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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2068—Ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

• the present invention relates to a method for producing a water-poor Enzyme preparation, the use of this enzyme preparation in washing and Detergents and a detergent and cleaning agent.
• Enzymes for industrial processing are generally called liquid Offered enzyme concentrates isolated from a fermentation broth and in in a concentrated form.
• the stability of the enzymes in water Environment is limited.
• To convert the enzyme concentrates obtained into an anhydrous To convert form, the concentrate z. B. in the presence of a polymer Binder are spray dried, wherein the dried enzyme particles from Binders are absorbed and aggregates form. For production of The spray-dried particles are redispersed in liquid preparations.
• a method for producing enzyme dispersions is described in WO94 / 25560 disclosed.
• the process described there involves emulsifying a solid Enzyme preparation in a water-immiscible liquid in the presence of a polymeric dispersion stabilizer, whereby a stable dispersion of the aqueous Enzyme particles, which have a particle size below 30 microns, is formed, and Dehydrate the dispersed particles by azeotropic distillation.
• An essential feature of the method described is that during or after the Dehydrating the particles an organic liquid that is less volatile than that liquid which is not miscible with water and which is selected from surfactants and with Water-miscible liquids are added with redispersion, and not with Water-miscible liquid is distilled from the dispersion until the amount of this initially submitted liquid in the dispersion below 20 wt .-% based on the liquid phase of the dispersion.
• enzymes An important area of application for enzymes is detergents and cleaning agents. In These agents either incorporate the enzymes as solid components or in Form of liquid formulations.
• Liquid bleach-containing formulations require that the water content only is low to stabilize the bleach. That means the water content of the raw materials used must be correspondingly low.
• the present invention was accordingly based on the object To provide enzyme preparation that has a low water content and can be obtained in a simple form from aqueous enzyme concentrates without that the enzyme activity is significantly reduced.
• a low-water enzyme preparation can be obtained by a re-solubilization, namely by the aqueous Enzyme concentrate with an organic solvent that has a higher boiling point has added as water, and is subjected to distillation.
• the present invention accordingly relates to a method for the production a low-water enzyme preparation, wherein an aqueous enzyme preparation with mixed with an organic solvent with a boiling point above 100 ° C and that Mixture is then distilled.
• the advantage of this invention is that dehydration and redispersion be avoided.
• Organic solvent can be used in the process according to the invention Solvents are selected that have a boiling point above 100 ° C. These solvents should preferably be selected such that the water is can be removed by distillation without forming an azeotrope.
• liquid nonionic surfactants such as Fatty alcohol alkoxylates
• monohydric or polyhydric alcohols such as Ethylene glycol, propylene glycol, glycerin or low molecular weight polyethylene glycols with 2 up to 14 monomer units.
• solvents are also suitable for the production of liquid to gel-like detergents and cleaning agents called solvents, if they have a boiling point above 100 ° C
• the Distillation under vacuum and at a temperature preferably below 50 ° C carried out.
• the distillation in a water jet vacuum is at ambient temperature particularly suitable.
• the water content of the enzyme preparation produced according to the invention is preferably below 15% by weight, particularly preferably below 10% by weight and in particular below 7% by weight, based on the entire preparation.
• the enzymes can be made from any enzymes customary for detergents and cleaning agents to be selected.
• enzymes come primarily from microorganisms such as Bacteria or fungi, proteases obtained, lipases, amylases and / or cellulases in question. They are made in a known manner by suitable fermentation processes Microorganisms obtained, for example, in the German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, the United States US Pat. Nos. 3,632,957 and 4,264,738, the European patent application EP 006 638 and the international patent application WO 91/912792 are.
• the preparation produced according to the invention is a is a protease-containing preparation
• the protase activity is preferably 150,000 Protease units (PE, determined according to that described in Tenside 7 (1970), 125 Method) up to 1 500 000 PE, in particular 200 000 PE to 1 000 000 PE, per gram Preparation.
• the low-water enzyme preparations obtained according to the invention can in themselves Known way supplied to their uses and processed there become.
• the low-water enzyme preparations are in Detergents and cleaning agents used.
• Another object of the present invention is accordingly the use of Low-water enzyme preparation obtained by the method described above in detergents and cleaning agents, preferably in liquid to gel-containing bleaches Detergents and cleaning agents.
• Yet another object of the present invention are washing and Cleaning agents, the surfactants and builder substances and, if necessary, others Contain common ingredients, which are characterized by the fact that enzymes in the form a low-water preparation, such as the one described above can be obtained contains.
• the agents according to the invention contain surfactants, e.g. B. nonionic, anionic and amphoteric surfactants, and bleaches as well as other usual ingredients.
