WO2001034757A1 - Corps façonnes presentant une solubilite dans l'eau amelioree - Google Patents

Corps façonnes presentant une solubilite dans l'eau amelioree Download PDF

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Publication number
WO2001034757A1
WO2001034757A1 PCT/EP2000/010688 EP0010688W WO0134757A1 WO 2001034757 A1 WO2001034757 A1 WO 2001034757A1 EP 0010688 W EP0010688 W EP 0010688W WO 0134757 A1 WO0134757 A1 WO 0134757A1
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Prior art keywords
acid
weight
shaped body
body according
alcohol
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PCT/EP2000/010688
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German (de)
English (en)
Inventor
Karl Heinz Schmid
Bernd Fabry
Detlev Stanislowski
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Cognis Deutschland Gmbh & Co. Kg
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Priority to EP00972881A priority Critical patent/EP1228186A1/fr
Publication of WO2001034757A1 publication Critical patent/WO2001034757A1/fr

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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
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the invention is in the field of solid washing, rinsing and cleaning agents and relates to new moldings with improved water solubility, which are characterized by a content of surfactants, disintegrants and special defoamer granules.
  • a process for the production of the shaped bodies, which are particularly suitable for the production of tablets, is further claimed.
  • a typical feature of anionic surfactants is to develop foam. In many applications, such as in hand dishwashing detergents or hair shampoos, this effect is expressly desired by the consumer, since it equates it with performance, even if this is not readily the case from a scientific point of view. In the field of household and industrial detergents, especially those in tablet form, foam development is essentially undesirable, since it can quickly lead to over-foaming of the machine. Since anionic surfactants as a component of the recipes cannot generally be dispensed with because of their special performance profile, there is a need to provide detergent formulations with a sufficient amount of defoamers, which on the one hand limit the amount of foam to an acceptable level without on the other hand the recipe reduce their performance or make them too expensive. A large number of compounds are known from the prior art for this purpose, of which only the soaps, the paraffins and the silicones should be mentioned here.
  • defoamers have been produced either by drying the corresponding aqueous emulsions or dispersions or by spraying the defoamer component directly onto a carrier.
  • Known processes such as fluidized bed drying or granulation, spray mixing processes and conventional countercurrent drying in the spray tower are used for this purpose.
  • additives such as sodium sulfate or zeolite are generally also incorporated as carriers.
  • Auxiliaries and defoamer components - viewed macroscopically - are homogeneously distributed in the granules, although it turns out under the microscope that the product also has heterogeneous areas, for example zones in which the defoamer is concentrated.
  • the invention relates to moldings with improved water solubility, containing
  • 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, fatty acid (mono amide sulfate), monoglyme sulfate, monoglyme sulfate, (monoglyme sulfate), monoglyme sulfate, monoglyme sulfate - and dialkyl sulfosuccinates, mono- and Dialkylsulfosuccina- mate, sulfotriglycerides, amide
  • 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 stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph for a phenyl radical
  • X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.
  • Alkyl and / or alkenyl sulfates which are also often 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 (II)
  • R 2 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents 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, arylselyl alcohol, elaidyl alcohol alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be in the form of their alkali salts and in particular their sodium salts are used.
  • Alkyl sulfates based on Ci6 / 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 (III)
  • R 3 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X 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, elaidic acid, elaidic acid, elaidic acid, Linoleic 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 polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid-N-alkylhydroglyl fatty acids, in particular vegetable-based polyglycol amides, protein-based glyceryl fatty acid products , Sugar esters, sorbitan esters, polysorbates and amine oxides.
  • 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 (IV) R 0 (CH 2 CHR 5 0) nH (IV)
  • R 4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 5 represents hydrogen or methyl
  • n 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, isostearyl alcohol , Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elausestearyl 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
  • R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms
  • R 7 is hydrogen or methyl
  • R 8 is a linear or branched alkyl radical having 1 to 4 carbon atoms
  • m is a number 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 behenic acid and behenic acid.
  • 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, caicinated hydrotalcite. Reaction 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 (VI),
  • R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • 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 oligoglucosides.
  • 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 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronalcohol, 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. Alkyl oligoglucosides of chain length Cs-Ci are preferred.
  • the alkyl or alkenyl radical R 9 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 the technical mixtures described above.
  • Alkyl oligoglucosides based on hydrogenated Ci2 / i4 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. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VII),
  • R 10 CO for an acyl radical with 6 to 22 carbon atoms
  • R 1 and R 12 independently of one another for hydrogen or R 10 CO
