EP1321509B1 - Hydroxy-ethers mixtes et polymers en forme de pro-produits solides pour produits de lavage, de rinçage et de nettoyage - Google Patents

Hydroxy-ethers mixtes et polymers en forme de pro-produits solides pour produits de lavage, de rinçage et de nettoyage Download PDF

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EP1321509B1
EP1321509B1 EP02027904A EP02027904A EP1321509B1 EP 1321509 B1 EP1321509 B1 EP 1321509B1 EP 02027904 A EP02027904 A EP 02027904A EP 02027904 A EP02027904 A EP 02027904A EP 1321509 B1 EP1321509 B1 EP 1321509B1
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polymers
alcohol
acid
carbon atoms
solid
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EP1321509A1 (fr
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Ditmar Kischkel
Manfred Dr. Weuthen
Michael Elsner
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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

Definitions

  • the invention relates to solid compositions containing hydroxy mixed ethers and optionally other surfactants, polymers and inorganic or organic carriers, a process for their preparation and the use of solid agents as a precompound for the production of detergents, dishwashing detergents and cleaning agents.
  • rinse aids are mixtures of, for example, nonionic surfactants, solubilizers, organic acids and solvents, water and optionally preservatives and fragrances.
  • the object of the surfactants in these compositions is to influence the interfacial tension of the water so that it is in as thin as possible continuous film Run off the dishes, so that during the subsequent drying process no drops of water, streaks or films remain (so-called network effect).
  • surfactants in rinse aids must also damp the foam in the dishwasher caused by food particles. Since the rinse aid usually contain acids for improving the Klartrocknungs bin, the surfactants used must additionally be comparatively hydrolysis insensitive to acids.
  • Rinse aids are used both in the household and in the commercial sector. In186, the rinse aid is usually added after the pre-rinsing and cleaning process at about 40 to 65 ° C.
  • the commercial dishwashers work with only one cleaning liquor, which is renewed only by adding the rinse solution from the previous rinse. So there is no complete water exchange during the entire wash program. Therefore, the rinse aid must also foam-suppressing, be stable even at a strong temperature gradient of about 85 to about 35 ° C and prove to be inert to alkali and active chlorine compounds.
  • detergent tablets which contain hydroxy mixed ethers, a polymer and other solids.
  • the WO 00/27903 A1 describes solid detergents which, in addition to hydroxy mixed ethers, may contain further surfactants, polymers and carriers.
  • Surfactant granules are known which may contain 40% by weight of hydroxy mixed ether, 50% by weight of cellulose as carrier and 5% by weight of polycarboxylates.
  • solid detergents and cleaners are disclosed which, in addition to hydroxy mixed ethers, may contain polymers and carriers.
  • the object of the present invention has consisted of surfactants in solid form (solid) for the preparation of solid detergents, dishwashing detergents and cleaners, in particular solid dishwashing detergents, for example the so-called “2 in 1” or “3 in 1” dishwashing detergent , to provide.
  • the solid agents should be characterized in that they have excellent Klar micheigenschaften, even in the presence of protein soilings foam-suppressing, are stable even at high temperature gradient, do not gel during dissolution and in particular have a solubility kinetics, the carryover of the highest possible content of nonionic surfactant into the rinse of the machine process also made possible to produce simpler solid detergent formulations. Furthermore, the surfaces to be cleaned or rinsed should be equipped in such a way that it is easier to remove soiling during the next cleaning process.
  • the object was achieved by the provision of solid agents which contain a combination of hydroxy mixed ethers and polymers in the mixing ratio according to the invention, be solved.
  • these solid agents for example as a precompound in washing, rinsing and cleaning agent formulations, the surfactant content, in particular the content of hydroxy mixed ether, can be reduced while the cleaning power remains consistently high. Nevertheless, this results in a very good wetting ability and a spotless gloss of the surfaces to be cleaned.
  • the addition of polymers to rinse aids means that at the next cleaning otherwise strongly adhering and often critical stains such as starchy stains, can be completely removed. These soiling can be removed without additional manual processing of the items to be washed.