• surfactants e.g. B. nonionic, anionic and amphoteric surfactants, and bleaches as well as other usual ingredients.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic Surfactants used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters.
• alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
• Alkypolyglycosides which can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
• Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
• nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (II), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical
• [Z] is preferably obtained by reductive amination of a reduced sugar.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy or N-aryloxy substituted compounds can be exemplified by Reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the Desired polyhydroxy fatty acid amides are transferred.
• the surfactants are in total in the cleaning or washing agents according to the invention in an amount of preferably 2% by weight to 80% by weight, in particular 3% by weight up to 70 wt .-%, based on the finished agent.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved.
• Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.
• alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 12-C16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
• 2,3-Alkyl sulfates which are produced, for example, in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono- or dioder Triethanolamine.
• the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
• Sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are particularly important among the compounds which provide H 2 O 2 in water and which serve as bleaching agents.
• Other usable bleaching agents are, for example, persulfates and mixed salts with persulfates, such as the salts available under the trade name CAROAT®, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanoic acid or diperdodecanoic acid or diperdodecanoic acid.
• bleaching agents Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the shaped bodies. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, E-phthalimidanoic acid poxyaprooxy acid (E-phthalimidanoic acid) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacynbroxy acid, Decyldiperoxybutane-1,4-diacid
• Bleach activators are incorporated into the detergent tablets.
• bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 up to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used.
• Substances containing the O- and / or N-acyl groups are suitable mentioned number of carbon atoms and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluriie, especially 1,3,4,6-tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC), Carboxylic anhydrides, especially phthalic anhydride, isatoic anhydride and / or succinic anhydride, car
• German patent application DE-A-196 16 769 known hydrophilically substituted Acylacetale and those in the German patent application DE-A-196 16 770 and the international patent application WO-A-95/14075 described acyllactams also preferably used.
• German patent application DE-A-44 43 177 known combinations of conventional bleach activators can be used.
• nitrile derivatives such as cyanopyridines, nitrile quats, e.g. B. N-alkyammonium acetonitrile, and / or cyanamide derivatives are used.
• Preferred Bleach activators are sodium 4- (octanoyloxy) benzene sulfonate, n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).
• Such bleach activators are in the usual range of amounts from 0.01 to 20% by weight, preferably in amounts from 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the overall composition, contain.
• bleach catalysts can be included.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are suitable as bleaching catalysts.
• the content of the agents is 1 to 40% by weight and in particular 10 to 20% by weight, whereby perborate monohydrate or percarbonate is advantageously used.
• the agents according to the invention generally contain one or more builders, especially zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates. Latter are especially in detergent tablets for automatic dishwashing preferably used builders.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
• Amorphous sodium silicates with a module Na20: Si02 from 1: 2 to can also be used 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolving and have secondary washing properties.
• the release delay Compared to conventional amorphous sodium silicates, there are various options Way, for example by surface treatment, compounding, compacting / Compression or caused by overdrying. As part of this Invention is understood by the term “amorphous” also "X-ray amorphous”.
• the silicates are not sharp in X-ray diffraction experiments X-ray reflections provide, as they are typical for crystalline substances, but at most one or more maxima of the scattered x-rays, which have a width of have several degree units of the diffraction angle. However, it can very well even lead to particularly good builder properties if the silicate particles contribute Electron diffraction experiments blurred or even sharp diffraction maxima deliver. This is to be interpreted as meaning that the products have microcrystalline areas Size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Are particularly preferred compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2-2.5) SiO 2 ⁇ (3.5 - 5.5) H 2 O can be described.
• 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.
• Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
• NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
• Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O 7 when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
• Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) .
• Substances are colorless crystals that are soluble in water with an alkaline reaction.
• Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
• Potassium diphosphate potassium pyrophosphate
• K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
• Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates.
• a large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
• sodium tripolyphosphate sodium tripolyphosphate
• n 3
• Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
• sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 +2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
• these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
• organic cobuilders in the washing and Detergent tablets in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic Cobuilder (see below) and phosphonates are used. These substance classes are described below.
• Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, 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 have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents.
• Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
• copolymeric polycarboxylates especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
• Their relative molecular weight, based on free acids, is in general 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be either as a powder or as an aqueous Solution are used.
• the content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
• allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
• Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
• copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
• polymeric aminodicarboxylic acids to name their salts or their precursors.
• Particular preferred Polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained.
• Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their Mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid receive.
• Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained.
• the hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
• a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which a DE out of 100.
• DE dextrose equivalent
• oxidized derivatives of such dextrins are theirs Reaction products with oxidizing agents that are capable of at least one To oxidize the alcohol function of the saccharide ring to the carboxylic acid function.