  • R 13 for an alkyl radical with 1 to 4 carbon atoms or one (CH ⁇ CH ⁇ O ⁇ H group, x1, x2 and x3 in total for 0 or numbers from 1 to 12, x4 for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.
  • esterquats which 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 as well as their technical mixtures, such as those in the Technical Ci2 / i8 coconut fatty acids and in particular partially hardened Ci ⁇ / i ⁇ tallow or palm fatty acids as well as high-elicinic Ci6 / ⁇ .
  • Fatty acid cuts are preferably used.
  • the fatty acids and the triethanolamine can be produced in the molar to produce the quaternized esters Ratio of 1.1: 1 to 3: 1.
  • a ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C16 / 1. tallow or palm fatty acid (iodine number 0 to 40).
  • quaternized fatty acid triethanolamine ester salts of the formula (VII) have proven particularly advantageous, in which R 10 CO for an acyl radical having 16 to 18 carbon atoms, R 11 for R 10 CO, R 12 for hydrogen, R 13 for a methyl group , (x1 + x2 + x3) is 0 and X is methyl sulfate.
  • quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) are also suitable as esterquats.
  • R 14 CO for an acyl radical with 6 to 22 carbon atoms
  • R 15 for hydrogen or R 1 CO
  • R 16 and R 17 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • x5 and x6 in total for 0 or numbers from 1 to 12
  • X represents halide, alkyl sulfate or alkyl phosphate.
  • ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine,
  • R 23 CO represents an acyl radical with 6 to 22 carbon atoms
  • R 24 for hydrogen or R 23 CO
  • R 25 and R 26 independently of one another for alkyl radicals with 1 to 4 carbon atoms
  • X for halide, alkyl sulfate or alkyl phosphate.
  • amide ester quats are available on the market, for example, under the name Incroquat® (Croda).
  • amphoteric or zwitterionic surfactants are alkylbetaines, alkylamido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)
  • R 27 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 28 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 29 for alkyl radicals with 1 to 4 carbon atoms
  • y1 for numbers from 1 to 6 and Y for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C-12/14 Kokosal- kyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl- amine, oleyl dimethyl amine, Ci6 / 18 tallow alkyl dimethyl amine, and their technical mixtures.
  • Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable,
  • R 30 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • y2 represents numbers from 1 to 3 and R 27 , R 28 , y1 and Y have the meanings given above.
  • Typical examples are reaction products of Fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, launic acid, mypinsic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, technical acid, lamoleic acid and larmolene acid, technical acid, lamoleic acid and acidic acid, lamoleic acid and acidic acid, lamoleic acid and acidic acidic acid, lamoleic acid and acidic acidic acid Mixtures with N, N-dimethylaminoethylamine, N, N-dimethylamino-propylamine, N, N-diethylaminoethylamine and N, N-dimethylamino-propylamine, which are condensed with sodium umchloroacetate.
  • the use of a condensation product of C ⁇ / is-coconut fatty acid
  • 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.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different substances open-chain betaines are typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on launic acid or again Ci2 / i4-coconut fatty acid, which are subsequently betainized with sodium chloroacetate
  • the preparations according to the invention usually contain the anionic, nonionic, cationic and / or amphoteric surfactants in amounts of 1 to 50, preferably 5 to 35 and in particular
  • the moldings also contain disintegrants as component (b). These are substances which are added to the moldings in order to prevent them from disintegrating when they come into contact with water. to speed it up. Overviews can be found, for example, in J.Pharm.Sci. 61 (1972) or Römpp Chemilexikon, 9th edition, volume 6, p. 4440.
  • the disintegrants can be macroscopically distributed homogeneously in the molded 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,
  • 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). 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.
  • the defoamer granules which are mandatory as component (c) are the subject of a further patent application by the applicant.
  • Soft waxes which form component (d) and have a melting point in the range from 35 to 50 ° C., preferably belong to the group of petrolates and their hydrogenation products. They consist of microcrystalline paraffins and up to 70% by weight oil, have an ointment-like to plastically firm consistency and represent bitumen-free residues from petroleum processing. Distillation residues (petrolatum stocks) of certain paraffin-based and mixed-base crude oils, which are further processed to petroleum jelly, are particularly preferred become.
  • Hard waxes which represent the defoamer component (c2) are to be understood as those wax-like substances which have a melting point at atmospheric pressure above 50 ° C. (room temperature), preferably above 56 ° C. and in particular above 70 ° C.
  • the hard waxes are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water.
  • 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.
  • Bisamides are suitable 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, hexamethylene diamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoylethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic 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, methanol, ethanol, isopropanol, vinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of methanol, 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, pentaerythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan ditane mono-ether and sorbitan ditane dandiolate.
  • 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 examples include glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate.
  • suitable natural esters are bees and carnau wax, the latter being a mixture of camauba acid alkyl esters, often in combination with small proportions of free carnauba acid, other long-chain acids, high molecular weight 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 14 to 18, carbon atoms are preferred. Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • the paraffin wax preferred as a further defoamer compound in the sense of the invention generally represents a complex mixture of substances without a sharp melting point.
