin wax mixtures, still below 85 ° C., in particular at 75 ° C. to 82 ° C.
- the paraffin waxes may be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
- Suitable bisamides as defoamers are those which are derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
- Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
- Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
- Preferred diamines are ethylenediamine and hexamethylenediamine.
- Particularly preferred bisamides are bis-myristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
- Suitable carboxylic esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
- the alcohol portion of the carboxylic acid ester contains a monohydric or polyhydric alcohol having 1 to 28 carbon atoms in the hydrocarbon chain.
- suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut oil, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
- Preferred esters are those of ethylene glycol, glycerol and sorbitan, wherein the acid portion of the ester is selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
- Candidate polyhydric alcohol esters include xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters.
- Useful glycerol esters are the mono-, di- or triesters of glycerol and said carboxylic acids, the mono- or diesters being preferred.
- Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glyceryl distearate are examples of this.
- suitable natural esters as defoamers are beeswax, which consists mainly of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
- carnauba wax which is a mixture of carnaubaic acid alkyl esters, often in combination with low levels of free carnaubaic acid, other long chain acids, high molecular weight alcohols and hydrocarbons.
- Suitable carboxylic acids as further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, which are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil.
- Preferred are saturated fatty acids having 12 to 22, in particular 18 to 22 C-atoms.
- Suitable fatty alcohols as further antifoam compounds are the hydrogenated products of the described fatty acids.
- dialkyl ethers may additionally be present as defoamers.
- the ethers may be asymmetric or symmetrical, ie containing two identical or different alkyl chains, preferably containing 8 to 18 carbon atoms.
- Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers having a melting point above 25 ° C, in particular above 40 ° C.
- Suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. They are prepared , for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with elimination of carbon dioxide and water, for example in accordance with German laid-open specification DE 2553900 OS .
- Suitable fatty ketones are those prepared by pyrolysis of the magnesium salts of lauric, myristic, palmitic, palmitoleic, stearic, oleic, elaidic, petroselic, arachidic, gadoleic, behenic or erucic acid.
- fatty acid polyethylene glycol esters which are preferably obtained by basic homogeneously catalyzed addition of ethylene oxide to fatty acids.
- the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
- alkanolamines especially triethanolamine, results in extremely selective ethoxylation of the fatty acids, especially when it comes to producing low ethoxylated compounds.
- the paraffin waxes described are particularly preferably used alone as waxy defoamers or in admixture with one of the other waxy defoamers, wherein the proportion of paraffin waxes in the mixture is preferably more than 50% by weight, based on waxy defoamer mixture.
- the paraffin waxes can be applied to carriers as needed.
- carrier material all known inorganic and / or organic carrier materials are suitable. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble phyllosilicates, alkali metal silicates, alkali metal sulphates, for example sodium sulphate, and alkali metal phosphates.
- the alkali metal silicates are preferably a compound having a molar ratio of alkali metal oxide to SiO 2 of from 1: 1.5 to 1: 3.5.
- the use of such silicates results in particularly good grain properties, in particular high abrasion stability and yet high dissolution rate in water.
- the aluminosilicates referred to as support material include, in particular, the zeolites, for example zeolite NaA and NaX.
- the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
- silicates can be used which are under the name Aerosil® or Sipemat® commercially.
- Suitable organic support materials are, for example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
- Useful cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called cellulose mixed ethers, such as, for example, methylhydroxyethylcellulose and methylhydroxypropylcellulose, and mixtures thereof.
- Particularly suitable mixtures are composed of sodium carboxymethylcellulose and methylcellulose, wherein the carboxymethylcellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose has a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
- the mixtures preferably contain alkali metal carboxymethylcellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50.
- Native starch composed of amylose and amylopectin is also suitable as the carrier. Native starch is starch, as it is available as an extract from natural sources, such as rice, potatoes, corn and wheat. Native starch is a commercial product and thus easily accessible.
- one or more of the abovementioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulphates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate polymethacrylate and starch.
- Particularly suitable are mixtures of alkali metal carbonates, in particular sodium carbonate, alkali metal silicates, in particular sodium silicate, alkali metal sulphates, in particular sodium sulphate and zeolites.
