Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
• • 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
• • 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 grease stains have. Their properties complement those of anionic surfactants which they are usually used together have the advantage over them inverse solubility, i.e. nonionic surfactants dissolve at low temperatures while they in the heat by breaking polar hydrogen bonds and are therefore suitable especially for the production of liquid detergents.
• Ethoxylated fatty alcohols are usually used for the production of detergents, but they do for a number of particularly stubborn stains, e.g. Make up or lipstick Have weaknesses. Incorporation into solid detergents, especially detergent tablets, is problematic because the fatty alcohol ethoxylates have a tendency to bleed out, i.e. separate from the homogeneous preparation, which is a whole series of undesirable side effects causes: the washing power is reduced, the cardboard is softened and not infrequently Partially deactivated defoamer used.
• the complex object of the present invention was to provide new nonionic surfactants for the production of solid or liquid washing, rinsing and cleaning agents, preferably those in tablet form, which reliably avoid the disadvantages mentioned above.
• the invention relates to the use of ethoxylation products of partial glycerides Production of detergents, dishwashing detergents and cleaning agents, which are characterized in that they are made of Mixtures of partial glyceride ethoxylates and glycerol ethoxylates in a weight ratio of 3.3: 1 to 6 : 1 and preferably 3.5: 1 to 4.5: 1.
• R 1 CO represents 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 independently of one another are R 1 CO or hydrogen, with the proviso that either R 2 or R 3 means hydrogen.
• the starting materials are usually placed in a pressure reactor, the alkaline catalyst, for example sodium methylate or calcined hydrotalcite, is added, and the desired amount of ethylene oxide is injected.
• the alkaline catalyst for example sodium methylate or calcined hydrotalcite
• the temperature is usually in the range of 110 to 180 ° C, the autogenous pressure can rise to 5 bar.
• the mixture is left to react for about 30 minutes before the autoclave is cooled, decompressed and the alkaline catalyst is neutralized or filtered, for example by adding lactic acid.
• the mixtures can also be prepared by reacting triglycerides with ethylene oxide in a first step - forcing 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 process can be found, for example, by Ropuszynski in IV. International Conference on Interface- Active Substances, Berlin, 1974, Treatises by the GDR Academy of Sciences, Born in 1976, No. 1N, Akademieverlag Berlin, 1977, pp. 119-121.
• the ethoxylation products can be used for the production of both liquid and solid preparations are used and are usually used in amounts of 1 to 30, preferably 2 up to 15 and in particular 5 to 10% by weight, based on the composition.
• the preparations can also contain a variety of other common auxiliaries and additives.
• Primary constituents of the solid and liquid washing, rinsing, cleaning and finishing agents which can be prepared using the ethoxylated partial glycerides are anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants, but preference is given to anionic surfactants or combinations of anionic ones and nonionic surfactants.
• anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, mono (sulfide) sulfate, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids
• anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
• Alkyl benzene sulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are preferably used.
• 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 to be understood as meaning 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 in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, petroselachcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
• the sulfation products can preferably be used in the form of their alkali metal salts and in particular 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 are particularly preferred.
• these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method.
• Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
• oxo alcohols such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins.
• These alcohol mixtures are a mixture of strongly branched alcohols.
• Such alcohol mixtures are commercially available under the trade name Lial®.
• Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
• soaps are to be understood as meaning fatty acid salts of the formula (IV) R 6 CO-OX 3 (IV) in which R 6 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X 3 represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
• Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petol acid Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
• coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.
• nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (in particular vegetable products based on wheat), polyol, Zuckerester, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides are preferably used.
• the preferred fatty alcohol polyglycol ethers follow the formula (V) R 7 O (CH 2 CHR 8 O) n1 H (V) in which R 7 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 8 represents hydrogen or methyl and n1 represents numbers from 1 to 20.
• Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.
• Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI) R 9 CO- (OCH 2 CHR 10 ) n2 OR 11 (VI) in which R 9 CO is a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R 10 for hydrogen or methyl, R 11 for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers from 1 to 20 stands.
• Typical examples are the formal insert 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, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and technical grade mixtures and erucas.
• the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
• 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 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As 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 with 5 or 6 carbon atoms, preferably glucose.
• the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .
• the index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
• Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
• 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, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
• the alkyl or alkenyl radical R 12 can 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 their technical mixtures, which can be obtained as described above.
• Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
• cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats .
• quaternized fatty acid triethanolamine ester salts of the formula (VIII) in which R 13 CO represents an acyl radical with 6 to 22 carbon atoms, R 14 and R 15 independently of one another for hydrogen or R 13 CO, R 16 represents an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate.
• VIII quaternized fatty acid triethanolamine ester salts of the formula (VIII) , in which R 13 CO represents an acyl radical with 6 to 22 carbon atoms, R 14 and R 15 independently of one another for hydrogen or R 13 CO, R 16 represents an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) m4 H- Group, m1, m2 and m3 in total for
• ester quats 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, arachic 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.
• Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as high elaidic acid C 16/18 fatty acid cuts are preferably used.
• the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
• an application 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 ester quats 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).
• quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven particularly advantageous, in which R 13 CO for an acyl radical having 16 to 18 carbon atoms, R 14 for R 13 CO, R 15 for hydrogen, R 16 for a methyl group, m1 , m2 and m3 stands for 0 and Y for methyl sulfate.
• quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) may also be used as ester quats.
• R 17 CO for an acyl radical with 6 to 22 carbon atoms
• R 18 for hydrogen or R 17 CO
• R 19 and R 20 independently of one another for alkyl radicals with 1 to 4 carbon atoms
• m1 and m2 in total for 0 or numbers from 1 to 12
• Y represents halide, alkyl sulfate or alkyl phosphate.
• ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (X) should be mentioned as a further group of suitable ester quats, in which R 21 CO for an acyl radical with 6 to 22 carbon atoms, R 22 for hydrogen or R 21 CO, R 23 , R 24 and R 25 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m1 and m2 in total for 0 or numbers from 1 to 12 and Y represents halide, alkyl sulfate or alkyl phosphate.
• suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine, in which R 26 CO stands for an acyl radical with 6 to 22 carbon atoms, R 27 for hydrogen or R 26 CO, R 28 and R 29 independently of one another for alkyl radicals with 1 to 4 carbon atoms and Y for halide, alkyl sulfate or alkyl phosphate.
• Such amide ester quats are available on the market, for example, under the name Incroquat® (Croda).
• alkyl betaines examples include alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
• alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII) in which R 30 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 31 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 32 for alkyl radicals with 1 to 4 carbon atoms, q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium.
• Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C 16/18 tallow alkyl dimethyl amine and technical mixtures thereof.
• Carboxyalkylation products of amidoamines which follow the formula (III) are also suitable , in which R 33 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 34 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 35 for alkyl radicals with 1 to 4 carbon atoms, q2 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.
• R 33 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
• R 34 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
• R 35 for alkyl radicals with 1 to 4 carbon atoms
• q2 for numbers from 1 to 3
• q3 represents numbers from 1 to 6
• Z represents an alkali and / or alkaline earth metal or ammonium.
• Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
• 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 diethylene triamine.
• polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
• AEEA aminoethylethanolamine
• the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
• Typical examples are condensation products of the above-mentioned 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 finishing agents according to the invention can furthermore additionally contain inorganic and organic builder substances, whereby as inorganic builder substances mainly zeolites crystalline layered silicates, amorphous silicates and - as far as permissible - also Phosphates, e.g. Tripolyphosphate are used.
• inorganic builder substances mainly zeolites crystalline layered silicates, amorphous silicates and - as far as permissible - also Phosphates, e.g. Tripolyphosphate are used.
• the amount of co-builder is based on that allowance for preferred amounts of phosphates.
• the fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a 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 and Y are also suitable.
• a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
• the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 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 delayed release and have secondary washing properties.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
• Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons.
• Suitable are in particular the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphate.
• Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent.
• tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances for a synergistic improvement of secondary washing power.
• Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric 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 value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used.
• a preferred dextrin is described in British patent application GB 9419091 A1 .
• the 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 as well as from 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 are known.
• An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates , preferably ethylenediamine disuccinate .
• glycerol disuccinates and glycerol trisuccinates are particularly preferred in this context, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 .
• Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may 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 .
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic 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.
• the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case 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 subsequently mixed into one or more basic granules.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon 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 their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• the agents can also contain components that make the oil and fat washable made of textiles.