  • 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. It is preferably, for example, bitumen-free, oil-like to solid hydrocarbons separated from distillation residues of paraffin- and mixed-base crude oils and cylinder oil distillates by means of solvents. They are of semi-solid, quick, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C.
  • These petrolates represent the main starting The basis for the production of micro waxes.
  • 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. to 90 ° C., 20% by weight to 49% by weight can also be used.
  • paraffin with a solidification point from 42 ° C to 56 ° C and 2% by weight to 25% by weight soft paraffin with a solidification point from 35 ° C to 40 ° C.
  • Paraffins or paraffin mixtures which solidify in the range from 50 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the case of paraffin waxes of component (b), this liquid fraction is as low as possible and is preferably absent entirely.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid content of less than 30% by weight, preferably 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 particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
  • paraffin waxes of the type described are used in particular.
  • suitable silicones which form component (c3) are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated.
  • 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 are used in the form of their aqueous emulsions.
  • the silicone is added to the water initially introduced with stirring.
  • 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 non-ionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40. In general, and especially when adding the described thickener mixtures, use concentrations of approximately 0.
  • 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 previously 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.
  • carrier material for the purposes of the invention, all known inorganic and / or organic carrier materials can be used as carrier material (component c4).
  • typical inorganic carrier materials 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 dissolving speed 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.
  • 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 mixed cellulose ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and their mixtures.
  • 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.
  • Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way.
  • the native starch which is composed of amylose and amylopectin is particularly preferred as the carrier.
  • 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. Native starch is a commercially available product and is therefore easily accessible.
  • Carrier materials which can be used are one or more 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, carboxymethyl cellulose, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate, zeolites, polycarboxylates, in particular poly (meth) acrylate, and cellulose ether and native starch are particularly suitable.
  • the carrier materials can be composed as follows:
  • alkali silicate 0 to 30% by weight alkali silicate
  • alkali sulfate 0 to 75% by weight alkali sulfate
  • polycarboxylates 0 to 5% by weight of polycarboxylates, the sum having to add up to 100% by weight.
  • the defoamer granules can be made from
  • the defoamer granules can be produced, for example, by applying silicones in the form of aqueous emulsions to an admixed preliminary product of soft waxes, hard waxes and carrier materials and simultaneously drying and granulating the products in the fluidized bed.
  • aqueous preparations of the four components can be subjected to spray drying or fluid bed drying in a conventional manner.
  • a preliminary product is first produced from the carrier materials and the defoamer waxes.
  • the proportion by weight of carrier materials is preferably 20 to 98% by weight, in particular 35 to 95% by weight, and that of the soft and hard waxes in total is preferably 2 to 80% by weight, in particular 5 to 65% by weight. calculated on preliminary product.
  • the carrier material can be produced in a conventional manner by spray drying an aqueous slurry.
  • the waxes can be applied, for example, by applying the molten wax-like defoamer substances to the spray-dried, granular carrier material, for example by successive admixing, in particular in the form of a spray.
  • the carrier material is preferably kept in motion by mixing elements or by fluidization in order to ensure a uniform loading of the carrier material.
  • the spray mixers used for this can be operated continuously or discontinuously.
  • the preliminary products can be produced by dissolving or slurrying the carrier material in water, dispersing the waxes therein and then spray-drying this slurry.
  • a water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer can be added to the dispersion. Examples of these are the cellulose ethers mentioned, homo- and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene.
  • the addition of such compounds which act as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the resulting precursor.
  • the water content of the slurry can be 30% by weight to 60% by weight.
  • the spray drying of the dispersion can be carried out in a known manner in systems provided for this purpose, so-called spray towers, using hot drying gases conducted in cocurrent or countercurrent. Drying by drying gases carried in cocurrent with the sprayed material is preferred, since in particular in the case of paraffin-containing preliminary products, the loss of activity attributable to the potential hot air volatility of some constituents of the paraffin can be reduced to a minimum.
  • the spraying of the aqueous silicone emulsions onto the preliminary product is preferably carried out continuously onto the solid preliminary product with simultaneous drying and granulation in a fluidized bed, in particular in a continuously operating fluidized bed according to the so-called SKET process.
  • the aqueous silicone emulsions over one or several nozzles introduced into the fluidized bed.
  • the preliminary product of carrier material and wax-like defoamer substances are mixed in simultaneously with the aqueous silicone emulsions, but separately from them, preferably by means of an automatically controlled solids metering.