- Suitable silicones are customary organopolysiloxanes which may have a finely divided silica content, which in turn may also be silanated. Such organopolysiloxanes are described, for example, in European Patent Application EP 0496510 A1 . Particularly preferred are polydiorganosiloxanes and especially polydimethylsiloxanes known in the art. Suitable polydiorganosiloxanes have a nearly linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
- silicones which may be both liquid and resinous at room temperature.
- simethicones which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates.
- the silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which may also be silanated.
- siliceous dimethyl polysiloxanes are particularly suitable for the purposes of the present invention.
- the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
- the silicones are used in the form of their aqueous emulsions.
- the silicone is added to the initially charged water with stirring.
- thickening agents known in the art may be added to increase the viscosity of the aqueous silicone emulsions.
- nonionic cellulose ethers such as methylcellulose, ethylcellulose and mixed ethers such as methylhydoxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose and anionic carboxycellulose types such as the carboxymethylcellulose sodium salt (abbreviation CMC).
- Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
- concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion use concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion.
- the content of silicones of the type described in the aqueous emulsions is advantageously in the range of 5 to 50 wt .-%, in particular from 20 to 40 wt .-% - calculated as silicones and based on aqueous silicone emulsion.
- the aqueous silicone solutions as thickener starch which is accessible from natural sources, such as rice, potatoes, corn and wheat.
- the starch is advantageously present in amounts of from 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethylcellulose and a nonionic cellulose ether in the quantities already mentioned.
- aqueous silicone emulsions it is expedient to proceed in such a way that the thickeners, if present, are allowed to pre-swell in water before the addition of the silicones takes place.
- the incorporation of the silicones is expediently carried out with the aid of effective stirring and mixing devices.
- the solid preparations are, for example, detergent tablets or granules, they may further contain disintegrants. These are substances which are added to the shaped bodies in order to accelerate their decomposition upon contact with water. Overviews can be found, for example, in J. Pharm. Sci. 61 (1972) or Römpp Chemilexikon, 9th edition, volume 6, p. 4440 .
- the disintegrating agents can be homogeneously distributed macroscopically in the molded body, but microscopically they form zones of increased concentration due to their production.
- Preferred disintegrants include polysaccharides such as natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins, etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinyl pyrrolidone, collidone, alginic acid and their alkali metal salts, amorphous or partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
- polysaccharides such as natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins, etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinyl pyrrolidone, collidone, alginic acid and their
- the moldings may contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 wt .-% - based on the moldings.
- fragrance compounds e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g.
- the hydrocarbons mainly include the terpenes such as limonene and pinene.
- Such perfume oils may also contain natural fragrance mixtures, as available from plant sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-ylang oil.
- Muscat sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.
- the perfumes can be incorporated directly into the compositions of the invention, but it can also be advantageous to apply the perfumes on carriers, which the adhesion of the perfume on the laundry strengthen and ensure a long-lasting scent of textiles through a slower release of fragrance.
- carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes additionally can be coated with other excipients.
- the final preparations may also contain inorganic salts as fillers or leveling agents, such as, for example, sodium sulfate, which is preferably present in amounts of from 0 to 10, in particular from 1 to 5,% by weight, based on the composition.
- inorganic salts such as, for example, sodium sulfate, which is preferably present in amounts of from 0 to 10, in particular from 1 to 5,% by weight, based on the composition.
- the detergents obtainable using the additives according to the invention can - if it is are solid preparations - in the form of powders, extrudates, granules or agglomerates be manufactured or used. It can be both universal and fine or color detergents, optionally in the form of compactates or supercompacts.
- the agents are the corresponding methods known in the art suitable.
- the agents are prepared by mixing various particulate components, containing the detergent ingredients are mixed together.
- the particulate Components can be prepared by spray-drying, simple mixing or complex granulation processes, For example, fluidized bed granulation can be produced. Preference is given in particular in that at least one surfactant-containing component is produced by fluidized-bed granulation. Further it may be particularly preferred if aqueous preparations of the alkali metal silicate and the alkali metal carbonate sprayed together with other detergent ingredients in a drying device which can take place simultaneously with the drying granulation.
- the drying device in which the aqueous preparation is sprayed, it may be any dry equipment. In a preferred process, the drying is carried out as a spray drying in a drying tower .
- the aqueous preparations are exposed in a known manner a drying gas stream in finely divided form.
- Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed therein is hereby expressly also made the subject of the present invention disclosure.
- a particularly preferred way to prepare the means is to subject the precursors to fluidized bed granulation ("SKET" granulation).