• the preferred oil and fat dissolving components include, for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives known in the art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
• Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these;
• alkali carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 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 in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
• the agents can include other known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, minor Contain amounts of neutral filler salts as well as colors and fragrances and the like.
• sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H202-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
• the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
• 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.
• Multi-acylated 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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications
• hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
• the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
• the sulfonimines 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 bleaching catalysts.
• the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 19529905 A1 and their N-analog compounds 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 complexes, 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, the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese Complexe
• Bleach-enhancing transition metal complexes in particular with 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% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
• Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and micro
• Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
• Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
• the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
• the agents can contain further enzyme stabilizers .
• enzyme stabilizers 0.5 to 1% by weight 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 pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
• Graying inhibitors have the task of suspending the dirt detached from the fiber in the liquor to keep and thus prevent the dirt from re-opening.
• water soluble Colloids mostly of an organic nature are suitable, for example the water-soluble salts of polymers Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose.
• Farther soluble starch preparations and starch products other than those mentioned above can be used, e.g. degraded starch, aldehyde starches, etc.
• Polyvinylpyrrolidone can also be used.
• cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and polyvinylpyrrolidone, for example in amounts of 0.1 up to 5 wt .-%, based on the agent used.
• the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. 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 instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type may also 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) diphenyl. Mixtures of the aforementioned brighteners can also be used.
• Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
• a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
• Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can 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 5000, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approx. 15 up to 100.
• the polymers have an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure.
• Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20 Preferred are those polymers which link polyethylene glycol units with a molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
• Wax-like compounds can be used as defoamers. Such are called “waxy” Understood compounds that have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably have above 50 ° C and in particular above 70 ° C.
• the waxy defoamer substances are practically insoluble in water, i.e. at 20 ° C in 100 g of water solubility below 0.1% by weight.
• Suitable waxy compounds are, for example Bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols and paraffin waxes or mixtures thereof. Alternatively, of course, you can also use them Purpose known silicone compounds are used.
• Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines 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 changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention.
• the soft waxes which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products.
• solid hydrocarbons with melting points between 63 and 79 ° C which are separated from the highly viscous, paraffin-containing lubricating oil distillates during the dewaxing.
• These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins.
• the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
• paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
• Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight.
• the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
• the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
• Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
• Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated 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 bismyristoylethylene diamine, bispalmitoylethylene diamine, bisstearoylethylene diamine and mixtures thereof and the corresponding derivatives of hexamethylene diamine.
• Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
• these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
• the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
• suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
• Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
• Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate, and sorbitan dandebehenate, as well as sorbitan dandebehenate and mixed sorbitan dibehenate.
• Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
• esters as defoamers are beeswax, which mainly consists 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 , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
• beeswax which mainly consists 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 carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
• Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
• Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
• Dialkyl ethers may also be present as defoamers.
• the ethers can be constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms.
• Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
• Suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts, for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS .
• Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid.
• Suitable defoamers are fatty acid polyethylene glycol esters , which are preferably obtained by base-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, leads to an 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 wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
• the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
• the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
• the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
• the aluminosilicates referred to as carrier 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 which are commercially available under the name Aerosil® or Sipernat® can also be used.
• suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
• Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
• Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
• the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
• native starch which is composed of amylose and amylopectin. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
• Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
• alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
• Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an almost 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 in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanated.
• Silicic acid-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
• the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C.
• silicones in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
• the silicones are preferably used in the form of their aqueous emulsions. As a rule, the silicone is added to the water initially introduced with stirring. If desired, thickeners such as are known from the prior art can be added to increase the viscosity of the aqueous silicone emulsions.
• nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyoxy cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC) are particularly preferred.
• 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.
• aqueous silicone solutions are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat.
• the starch is advantageously present in amounts of 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 carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
• the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added.
• the silicones are expediently incorporated with the aid of effective stirring and mixing devices.
• the solid preparations are, for example, detergent tablets or granules, these may also contain disintegrants.
• the disintegrants can be macroscopically homogeneously distributed in the shaped body, but microscopically they form zones of increased concentration due to the manufacturing process.
• the preferred disintegrants include polysaccharides, such as, for example, 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), polyvinylpyrrolidone, collidone, alginic acid and their alkali salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
• polysaccharides such as, for example, 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), polyvinylpyrrolidone, collidone, alg
• disintegrants which may be present in the sense of the invention are, for example, the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 (Henkel) refer to. Reference is expressly made to the teaching of these writings.