  • the product streams of aqueous silicone emulsion and admixed preliminary product are controlled in such a way that defoamer granules are obtained which preferably contain 1 to 10% by weight, in particular 2 to 8% by weight, of silicone, calculated as silicone and based on defoamer granules.
  • the remaining 100% by weight of the defoamer granulate is the preliminary product already described.
  • the aqueous silicone emulsion meets the mixed preliminary products with simultaneous evaporation of the water, whereby dried to dried germs are formed, which are coated with further introduced aqueous silicone emulsions or with the mixed preliminary products, granulated and again dried at the same time.
  • the simultaneous drying and granulation takes place in the fluidized bed above a circular inflow floor provided with through-openings for the drying air, the product to be dried remaining stationary above the inflow floor during this drying phase, so that a build-up granulation takes place.
  • SKET process More information on the so-called SKET process can be found in European patent EP 0603207 B1.
  • a particular advantage of the process is that the defoamer granules that are produced are classified or classified by the incoming drying air with regard to their particle size and thus also with regard to their weight, so that those granules which have reached the desired particle size or weight fall out of the fluidized bed the fluidized bed in a discharge lock.
  • Fluidized bed apparatuses which are preferably used have circular base plates (inflow base) with a diameter between 0.4 and 5 m, for example 1, 2 m or 2.5 m.
  • Perforated floor slabs a Contidur slab (commercial product from Hein & Lehmann, Federal Republic of Germany) or perforated floor slabs can be used as the floor slab, the holes (passage openings) of which are covered by a grid with mesh sizes of less than 600 ⁇ m.
  • the grid can be arranged inside or above the passage openings. However, the grid preferably lies directly below the passage openings of the inflow floor. This is advantageously realized in such a way that a metal gauze with the appropriate mesh size is sintered on.
  • the metal gauze preferably consists of the same material as the inflow floor, in particular of stainless steel.
  • the mesh size of said grid is preferably between 200 and 400 ⁇ m.
  • the process is preferably carried out at swirl air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s.
  • the granules are advantageously discharged via a size classification of the granules. This classification is preferably carried out by means of an opposite flow of drying air (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 composed of the heated or unheated classifier air and the heated soil air.
  • the soil air temperature is preferably between 80 and 400 ° C.
  • the Eddy air cools down through heat losses and through the heat of vaporization and is preferably about 5 cm above the base plate 60 to 120 ° C., preferably 65 to 90 and in particular 70 to 85 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, in particular below 80 ° C.
  • the residence time for the product to be dried, which remains stationary above the inflow floor, is preferably in the range from 5 to 60 minutes.
  • the defoamer granules are regarded as dried if the free water content is below 10% by weight, preferably from 0.1 to 2% by weight, based in each case on the finished granules.
  • a starting mass is necessary for a starting mass to be present at the beginning of the process, which serves as an initial carrier for the sprayed-in aqueous silicone emulsion.
  • Suitable starting materials are the admixed preliminary products or, in particular, the defoamer granules themselves, which have already been obtained in a previous process.
  • defoamer granules with a grain size in the range above 0.2 and below 0.9 mm are used as starting mass and are preferably fed in via a roller mill.
  • the defoamer granules obtained from the fluidized bed are then preferably cooled in a separate fluidized bed and classified by means of a sieve into granules with particle sizes between 0.4 and 1.5 mm as good-grain fraction, in granules over 1.5 mm as oversize fraction and in granules below 0. 4 mm as undersize fraction.
  • the granules of the undersize fraction are returned to the fluidized bed.
  • the oversize fraction is ground, preferably in grain sizes below 0.4 mm, and also returned to the fluidized bed.
  • the solid moldings according to the invention can furthermore contain additional inorganic and organic builder substances, the inorganic builder substances being mainly zeolites, crystalline phyllosilicates, amorphous silicates and - where permissible - also phosphates, such as e.g. Tripolyphosphate are used.
  • the inorganic builder substances being mainly zeolites, crystalline phyllosilicates, amorphous silicates and - where permissible - also phosphates, such as e.g. Tripolyphosphate are used.
  • the washing, rinsing, cleaning and finishing agents according to the invention can furthermore contain additional inorganic and organic builder substances, zeolites mainly being crystalline phyllosilicates, amorphous silicates and - as far as permissible - also phosphates, such as e.g. Tripolyphosphate are used.
  • zeolites mainly being crystalline phyllosilicates, amorphous silicates and - as far as permissible - also phosphates, such as e.g. Tripolyphosphate are used.
  • the amount of co-builder is to be counted against the 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
  • zeolite is also suitable X and mixtures of A, X and / or P and Y.
  • zeolite is also suitable X and mixtures of A, X and / or P and Y.
  • zeolite is also suitable cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX ® (commercial product from Condea Augusta SpA) im Trade is 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 can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-C ⁇ -fatty alcohols with 2 to 5 ethylene oxide groups, Ci2 -Ci4 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.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2x + - ⁇ yH2 ⁇ , 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 is preferred Values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1.
  • Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si2 ⁇ 5-yH2 ⁇ are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
  • Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Suitable sheet silicates, which belong to the group of water-swellable smectites are, for example, those of the general formulas
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1.
  • preferential Layered silicates are used that are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na :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 have been caused in various ways, for example by surface treatment, compounding, compaction / 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 deliver 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 release delay compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1. Compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
  • 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, wine 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.
  • Suitable organic builder substances are 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 molar masses 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 AI is also suitable.
  • a product oxidized on C ⁇ 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 also particularly preferred, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0150930 A1 and 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 at most 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, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or 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 contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids are also to be mentioned as further preferred builder 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 which have a positive influence on the oil and fat washability from textiles.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic Cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art. ten, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • 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 0: SiO 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
  • the content of sodium silicate 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 contain other known additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, small amounts of neutral filler salts and colorants 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 H2O2-delivering 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 boron 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.
  • 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 patent 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, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411 A1, the manganese, copper and cobalt described in German patent application DE 4416438 A1.
  • 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.
  • stains such as stains containing protein, fat or starch
  • Oxidoreductases can also be used to bleach or inhibit color transfer.
  • 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 are, 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 lipolytically active enzymes and cellulase, in particular, however, mixtures containing protease and / or lipase or mixtures with lipolytically active 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, pululanases 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 For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use 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 (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts poly- merer carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, are preferred on the means.
  • 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 the same structure which instead of the morpho- linino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyrene 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 % by weight, preferably around 10 * 5 % by weight, 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 of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
  • the polymers are characterized by an average molecular weight of approximately 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.
  • Further preferred are those polymers which have linking polyethylene glycol units with a molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000.
  • Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropionate, stally.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, ⁇ -isomethylionone and methylcedrylke - clay, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpinol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are 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 it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further 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 molded articles 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, with dusty or at least finely divided ingredients (the so-called fine particles) are adhered to the particulate process end products produced according to the invention, which serve as the core, and thus agents are formed which have these so-called fine particles as an outer shell. In turn, this advantageously takes place by melting agglomeration.
  • 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, prior to pressing, have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10,% by weight.
  • a particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
  • the defoamer granules H1 according to the invention and the two defoamers Dehydran® 760 and Dow Corning Powdered Antifoam® were used in detergent formulations.
  • the preparations were pressed into tablets (weight 40 g), packed airtight and then stored at 40 ° C. for 2 weeks.
  • the composition of the detergent tablets is shown in Table 1.
  • Recipe 1 is according to the invention, recipes V1 and V2 are used for comparison.
  • the detergent tablets were then tested in washing tests. For this purpose, 3.5 kg of standard laundry were washed in a full wash at 90 ° C in a washing machine (Miele W 918). Two detergent tablets are unpacked immediately before the experiment and placed in a net for washing.
  • the results of the washing tests are also shown in Table 1.
  • the tablets were placed on a wire rack, which was in water (0 ° d, 25 ° C). The tablets were completely surrounded by water. The disintegration time from immersion to complete dissolution was measured. The composition of the tablets and the disintegration times are also summarized in Table 1.