- SKET fluidized bed granulation
- the precursors can be used both in the dried state and as an aqueous preparation.
- Preferably used fluidized bed apparatus have bottom plates with dimensions of 0.4 to 5 m.
- the granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s.
- the discharge of the granules from the fluidized bed is preferably carried out via a size classification of the granules.
- the classification can be carried out, for example, by means of a sieve device or by a countercurrent air stream (classifier air) which is regulated so that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
- the incoming air is composed of the heated or unheated classifier air and the heated bottom air.
- the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
- a starting material for example a granular material from a previous experimental batch, is introduced.
- the mixtures are then subjected to a Kompakberungs Colour, with more Ingredients are added to the funds only after the compaction step.
- the compaction the ingredients are found in a preferred embodiment of the invention in a press-agglomeration process instead of.
- the press agglomeration process involving the solid premix (dried base detergent) is subjected, can be realized in various apparatuses. Depending on Type of agglomerator used are different Preßagglomerations vide distinguished.
- Preßagglomerations Process The four most common and preferred in the present invention Preßagglomerationsclar are the extrusion, the roll pressing or compacting, the hole pressing (Pelletizing) and tableting, so that in the present invention preferred Preßagglomerationsvor Cyprus Extrusion, roll compaction, pelletizing or tabletting operations are.
- binders can be used as an aid for compaction.
- a binder is used, that at temperatures up to 130 ° C, preferably up to 100 ° C and especially to 90 ° C is already completely present as a melt.
- the binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature must - if a particular binder is desired - be adapted to the binder.
- the actual compression process is preferably carried out at processing temperatures which correspond at least in the compression step at least the temperature of the softening point, if not even the temperature of the melting point of the binder.
- the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt.
- the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder.
- Such a temperature control has the further advantage that even thermally sensitive raw materials, such as peroxy bleach such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substance.
- thermally sensitive raw materials such as peroxy bleach such as perborate and / or percarbonate, but also enzymes
- the possibility of precise temperature control of the binder in particular in the decisive step of the compression, ie between the mixing / homogenization of the premix and the shaping allows an energetically very favorable and extremely gentle for the temperature-sensitive components of the premix process, since the premix for a short time the is exposed to higher temperatures.
- the working tools of the Preßagglomerators (the worm (s) of the extruder, the roller (s) of the Walzenkompaktors and the press roll (s) of the pellet press) a temperature of at most 150 ° C, preferably at most 100 ° C and in particular at most 75th ° C and the process temperature is 30 ° C and in particular at most 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
- the duration of the effect of temperature in the compression region of the pressing agglomerators is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
- Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols.
- the modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
- Another group consists of mono- and / or disuccinates of the polyalkylene glycols in turn, have molecular weights between 600 and 6,000, preferably between 1,000 and 4,000.
- polyethylene glycols include polymers in the production of which, in addition to ethylene glycol, C 3 -C 5 glycols and also glycerol and mixtures thereof are used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
- the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.
- Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols having a molecular weight of about 4,000 can be used and Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols having a molecular weight between 3,500 and 5,000.
- polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech.
- these per se liquid polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must meet the requirements of the invention again, ie must have a melting point or softening point of at least above 45 ° C.
- suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of not more than 30,000. Preference is given here to molecular weight ranges between 3,000 and 30,000, for example around 10,000.
- Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others. especially in combination with polyethylene glycols used.
- the compacted material preferably has temperatures directly after leaving the production apparatus not above 90 ° C, with temperatures between 35 and 85 ° C being particularly preferred are. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
- the detergent according to the invention is prepared by means of an extrusion , as described for example in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 .
- a solid premix is extruded under pressure extruded and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension.
- the homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work.
- Preferred plasticizers and / or lubricants are surfactants and / or polymers.
- the pre-mixture is preferably supplied to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature.
- the premix under pressure which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally
- the extrudate is reduced to about spherical to cylindrical granules by means of a rotating bladed knife.
- the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
- the production of granules succeeds a substantially uniformly predictable particle size, in particular, the absolute particle sizes can be adapted to the intended use. In general, particle diameters of at most 0.8 cm are preferred.
- Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm.
- the length / diameter ratio of the chopped primary granules is preferably in the range from about 1: 1 to about 3: 1. It is furthermore preferred to feed the still plastic primary granulate to a further shaping processing step; In this process, edges present on the raw extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained.