• the moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.
• fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
• Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
• the ethers include, for example, benzyl ethyl ether, 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.
• perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil.
• muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• the fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the perfume adheres to the laundry intensify and ensure a long-lasting fragrance of the textiles through a slower fragrance release.
• Cyclodextrins for example, have proven successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
• the final preparations can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
• inorganic salts such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 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 are manufactured or used. It can be both universal and fine or color detergents, if necessary, act in the form of compact or super compact. For the production such means, the corresponding methods known from the prior art are suitable.
• the agents are preferably prepared in that various particulate components, the detergent ingredients are mixed together.
• the particulate Components can be spray dried, simple mixed or complex granulation processes, for example, fluidized bed granulation. It is particularly preferred 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 silicate and the alkali carbonate sprayed together with other detergent ingredients in a drying facility be, whereby granulation can take place simultaneously with the drying.
• the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
• the drying is carried out as spray drying in a drying tower.
• the aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner.
• Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
• a particularly preferred way of producing the agents is to subject the preliminary products to fluidized bed granulation (“SKET” granulation).
• SKET fluidized bed granulation
• the preliminary products can be used both in the dried state and as an aqueous preparation.
• Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m.
• the granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s.
• the granules are preferably discharged from the fluidized bed via a size classification of the granules.
• the classification can take place, for example, by means of a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
• the inflowing air is usually 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 mass for example a granulate from an earlier test batch, is presented at the beginning of the granulation.
• the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step.
• the compacting of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process instead of.
• the press agglomeration process to which the solid premix (dried basic detergent) subject can be realized in various devices. Depending on A distinction is made between the type of agglomerator used and different press agglomeration processes.
• the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting processes are.
• binders can be used as an aid to compaction.
• a binder is used which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C.
• 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 preferably takes place at processing temperatures which, at least in the compression step, correspond at least to 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 in the form of 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. It is technically possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages.
• thermoly sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious loss of active substance.
• peroxy bleaching agents 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 compaction, i.e. between the mixing / homogenization of the premix and the shaping, permits an energetically very economical and extremely gentle process control for the temperature-sensitive components of the premix, since the premix only lasts for a short time exposed to higher temperatures.
• the work tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
• the duration of the temperature effect in the compression range of the press agglomerators is preferably 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 a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also 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 with a relative 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, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000.
• polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
• the polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred.
• the particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000.
• polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
• these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
• suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred.
• Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.
• the compressed material preferably has temperatures immediately after it leaves the production apparatus not above 90 ° C, with temperatures between 35 and 85 ° C 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 produced 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 pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
• the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
• Preferred plasticizers and / or lubricants are surfactants and / or polymers.
• the premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
• the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
• the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
• particle diameters up to 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 from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
• the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off 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, can also be used in this step.
• extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
• the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
• the duration of the temperature influence in the compression range 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 produced by means of roller compaction .
• the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
• the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
• smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified.
• the sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in an approximately spherical shape.
• the temperature of the pressing tools that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
• Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
• the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is 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 pelleting .
• the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
• the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
• the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
• the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
• An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 .
• the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
• the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
• the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
• Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
• Shaped bodies are generally produced by tableting or press agglomeration .
• the particulate press agglomerates obtained can either be used directly as detergents or aftertreated and / or prepared beforehand by customary methods.
• the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density.
• a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1, in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to agents , 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 can be circular or rectangular, for example.
• Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
• the tablets can also contain pressed and unpressed parts.
• Shaped articles with a particularly advantageous dissolution rate are obtained if the granular constituents have a proportion of particles, which have a diameter outside the range of 0.02 to 6 mm, of less than 20, preferably less than 10% by weight, prior to pressing.
• 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 tests were carried out in a Launder-ometer (temperature: 40 ° C, dosage: 6 g / l, water hardness 20 ° dH, loading: 2 kg).
• Example 1 is according to the invention, example V1 corresponds to the blank value without the addition of surfactant, examples V2 to V4 with different contents of glycerol ethoxylates serve for comparison.

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• 1999
  • 1999-12-03 DE DE19958398A patent/DE19958398A1/de not_active Ceased
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