  • the invention relates to solid precompounds for the production of detergents, dishwashing detergents and cleaning compositions, characterized in that hydroxy mixed ethers (a) and optionally further surfactants (a), cationic polymers (b) which have monomer units of the formula (Ia) , in which n3 is a number between 2 and 4, R 1a is hydrogen or a methyl group and R 2a , R 3a and R 4a may be identical or different and represent hydrogen or a C 1-4 -alk (en) yl group and X - represents an anion from the group of the halide anions or a monoalkyl anion of the sulfuric monoesters and optionally further, typical for washing, rinsing and cleaning agents auxiliaries and additives (c) and support (d) in the ratio (a + b + c): (d) 1: 1 to 1:40 are included.
  • the weight ratio is calculated based on the active substance content.
  • Hydroxy mixed ethers are known non-ionic surfactants having unsymmetrical ether structure and polyalkylene glycol moieties which are obtained, for example, by subjecting olefin epoxides to a ring opening reaction with fatty alcohol polyglycol ethers.
  • HME Hydroxy mixed ethers
  • Corresponding products and their use in the field of cleaning hard surfaces are for example the subject of the European patent specification EP 0693049 B1 as well as the international patent application WO 94/22800 (Olin ) and the writings mentioned therein.
  • R 1 is a linear or branched alkyl radical having 2 to 18, preferably 6 to 16 carbon atoms, in particular 8 to 12 carbon atoms
  • R 2 is hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
  • R 3 is a linear or branched Alkyl and / or alkenyl radical having 1 to 22, preferably 8 to 18 carbon atoms
  • n1 and n2 independently of one another, are 0 or numbers from 1 to 60, preferably 2 to 60 and in particular 20 to 40 and
  • m is 0 or numbers of 0.5 to 5, preferably 1 to 2, with the provisos that the sum of the carbon atoms in the radicals R 1 and R 2 is at least 6 and preferably 8 to 18 and the sum (n1 + m + n2) is different from 0.
  • the HME ring opening products may be both internal olefins (R 2 not hydrogen) or terminal olefins (R 2 hydrogen), the latter being preferred for ease of preparation and more advantageous performance properties.
  • the polar portion of the molecule may be a polyethylene (PE) or a polypropylene (PP) chain; Also suitable are mixed chains of PE and PP units, whether in statistical or block distribution.
  • Typical examples are ring opening products of 1,2-hexene epoxide, 2,3-hexene epoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 Decene epoxide, 4,5-decene epoxide, 1,2-dodecene epoxide, 2,3-dodecene epoxide, 3,4-dodecene epoxide, 4,5-dodecene epoxide, 5,6-dodecene epoxide, 1,2-tetradecenepoxide, 2,3-tetradecenepoxide , 3,4-tetradecenepoxide, 4,5-tetradecenepoxide, 5,6-tetradec
  • Caproic alcohol caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical mixtures thereof.
  • cationic polymers having monomer units of the formula (Ia) , wherein n3 is a number between 2 and 4, preferably 3, R 1a is hydrogen or a methyl group and R 2a , R 3a and R 4a may be the same or different and represent hydrogen or a C 1-4 alkoxy group , X - represents an anion from the group of halide anions or a monoalkyl the Schwefelklandester.
  • the polymers preferably contain the monomer units of the formula (Ia) in an amount of from 10 mol% to 80 mol%, particularly preferably from 20 mol% to 60 mol%.
  • the polymers thus have a significant soil release effect.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like, olefins, such as ethylene, propylene and butene, alkyl esters of unsaturated carboxylic acids, in particular esters of acrylic acid and methacrylic acid, their alcohol components of alkyl groups of 1 to 6 carbon atoms, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and their hydroxy derivatives such as 2-hydroxy-ethyl methacrylate, provided with unsaturated groups, optionally further substituted, aromatic compounds such as styrene, methylstyrene, vinylstyrene and heterocyclic compounds such as vinylpyrrolidone can be used.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like
  • olefins such as ethylene, propylene and butene
  • Acrylic acid, methacrylic acid and their C 1 -C 6 esters are preferably used as comonomers.