- small amounts of dry powder for example, zeolite powder, such as zeolite NaA powder, may be included in this stage. This shaping can be done in commercially available Rondierettin.
- extrusions can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bexx Bextruder.
- the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded.
- the duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
- the detergents according to the invention can also be prepared by means of roll compaction .
- the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a sheet-like Kompaktat, the so-called scoop.
- the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
- smooth rolls smooth, unstructured flake tapes are obtained, while by using structured rolls, correspondingly structured flakes can be produced in which, for example, certain shapes of the later detergent particles can be specified.
- the sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to Granulatkömem, which can be refined by further known per se surface treatment methods, in particular brought into approximately spherical shape.
- the temperature of the pressing tools, ie the rolls is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.
- Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
- the duration of the action of temperature in the compression region of the smooth rolls or rolls provided with depressions of defined shape amounts to a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
- the detergent according to the invention can also be produced by means of pelleting .
- the premix is applied to a perforated surface and pressed by means of a pressure-emitting body under plasticization through the holes.
- the premix is compacted under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted with a knock-off device to granules.
- pressure roller and perforated die conceivable.
- flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers.
- the press rollers may also be conically shaped in the plate devices, in the annular devices can matrices and press roll (s) have co-rotating or opposite sense of rotation.
- An apparatus suitable for carrying out the method is described, for example, in German Offenlegungsschrift DE 3816842 A1 .
- the ring die press disclosed in this document consists of a rotating ring die interspersed by press channels and at least one press roll operatively connected to its inner surface, which presses the material supplied to the die space through the press channels into a material discharge.
- ring die and pressing roller are drivable in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized.
- pelletizing with heatable or coolable rollers in order to set a desired temperature of the premix.
- the temperature of the pressing tools, so the pressure rollers or press rolls preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C.
- Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
- the production of moldings is usually carried out by tabletting or press agglomeration .
- the resulting particulate Preßagglomerate can either be used directly as a detergent or aftertreated by conventional methods and / or processed.
- the usual post-treatments include, for example, powdering with finely divided ingredients of detergents or cleaners, whereby the bulk density is generally further increased.
- a preferred aftertreatment is also the procedure according to the German patent applications DE 19524287 A1 and DE 19547457 A1 , wherein dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products according to the invention, which serve as a core, and thus means arise , which have these so-called fines as an outer shell.
- the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
- the base of these tablets may, for example, be circular or rectangular.
- Multi-layer tablets, in particular tablets with 2 or 3 layers, which may also be different in color, are especially preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
- the tablets can also contain pressed and unpressed portions.
- Moldings having a particularly advantageous dissolution rate are obtained when the granular constituents before pressing have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight.
- a particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
- the investigations were carried out in Launder-ometer (temperature: 40 ° C, dosage: 6 g / l, water hardness 20 ° dH, load: 2 kg).
- Example 1 is according to the invention, example V1 corresponds to the blank value without addition of surfactant, examples C2 to V4 with differing contents of glycerol ethoxylates serve for comparison.
Description
46 bis 90 Gew.-% Monoester
9 bis 30 Gew.-% Diester und
1 bis 15 Gew.-% Triester
- mit der Maßgabe, daß sich die Mengenangaben zu 100 Gew.-% ergänzen - bezieht sich vielmehr auf das nach der Ethoxylierung erhaltene Gemisch. In welcher Weise sich die Ethylenoxidgruppen auf das Molekül verteilen ist analytisch nur schwer nachzuweisen. Es ist jedoch davon auszugehen, daß es sich bei Einsatz von homogenen alkalischen Katalysatoren im wesentlichen um eine Anlagerung an die freien Hydroxylgruppen und nur untergeordnet um eine Insertion in die Carbonylesterbindung handelt. Des weiteren wird bei der Ethoxylierung die Anlagerung an primäre gegenüber sekundären Hydroxylgruppen bevorzugt sein. Werden heterogene Katalysatoren, wie z.B. calcinierter oder mit Fettsäuren hydrophobierter Hydrotalcit eingesetzt, kann es auch zur Bildung von nennenswerten Mengen an Insertionsprodukten kommen. Wie schon oben erläutert, findet während der Ethoxylierung eine weitere Umesterung statt, in deren Verlauf auch freies Glycerin gebildet wird. Dieses steht mit den Partialglyceriden bei der Anlagerung des Ethylenoxids in Konkurrenz, wobei durch die größere Zahl freier, vorzugsweise primärer Hydroxylgruppen naturgemäß sogar eine Präferenz zur Bildung von Glycerinethoxylaten besteht. Entsprechende Produkte sind im übrigen beispielsweise unter der Marke Cetiol® HE (Cognis Deutschland GmbH) im Handel.