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

Abstract

L'invention concerne des corps façonnés présentant une solubilité dans l'eau améliorée, contenant (a) des tensioactifs anioniques, non ioniques, cationiques et/ou amphotères, (b) des accélérateurs de dispersion et (c) des granulés d'antimousse qui contiennent (c1) au moins une cire molle présentant un point de fusion compris entre 35 et 50 DEG C, (c2) au moins une cire dure présentant un point de fusion supérieur à 50 DEG C, (c3) des silicones et (c4) des matériaux supports.
PCT/EP2000/010688 1999-11-09 2000-10-31 Corps façonnes presentant une solubilite dans l'eau amelioree WO2001034757A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00972881A EP1228186A1 (fr) 1999-11-09 2000-10-31 Corps fa onnes presentant une solubilite dans l'eau amelioree

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999153794 DE19953794A1 (de) 1999-11-09 1999-11-09 Formkörper mit verbesserter Wasserlöslichkeit
DE19953794.1 1999-11-09

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WO2001034757A1 true WO2001034757A1 (fr) 2001-05-17

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DE (1) DE19953794A1 (fr)
WO (1) WO2001034757A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0094250A1 (fr) * 1982-05-11 1983-11-16 Unilever Plc Procédé pour la préparation de granules contenant un agent antimousse à base de silicone
EP0206522A2 (fr) * 1985-05-23 1986-12-30 Unilever Plc Agent antimousse pour compositions détergentes
WO1995004124A1 (fr) * 1993-08-02 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Granule regulateur du moussage et son procede de preparation
WO1998055575A1 (fr) * 1997-06-03 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Granules adjuvants pour corps moules detergents et lavants
WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
WO1999067354A1 (fr) * 1998-06-24 1999-12-29 Cognis Deutschland Gmbh Procede pour preparer des granulats antimousse

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0094250A1 (fr) * 1982-05-11 1983-11-16 Unilever Plc Procédé pour la préparation de granules contenant un agent antimousse à base de silicone
EP0206522A2 (fr) * 1985-05-23 1986-12-30 Unilever Plc Agent antimousse pour compositions détergentes
WO1995004124A1 (fr) * 1993-08-02 1995-02-09 Henkel Kommanditgesellschaft Auf Aktien Granule regulateur du moussage et son procede de preparation
WO1998055575A1 (fr) * 1997-06-03 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Granules adjuvants pour corps moules detergents et lavants
WO1998055590A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions detergentes
WO1999067354A1 (fr) * 1998-06-24 1999-12-29 Cognis Deutschland Gmbh Procede pour preparer des granulats antimousse

Also Published As

Publication number Publication date
EP1228186A1 (fr) 2002-08-07
DE19953794A1 (de) 2001-05-17

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