  • suitable cationic cellulose derivatives such as a quaternized hydroxyethylcellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF), condensation products of polyglycols and Amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers
  • polymers are also selected which are selected from the group consisting of polymers or copolymers of monomers such as trialkylammoniumalkyl (meth) acrylate or acrylamide, dialkyldiallyldiammonium salts, polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, Guar, cellulose and starch derivatives, polyadducts of ethylene oxide with ammonium groups, polyesters and polyamides with quaternary pendant groups.
  • monomers such as trialkylammoniumalkyl (meth) acrylate or acrylamide, dialkyldiallyldiammonium salts, polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, Guar, cellulose and starch derivatives, polyadducts of ethylene oxide with ammonium groups, polyesters and polyamides with quaternary pendant groups.
  • polyacrylic acid copolymers eg Versicol E11® or Glascol E11® (Allied Colloids), polyacrylamidopropanesulfonic acid eg Rheothik 80-11® (Cognis), trimethylammoniumpropylmethacrylamide-sodium acrylate-ethylacrylate polymer eg Polyquart Ampho 149® Cognis.
  • quaternized protein hydrolysates for example Gluadin WQ® (Cognis).
  • anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, unvarnished polyols crosslinked with polyols, acrylamidopropyltrimethylammonium chloride / Acrylate copolymers, octylacrylamide / methylmethacrylate / tert.butylaminoethylmethacrylate / 2-hydroxypropro pylmethacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinyl
  • suitable substances are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, it being possible for the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate to be in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units ranges from 750 to 5,000, that is, ethoxylicity degree of the polymers containing polyethylene glycol groups may be about 15 to 100.
  • the polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure.
  • Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).
  • compositions according to the invention comprise the components of hydroxy mixed ethers and polymers of the formula (Ia) in a weight ratio of 0.1: 1 to 1000: 1, preferably 1: 1 to 100: 1, particularly preferably 5: 1 to 50: 1.
  • the solid agents include inorganic or organic carriers selected from the group consisting of zeolites, alkali metal sulfates, alkali phosphates, alkali carbonates, alkali hydrogencarbonates, alkali silicates, alkali citrates, polysaccharides and their derivatives such as celluloses, carboxymethylcelluloses, cyclodextrins, starches , Starch degradation products and polyacrylates, as well as mixtures thereof.
  • inorganic or organic carriers selected from the group consisting of zeolites, alkali metal sulfates, alkali phosphates, alkali carbonates, alkali hydrogencarbonates, alkali silicates, alkali citrates, polysaccharides and their derivatives such as celluloses, carboxymethylcelluloses, cyclodextrins, starches , Starch degradation products and polyacrylates, as well as mixtures thereof.
  • the detergency builders zeolite A and / or P are particularly preferred.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite A and zeolite X are co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ® (commercial product from Condea Augusta SpA) is commercially available.
  • VEGOBOND AX ® commercial product from Condea Augusta SpA
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • zeolite In the event that the zeolite is used as a suspension, these may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution;
  • Coulter Counter and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • phosphates as carriers are possible in particular.
  • alkali silicates crystalline, layered alkali and especially sodium silicates of the general formula NaMSi x O 2x + 1 ⁇ yH 2 O to understand, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 is and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in the European patent application EP 0164514 A1 described.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in International Patent Application WO 91/08171 is described.
  • Further suitable phyllosilicates are, for example, from the patent applications DE 2334899 A1 .
  • EP 0026529 A1 and DE 3526405 A1 known. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas.
  • the phyllosilicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na + and Ca 2+ , due to their ion-exchanging properties.
  • the amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing.
  • Useful phyllosilicates are for example US 3,966,629 . U.S. 4,062,647 .
  • EP 0026529 A1 and EP 0028432 A1 known.
  • phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.
  • the preferred inorganic carrier substances also include amorphous sodium silicates having a modulus of Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and in particular of 1: 2 to 1: 2.6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay over conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction nebulization or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances, but at most one or more maxima of the scattered X-rays which are several angstroms in width of the diffraction angle. However, it may even lead to particularly good performance properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in the German patent application DE 4400024 A1 described.
  • Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • polysaccharides are cellulose, carboxymethylcellulose, cyclodextrin or starch and their degradation products, as polymeric supports (d) are in particular polyacrylates having molecular weights in the range of 1,000 to 50,000 in question.
  • the solid compositions may contain other auxiliary substances and additives typical of detergents, dishwashing detergents and cleaning agents, as well as other surfactants.
  • auxiliary substances and additives typical of detergents, dishwashing detergents and cleaning agents, as well as other surfactants.
  • these are, for example, low-foaming, preferably nonionic cosurfactants, anionic cosurfactants, co-builders, oil and grease solvents, bleaches, bleach activators, grayness inhibitors, enzymes, enzyme stabilizers, optical Brighteners, defoamers, disintegrants, fragrances, inorganic salts and the like, as they are explained in more detail below.
  • solid agents which, in addition to the hydroxy mixed ethers, comprise nonionic surfactants, especially adducts of ethylene oxide and / or propylene oxide with fatty or oxo alcohols, as further surfactant component.
  • nonionic cosurfactants 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, alk (en) yl oligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters , Sugar esters, sorbitan esters, polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters, alkyl oligoglucosides or mixed ethers.
  • the preferred fatty alcohol polyglycol ethers follow the formula (II) , R 4 O (CH 2 CHR 5 O) p1 H (II) in which R 4 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 5 is hydrogen or methyl and p 1 is a number from 1 to 20.
  • Typical examples are the addition products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol and Brassidylalkohol as well as their technical mixtures. Particularly preferred are addition products of 3, 5 or 7 moles of ethylene oxide to technical Kokosfettalkohole.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula ( III ), R 6 CO- (OCH 2 CHR 7) p2 OR 8 (III) in 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 linear or branched alkyl radicals having 1 to 4 carbon atoms and p 2 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 into the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
  • the products are prepared by insertion of the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite.
  • catalysts such as, for example, calcined hydrotalcite.
  • Particularly preferred are reaction products of on average 5 to 10 moles of ethylene oxide in the ester bond of technical Kokosfettklamethylestem.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (IV), R 9 O- [G] q (IV) in which R 9 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and q is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representatives of the extensive literature are here on the writings EP 0301298 A1 and WO 90103977 directed.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
  • Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • 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 technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
  • preferred nonionic surfactants are mixed ethers which follow, for example, the formula (V) R 10 O (CH 2 CH 2 O) rl (CH (CH 3) CH 2 O) s (CH 2 CH 2 O) r2 R 11 (V) in the R 10 is a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 11 is an alkyl radical having 1 to 8 carbon atoms or a benzyl radical, r1 and r2 are independently 0 or numbers of 1 to 20 and s stands for 0 or numbers from 0.5 to 5, with the proviso that the sum (r1 + r2 + s) must be different from 0.
  • Typical examples are, for example, coconut fatty alcohol + 10EO-butyl ether, coconut fatty alcohol + 5PO + 4EO-butyl ether or coconut fatty alcohol + 10EO-benzyl ether.
  • anionic cosurfactants are soaps, alkylbenzenesulfonates, secondary alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids.
  • anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.
  • the surfactant mixtures may particularly preferably comprise anionic surfactants selected from the group formed by alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, monoglyceride (ether) sulfates and alkanesulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkanesulfonates and linear alkylbenzenesulfonates.
  • Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary alcohols which follow the formula (VIII) , R 16 O-SO 3 X (VIII) in which R 16 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxo synthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • ether sulfates are known anionic surfactants which are industrially produced by SO 3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxoalcohol polyglycol ethers and subsequent neutralization.
  • ether sulfates come into consideration, which follow the formula (IX), R 17 O- (CH 2 CH 2 O) a SO 3 X (IX) in which R 17 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, a is a number from 1 to 10 and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products of an average of 1 to 10 and especially 2 to 5 moles of ethylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts.