Der eigentliche Verdichtungsprozeß erfolgt dabei vorzugsweise bei Verarbeitungstemperaturen, die zumindest im Verdichtungsschritt mindestens der Temperatur des Erweichungspunkts, wenn nicht sogar der Temperatur des Schmelzpunkts des Bindemittels entsprechen. In einer bevorzugten Ausführungsform der Erfindung liegt die Verfahrenstemperatur signifikant über dem Schmelzpunkt bzw. oberhalb der Temperatur, bei der das Bindemittel als Schmelze vorliegt. Insbesondere ist es aber bevorzugt, daß die Verfahrenstemperatur im Verdichtungsschritt nicht mehr als 20 °C über der Schmelztemperatur bzw. der oberen Grenze des Schmelzbereichs des Bindemittels liegt. Zwar ist es technisch durchaus möglich, auch noch höhere Temperaturen einzustellen; es hat sich aber gezeigt, daß eine Temperaturdifferenz zur Schmelztemperatur bzw. zur Erweichungstemperatur des Bindemittels von 20 °C im allgemeinen durchaus ausreichend ist und noch höhere Temperaturen keine zusätzlichen Vorteile bewirken. Deshalb ist es - insbesondere auch aus energetischen Gründen - besonders bevorzugt, zwar oberhalb, jedoch so nah wie möglich am Schmelzpunkt bzw. an der oberen Temperaturgrenze des Schmelzbereichs des Bindemittels zu arbeiten. Eine derartige Temperaturführung besitzt den weiteren Vorteil, daß auch thermisch empfindliche Rohstoffe, beispielsweise Peroxybleichmittel wie Perborat und/oder Percarbonat, aber auch Enzyme, zunehmend ohne gravierende Aktivsubstanzverluste verarbeitet werden können. Die Möglichkeit der genauen Temperatursteuerung des Binders insbesondere im entscheidenden Schritt der Verdichtung, also zwischen der Vermischung/Homogenisierung des Vorgemisches und der Formgebung, erlaubt eine energetisch sehr günstige und für die temperaturempfindlichen Bestandteile des Vorgemisches extrem schonende Verfahrensführung, da das Vorgemisch nur für kurze Zeit den höheren Temperaturen ausgesetzt ist. In bevorzugten Preßagglomerationsverfahren weisen die Arbeitswerkzeuge des Preßagglomerators (die Schnecke(n) des Extruders, die Walze(n) des Walzenkompaktors sowie die Preßwalze(n) der Pelletpresse) eine Temperatur von maximal 150 °C, vorzugsweise maximal 100 °C und insbesondere maximal 75 °C auf und die Verfahrenstemperatur liegt bei 30 °C und insbesondere maximal 20 °C oberhalb der Schmelztemperatur bzw. der oberen Temperaturgrenze des Schmelzbereichs des Bindemittels. Vorzugsweise beträgt die Dauer der Temperatureinwirkung im Kompressionsbereich der Preßagglomeratoren maximal 2 Minuten und liegt insbesondere in einem Bereich zwischen 30 Sekunden und 1 Minute.