• oxidizing agents capable of at least one To oxidize the alcohol function of the saccharide ring to the carboxylic acid function.
• an oxidized oligosaccharide is suitable, such as one oxidized at C6 of the saccharide ring Product.
• Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 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 have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.
• phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
• hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g.
• the Class of phosphonates preferably uses HEDP.
• the aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, it is preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.
• the washing and Detergent liquid to gel form.
• Solvents used in the liquid to gel compositions can come, for example, from the group of mono- or polyvalent Alcohols, alkanolamines or glycol ethers, provided they are specified in the Concentration range are miscible with water. You can also use the above mentioned organic solvents are used to produce the Enzyme preparation can be used.
• the solvents are preferred selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl or ethyl propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.
• Solvents can be used in the invention liquid to gel detergents in amounts between 0.1 and 20% by weight, but preferably used below 15 wt .-
• composition according to the invention can be used to adjust the viscosity or several thickeners or thickening systems can be added.
• the viscosity of the Compositions according to the invention can be prepared using customary standard methods (e.g. Brookfield RVD-VII viscometer at 20 rpm and 20 ° C, spindle 3) be measured and is preferably in the range of 100 to 5000 mPas.
• Preferred compositions have viscosities of 200 to 4000 mPas, where Values between 400 and 2000 mPas are particularly preferred.
• Suitable thickeners are inorganic or polymeric organic compounds. This mostly organic high molecular substances, which are also called swelling agents, usually absorb the liquids and swell them, eventually turning into viscous to pass real or colloidal solutions.
• the inorganic thickeners include, for example, polysilicic acids, Clay minerals such as montmorillonites, zeolites, silicas and bentonites.
• the organic thickeners come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.
• Natural polymers that are used as thickeners for example agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, Polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and Casein.
• Modified natural products mainly come from the group of modified starches and celluloses, for example carboxymethyl cellulose and others Cellulose ether, hydroxyethyl and propyl cellulose as well as core meal ether called.
• a large group of thickeners that are widely used in the Find the most diverse fields of application are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, Polyethers, polyimines, polyamides and polyurethanes.
• the thickeners can be present in an amount of up to 5% by weight, preferably from 0.05 to 2% % By weight, and particularly preferably from 0.1 to 1.5% by weight, based on the finished product Composition.
• the washing and cleaning agent according to the invention can be used as a further conventional one Ingredients in particular sequestering agents, electrolytes, pH regulators and further auxiliaries, such as optical brighteners, graying inhibitors, Color transfer inhibitors, foam regulators, additional bleach activators, color and Contain fragrances.
• detergents can contain a A large number of compounds are used, examples being foam inhibitors, Phosphonates, enzymes and optical brighteners called.
• Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
• the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
• the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylene triamine pentamethylene phosphonate or ethylenediaminetetramethylenephosphonate in Amounts of 0.1 to 1.5 wt .-% used.
• the agents according to the invention can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear.
• Brighteners of the type of substituted diphenylstyryl e.g.
• the agent according to the invention is a so-called liquid to gel Heavy duty detergent used, it preferably contains from 0 to 20 wt .-% anionic Surfactants, 40 to 80% by weight nonionic surfactants, 2 to 25% by weight builder materials, 0 up to 20% by weight of bleach, 0 to 20% by weight of bleach activators, 0 to 5% by weight of enzymes, Fragrances and other ingredients.
• a harvest pulp obtained after the fermentation, as described in international patent application WO 91/2792, with 75,000 protease units per g (PE / g) was concentrated in an ultrafiltration system after removal of the fermentation residues by decanting and microfiltration. After further concentration by means of vacuum evaporation, the aqueous enzyme suspension contained 700,000 PE / g, the water content was about 70%.
• This concentrate was mixed with 1,2-propylene glycol ( Example 1 ) or glycerol ( Example 2 ) in an amount such that the mixture obtained contained 40% by weight of solvent and 40 water.
• the mixture was added in a water jet vacuum using a rotary evaporator Distilled room temperature until the mixture had the desired water content.
• Example 1 The formulation obtained in Example 1 contained 66% 1,2-propylene glycol, 9.5% water (determined according to Karl Fischer) and had an activity of about 700,000 ⁇ PE / g.
• Example 2 The preparation obtained in Example 2 contained 68% glycerol, 6.4% water (determined according to Karl Fischer) and had the same activity as the preparation from Example 1.

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• 1999
  • 1999-11-10 DE DE1999153870 patent/DE19953870A1/de not_active Withdrawn
• 2000
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