  • the ether sulfates may have both a conventional and a narrow homolog distribution. Particularly preferred is the use of ether sulfates based on adducts of an average of 2 to 3 moles of ethylene oxide to technical C 12/14 - or C 12/18 - Kokosfettalkoholfr hopeen in the form of their sodium and / or magnesium salts.
  • Useful organic builders which are suitable as co-builders are, for example, the polycarboxylic acids which 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), if such use is for ecological reasons not to complain about, as well as 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 thereof. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • an acidifying component In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Further 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, for example acid or enzyme catalyzed processes. Preferably, they are hydrolysis products having average molecular weights in the range of 400 to 500,000.
  • a polysaccharide having a dextrose equivalent (DE) in the range of 0.5 to 40, especially 2 to 30 is preferred, where DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100.
  • DE dextrose equivalent
  • Useful are both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2,000 to 30,000.
  • a preferred dextrin is disclosed in the British patent application GB 9419091 A1 described.
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and methods of their preparation are for example from European patent applications EP 0232202 A1 . EP 0427349 A1 . EP 0472042 A1 and EP 0542496 A1 as well as the 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 known.
  • oxidized Oligosaccharide according to the German patent application DE 19600018 A1 , A product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Glycerol disuccinates and glycerol trisuccinates, as used, for example, in the U.S. Pat. Nos. 4,524,009 . US 4,639,325 In which European patent application EP 0150930 A1 and Japanese Patent Application JP 93/339896 to be discribed.
  • Suitable amounts are in zeolith Wegner and / or silicate-containing formulations at 3 to 15 wt .-%.
  • Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in the international patent application WO 95/20029 described.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrenesulfonic acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their molecular weight relative to free acids is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (in each case measured against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually added later to one or more basic granules.
  • biodegradable polymers of more than two different monomer units for example those according to DE 4300772 A1 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE 4221381 C2 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Other preferred copolymers are those described in the German patent applications DE 4303320 A1 and DE 4417734 A1 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids, their salts or their precursors Particular preference is given to polyaspartic acids or their salts and derivatives.
  • polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP 0280223 A1 described, can be obtained.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • compositions may also contain components that positively affect oil and grease washability from fabrics.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the content of the bleaching agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, it being advantageous to use perborate monohydrate or percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2, 5-dihydrofuran and from the German patent applications DE 1961
  • WO 94/28102 WO 94/28103 .
  • WO 95/00626 WO 95/14759 and WO 95/17498 are known.
  • the from the German patent application DE 19616769 A1 known hydrophilic substituted acyl acetals and in the German patent application DE 196 16 770 as well as the international patent application WO 95/14075 Acyllactame described are also preferably used.
  • Such bleach activators are contained in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.
  • EP 0446982 B1 and EP 0453 003 B1 be known sulphonic imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts.
  • candidate transition metal compounds include in particular from German patent application DE 19529905 A1 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 19620267 A1 known N-analogues derived from the German patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes which are described in the German patent application DE 19605688 A1 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which from the German patent application DE 19620411 A1 known cobalt, iron, copper and ruthenium-amine complexes, which in the German patent application DE 4416438 A1 manganese, copper and cobalt complexes described in the European patent application EP 0272030 A1 Cobalt complexes described in the European patent application EP 0693550 A1 known manganese complexe
  • EP 0544490 A1 and EP 0544519 A1 described manganese complexes.
  • combinations from bleach activators and transition metal bleach catalysts are, for example, from the German patent application DE 19613103 A1 and the international patent application WO 95/27775 known.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the enzymes may in turn be adsorbed to carriers and / or embedded in encapsulants to protect them against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the agents may contain other enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds such as boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), the metaboric acid (HBO 2 ) and the pyroboric acid (tetraboric H 2 B 4 O 7 ).
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric 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 suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
  • Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).
  • waxy compounds can be used as defoamers.
  • "Waxy” is understood as meaning those compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C.
  • the waxy defoamer substances are practically insoluble in water, i. at 20 ° C in 100 g of water they have a solubility below 0.1 wt .-%.
  • Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic esters of monohydric and polyhydric alcohols and paraffin waxes or mixtures thereof.