Zusammensetzung von ethoxylierten Partialglyceriden und Waschleistung (Mengenangaben als Gew.-%) | |||||
Zusammensetzung / Performance | V1 | 1 | V2 | V3 | V4 |
Gehalt an ethoxyliertem Partialglycerid | - | 78 | 75 | 66 | 59 |
- Monoestergehalt | - | 58 | 58 | 58 | 58 |
- Diestergehalt | - | 30 | 30 | 30 | 30 |
- Triestergehalt | - | 12 | 12 | 12 | 12 |
Gehalt an ethoxyliertem Glycerin | - | 22 | 25 | 34 | 41 |
Ethoxyliertes Partialglycerid : Glycerinethoxylat | - | 3,5 : 1 | 3,0 : 1 | 1,9 : 1 | 1,4:1 |
Waschleistung [%-Rem.] | |||||
- Staub-Hautfett | 41,1 | 64,9 | 58,3 | 56,2 | 55,1 |
-Lippenstift | 28,2 | 64,5 | 52,1 | 50,0 | 50,3 |
- Make Up | 43,7 | 69,4 | 54,5 | 55,0 | 53,8 |
- Mineralöl | 20,2 | 22,7 | 22,6 | 21,0 | 21,5 |
- Olivenöl | 18,0 | 34,6 | 28,5 | 29,3 | 29,5 |
- Blut/Milch-Mischanschmutzung | 13,0 | 41,3 | 36,5 | 37,5 | 38,1 |
- Rotwein | 36,4 | 52,7 | 48,3 | 46,4 | 46.5 |
Claims (3)
- Verwendung von Ethoxylierungsprodukten von Partialglyceriden zur Herstellung von Wasch-, Spül- und Reinigungsmitteln, die aus Mischungen von Partialglyceridethoxylaten und Glycerinethoxylaten im Gewichtsverhältnis 3,3 : 1 bis 6 : 1 bestehen, wobei man Partialglyceride der Formel (I) einsetzt, in der R1CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen und R2 und R3 unabhängig voneinander für R1CO oder Wasserstoff stehen, mit der Maßgabe, dass entweder R2 oder R3 Wasserstoff bedeutet, dadurch gekennzeichnet, dass man Anlagerungsprodukte von durchschnittlich 5 bis 20 Mol Ethylenoxid an 1 Mol Partialglycerid einsetzt.
- Verwendung Anspruch 1, dadurch gekennzeichnet, dass man Partialglyceridethoxylate einsetzt, die
46 bis 90 Gew.% Monoester
9 bis 30 Gew.% Diester und
1 bis 15 Gew.% Triester mit der Maßgabe enthalten, dass sich die Mengenangaben zu 100 Gew.-% ergänzen. - Verwendung nach mindestens einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass man die Ethoxylierungsprodukte in Mengen von 1 bis 30 Gew.-% - bezogen auf die Mittel - einsetzt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19958398 | 1999-12-03 | ||
DE19958398A DE19958398A1 (de) | 1999-12-03 | 1999-12-03 | Verwendung von Partialgyceridpolyglycolethern |
Publications (3)
Publication Number | Publication Date |
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EP1106675A2 EP1106675A2 (de) | 2001-06-13 |
EP1106675A3 EP1106675A3 (de) | 2002-09-18 |
EP1106675B1 true EP1106675B1 (de) | 2005-02-09 |
Family
ID=7931354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP00125727A Expired - Lifetime EP1106675B1 (de) | 1999-12-03 | 2000-11-24 | Verwendung von Partialglyceridpolyglycolethern |
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EP (1) | EP1106675B1 (de) |
DE (2) | DE19958398A1 (de) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10259847A1 (de) * | 2002-12-20 | 2004-07-15 | Cognis Deutschland Gmbh & Co. Kg | Alkylmonoglycerinether-Derivate |
EP1844917A3 (de) | 2006-03-24 | 2008-12-03 | Entex Rust & Mitschke GmbH | Verfahren zur Verarbeitung von zu entgasenden Produkten |
ES2293825B1 (es) | 2006-06-07 | 2008-12-16 | Kao Corporation, S.A. | Composicion que contiene una mezcla de mono-di, y trigliceridos y glicerina. |
FR2910877B1 (fr) | 2006-12-28 | 2009-09-25 | Eurocopter France | Amelioration aux rotors de giravions equipes d'amortisseurs interpales |
DE102007059299A1 (de) | 2007-05-16 | 2008-11-20 | Entex Rust & Mitschke Gmbh | Vorrichtung zur Verarbeitung von zu entgasenden Produkten |
WO2012041411A1 (en) | 2010-09-30 | 2012-04-05 | Cognis Ip Management Gmbh | Air freshener gel with improved longevity |