  • Suitable paraffin waxes generally represent a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as in “ The Analyst “87 (1962), 420 , described, and / or its solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. In this case, at room temperature completely liquid paraffins, that is those with a solidification point below 25 ° C, according to the invention not useful. Soft waxes having a melting point in the range of 35 to 50 ° C preferably include the group of petrolates and their hydrogenation products.
  • These petrolatum are mixtures of microcrystalline waxes and refractory n-paraffins.
  • EP 0309931 A1 known paraffin wax mixtures of, for example, 26 wt .-% to 49 wt .-% microcrystalline paraffin wax having a freezing point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C.
  • paraffins or paraffin mixtures are used which solidify in the range of 30 ° C to 90 ° C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin.
  • this liquid fraction is as low as possible and is preferably completely absent.
  • particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10 wt .-%, in particular from 2 wt .-% to 5 wt .-%, at 40 ° C, a liquid content of less than 30 wt .-%, preferably from 5 Wt .-% to 25 wt .-% and in particular from 5 wt .-% to 15 wt .-%, at 60 ° C, a liquid content of 30 wt .-% to 60 wt .-%, in particular of 40 wt .-%.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is, in the case of particularly preferred paraffin wax mixtures, still below 85 ° C., in particular at 75 ° C. to 82 ° C.
  • the paraffin waxes may be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those which are derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine
  • Suitable carboxylic esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol portion of the carboxylic acid ester contains a monohydric or polyhydric alcohol having 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut oil, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, wherein the acid portion of the ester is selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters.
  • Useful glycerol esters are the mono-, di- or triesters of glycerol and said carboxylic acids, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glyceryl distearate are examples of this.
  • suitable natural esters as defoamers are beeswax, which consists mainly of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
  • carnauba wax which is a mixture of carnaubaic acid alkyl esters, often in combination with low levels of free carnaubaic acid, other long chain acids, high molecular weight alcohols and hydrocarbons.
  • Suitable carboxylic acids as further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, which are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil.
  • Preferred are saturated fatty acids having 12 to 22, in particular 18 to 22 C-atoms. In the same way, the corresponding fatty alcohols of the same C chain length can be used.
  • dialkyl ethers may additionally be present as defoamers.
  • the ethers may be asymmetric or symmetric, i. contain two identical or different alkyl chains, preferably having 8 to 18 carbon atoms.
  • Typical examples are di-n-octyl ether, di-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers having a melting point above 25 ° C, in particular above 40 ° C.
  • Suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts, for example, from carboxylic acid magnesium salts, which are pyrolyzed at temperatures above 300 ° C with elimination of carbon dioxide and water, for example according to the German Offenlegungsschrift DE 2553900 OS.
  • Suitable fatty ketones are those prepared by pyrolysis of the magnesium salts of lauric, myristic, palmitic, palmitoleic, stearic, oleic, elaidic, petroselic, arachidic, gadoleic, behenic or erucic acid.
  • fatty acid polyethylene glycol esters which are preferably obtained by basic homogeneously catalyzed addition of ethylene oxide to fatty acids.
  • the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine, results in extremely selective ethoxylation of the fatty acids, especially when it comes to producing low ethoxylated compounds.
  • the paraffin waxes described are particularly preferably used alone as waxy defoamers or in mixtures with one of the other waxy defoamers, wherein the proportion of paraffin waxes in the mixture is preferably more than 50% by weight, based on waxy defoamer mixture.
  • the paraffin waxes can be applied to carriers as needed.
  • carrier material all known inorganic and / or organic carrier materials are suitable. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble phyllosilicates, alkali metal silicates, alkali metal sulphates, for example sodium sulphate, and alkali metal phosphates.
  • the alkali metal silicates are preferably a compound having a molar ratio of alkali metal oxide to SiO 2 of from 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good Komeigenschaften, in particular high abrasion stability and yet high dissolution rate in water.
  • the aluminosilicates referred to as support material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass.
  • silicates can be used, which are under the name Aerosil® or Sipernat® commercially.
  • Suitable organic support materials are, for example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Useful cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called cellulose mixed ethers, such as, for example, methylhydroxyethylcellulose and methylhydroxypropylcellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethylcellulose and methylcellulose, wherein the carboxymethylcellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose has a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali metal carboxymethylcellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Native starch composed of amylose and amylopectin is also suitable as the carrier. Native starch is starch, as it is available as an extract from natural sources, such as rice, potatoes, corn and wheat. Native starch is a commercial product and thus easily accessible.
  • one or more of the abovementioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulphates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • Particularly suitable are mixtures of alkali metal carbonates, in particular sodium carbonate, alkali metal silicates, in particular sodium silicate, alkali metal sulphates, in particular sodium sulphate and zeolites.
  • Suitable silicones are customary organopolysiloxanes which may have a finely divided silica content, which in turn may also be silanated. Such organopolysiloxanes are for example in the European patent application EP 0496510 A1 described. Particularly preferred are polydiorganosiloxanes and especially polydimethylsiloxanes known in the art. Suitable polydiorganosiloxanes have a nearly linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • silicones which may be both liquid and resinous at room temperature.
  • simethicones which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates.
  • the silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which may also be silanated.
  • siliceous dimethyl polysiloxanes are particularly suitable for the purposes of the present invention.
  • the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • the silicones are used in the form of their aqueous emulsions.
  • the silicone is added to the initially charged water with stirring.
  • thickening agents known in the art may be added to increase the viscosity of the aqueous silicone emulsions.
  • nonionic cellulose ethers such as methylcellulose, ethylcellulose and mixed ethers such as methylhydoxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose and anionic carboxycellulose types such as the carboxymethylcellulose sodium salt (abbreviation CMC).
  • Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
  • concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion use concentrations of approximately 0.5 to 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion.
  • the content of silicones of the type described in the aqueous emulsions is advantageously in the range of 5 to 50 wt .-%, in particular from 20 to 40 wt .-% - calculated as silicones and based on aqueous silicone emulsion.
  • the aqueous silicone solutions as thickener starch which is accessible from natural sources, such as rice, potatoes, corn and wheat.
  • the starch is advantageously present in amounts of from 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethylcellulose and a nonionic cellulose ether in the quantities already mentioned.
  • aqueous silicone emulsions it is expedient to proceed in such a way that the optionally present Pre-thicken the thickener in water before adding the silicones.
  • the incorporation of the silicones is expediently carried out with the aid of effective stirring and mixing devices.
  • the solid agents may further contain disintegrants or disintegrants. These are substances which are added to the shaped bodies in order to accelerate their decomposition upon contact with water. Overviews can be found eg in J. Pharm. 61 (1972 ) Römpp Chemilexikon, 9th Edition, Volume 6, p. 4440 as well as and Voigt "textbook of pharmaceutical technology” (6th edition, 1987, pp. 182-184 ). These substances increase their volume upon ingress of water, whereby on the one hand the intrinsic volume increases (swelling), on the other hand a pressure can be generated by the release of gases which causes the tablet to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as optionally crosslinked polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention. Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the said cellulose derivatives are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
  • cellulose-based disintegrating agent which is free of cellulose derivatives.
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, the crystalline regions (ca. 70%) but leave undamaged.
  • microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • the disintegrating agents can be homogeneously distributed macroscopically in the molded body, but microscopically they form zones of increased concentration due to their production.
  • Disintegrating agents which may be present within the meaning of the invention, such as Kollidon, alginic acid and their alkali metal salts, amorphous or partially crystalline layered silicates (bentonites), polyacrylates, polyethylene glycols are, for example, the publications WO 98/40462 (Rettenmaier ) WO 98/55583 and WO 98/55590 (Unilever ) and WO 98/40463 . DE 19709991 and DE 19710254 (Henkel ) refer to. The teaching of these documents is expressly incorporated by reference.
  • the moldings may contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 wt .-% - based on the moldings.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have proven useful, wherein the cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.
  • compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which do not have outstanding builder properties, or mixtures of these;
  • alkali metal carbonate and / or amorphous alkali silicate especially sodium silicate with a molar ratio of Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the final preparations is preferably up to 40 wt .-%, advantageously between 2 and 35 wt .-%.