DE102011112081A1 (de) | 2011-05-11 | 2015-08-20 | Entex Rust & Mitschke Gmbh | Verfahren zur Verarbeitung von Elasten |
DE102011112080A1 (de) | 2011-09-03 | 2013-03-07 | Entex Rust & Mitschke Gmbh | Einarbeitung von Additiven und Füllstoffen in einem Planetwalzenextruder oder einem Planetwalzenextruderabschnitt |
DE102013000708A1 (de) | 2012-10-11 | 2014-04-17 | Entex Rust & Mitschke Gmbh | Verfahren zur Extrusion von Kunststoffen, die zum Kleben neigen |
GB201316619D0 (en) * | 2013-09-19 | 2013-10-30 | Croda Int Plc | A stain treatment additive |
DE102014206987A1 (de) * | 2014-04-11 | 2015-10-15 | Henkel Ag & Co. Kgaa | Glycerinesterderivate als schmutzablösevermögende Wirkstoffe |
DE102015001167A1 (de) | 2015-02-02 | 2016-08-04 | Entex Rust & Mitschke Gmbh | Entgasen bei der Extrusion von Kunststoffen |
DE102017001093A1 (de) | 2016-04-07 | 2017-10-26 | Entex Rust & Mitschke Gmbh | Entgasen bei der Extrusion von Kunststoffen mit Filterscheiben aus Sintermetall |
DE102015008406A1 (de) | 2015-07-02 | 2017-04-13 | Entex Rust & Mitschke Gmbh | Verfahren zur Bearbeitung von Produkten im Extruder |
DE102016002143A1 (de) | 2016-02-25 | 2017-08-31 | Entex Rust & Mitschke Gmbh | Füllteilmodul in Planetwalzenextruderbauweise |
DE102017004563A1 (de) | 2017-03-05 | 2018-09-06 | Entex Rust & Mitschke Gmbh | Entgasen beim Extrudieren von Polymeren |
DE102017003681A1 (de) | 2017-04-17 | 2018-10-18 | Entex Rust & Mitschke Gmbh | Kühlen beim Extrudieren von Schmelze |
DE102017005999A1 (de) | 2017-05-28 | 2018-11-29 | Entex Rust & Mitschke Gmbh | Herstellung von essbaren Wurstpellen aus Kollagen oder gleichartigen Stoffen durch Extrudieren |
DE102017005998A1 (de) | 2017-06-23 | 2018-12-27 | Entex Rust & Mitschke Gmbh | Chemische Prozeßführung für fließfähiges Einsatzgut in einem Planetwalzenextruder |
DE102017006638A1 (de) | 2017-07-13 | 2019-01-17 | Entex Rust & Mitschke Gmbh | Füllteilmodul in Planetwalzenextruderbauweise |
DE102018001412A1 (de) | 2017-12-11 | 2019-06-13 | Entex Rust & Mitschke Gmbh | Entgasen beim Extrudieren von Stoffen, vorzugsweise von Kunststoffen |
WO2019166125A1 (de) | 2018-02-28 | 2019-09-06 | Entex Rust & Mitschke Gmbh | Verfahren zur herstellung und verarbeitung von polymeren und polymermischungen in einem modular aufgebauten planetwalzenextruder |
DE102020007239A1 (de) | 2020-04-07 | 2021-10-07 | E N T E X Rust & Mitschke GmbH | Kühlen beim Extrudieren von Schmelzen |
EP3892441A1 (de) | 2020-04-07 | 2021-10-13 | Entex Rust & Mitschke GmbH | Nachrüstung für eine extruderanlage |
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JP3266421B2 (ja) * | 1994-09-13 | 2002-03-18 | 花王株式会社 | 低刺激性身体洗浄剤組成物 |
ES2165926T3 (es) * | 1994-11-15 | 2002-04-01 | Colgate Palmolive Co | Composiciones limpiadoras liquidas de uso general en microemulsion. |
WO1998000497A2 (en) * | 1996-06-28 | 1998-01-08 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning compositions |
DE19824359A1 (de) * | 1998-05-30 | 1999-12-02 | Henkel Kgaa | Duschgel |
PT1045021E (pt) * | 1999-04-13 | 2004-05-31 | Kao Corp Sa | Composicao que inclui uma mistura de mono- di- e trigliceridos alcoxilados e glicerina |
-
1999
- 1999-12-03 DE DE19958398A patent/DE19958398A1/de not_active Ceased
-
2000
- 2000-11-24 DE DE50009468T patent/DE50009468D1/de not_active Expired - Lifetime
- 2000-11-24 EP EP00125727A patent/EP1106675B1/de not_active Expired - Lifetime
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EP1106675A2 (de) | 2001-06-13 |
EP1106675A3 (de) | 2002-09-18 |
DE50009468D1 (de) | 2005-03-17 |
DE19958398A1 (de) | 2001-06-13 |
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