  • the content of sodium silicate (without any special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • Sodium sulfate in amounts of from 0 to 10, in particular from 1 to 5,% by weight, based on the composition, can furthermore be contained as fillers or leveling agents
  • the solid compositions according to the invention may, due to their production, have a residual moisture content of not more than 25, preferably not more than 10, and in particular not more than 8 and very particularly preferably less than 5% by weight.
  • the water content of the zeolites is not included.
  • such agents are used which contain 6 to 75, preferably 10 to 40 wt .-% of nonionic surfactants and 25 to 94, preferably 50 to 80 wt .-% of inorganic or organic carriers, with the proviso that the amounts are with the polymers, optionally further surfactants, other auxiliaries and additives and optionally with water and to 100 wt .-% complete.
  • the hydroxymethylene ether solid compositions according to the invention in combination with polymers on supports fulfill the desired complex profile of requirements to full satisfaction.
  • these surfactants can be processed with inorganic or organic carriers with little effort to solids that do not gel, but have the desired delayed solubility kinetics.
  • the solid agents for example in the form of granules, it is possible in particular to formulate powders or else tablets with a simultaneous rinse effect.
  • cleaners or regeneration agents for the ion exchanger so-called "3 in 1" systems can be realized.
  • the solid means can also be used for the conventional cleaning of hard surfaces and for the production of detergents.
  • the invention includes the recognition that the use of the agents according to the invention is not only particularly good Provides clear drying effects, but also provides the best results in terms of foam attenuation, especially in the presence of proteins and temperature stability.
  • the invention further relates to a process for the preparation of the solid compositions according to the invention as a precompound in detergents, dishwashing detergents and dishwashing detergents, preferably dishwashing detergents, characterized in that hydroxy mixed ethers of the formula (I) and polymers, optionally further surfactants and optionally further auxiliary agents are used. and applying additives to inorganic or organic carriers.
  • the preparation can be carried out in such a way that there is an intimate mixing of hydroxy mixed ethers, polymers, optionally other surfactants and auxiliaries and additives with carriers. It is further preferred that only the surface of the support is coated with hydroxy mixed ethers, polymers, optionally further surfactants and auxiliaries and additives.
  • the agents are preferably prepared by mixing and agglomerating the hydroxy mixed ethers and polymers, and optionally further surfactants and the carriers, as well as optionally the further additives.
  • the solid agents can be prepared in a preferred embodiment by mixing the components in the ploughshare, Lödige or Eirichmischer.
  • aqueous preparations of the carrier for example of the alkali metal silicate or of the alkali metal carbonate, are sprayed together with other remaining components in a drying device, wherein granulation can take place simultaneously with the drying.
  • the drying device in which the aqueous preparation is sprayed, may be any dry equipment.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed in a known manner a drying gas stream in finely divided form.
  • Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed therein is hereby expressly also made the subject of the present invention disclosure.
  • a particularly preferred way to prepare the means is to subject the precursors to fluidized bed granulation ("SKET" granulation).
  • SKET fluidized bed granulation
  • the precursors can be used both in the dried state and as an aqueous preparation.
  • Preferably used fluidized bed apparatus have bottom plates with dimensions of 0.4 to 5 m.
  • the granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s.
  • the discharge of the granules from the fluidized bed is preferably carried out via a size classification of the granules.
  • the classification can be carried out, for example, by means of a sieve device or by a countercurrent air stream (classifier air), which is regulated in such a way that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the incoming air is composed of the heated or unheated classifier air and the heated bottom air.
  • the soil air temperature is between 80 and 400, preferably 90 and 350 and in particular less than 70 ° C.
  • a starting material for example a granulate from a previous experimental batch, is initially introduced at the beginning of the granulation.
  • the mixtures are subsequently subjected to a compaction step, with further ingredients being added to the compositions only after the compaction step.
  • the compaction of the ingredients takes place in a preferred embodiment of the invention in a press-agglomeration process.
  • the press agglomeration process to which the solid premix (dried base detergent) is subjected, can be realized in various apparatuses. Depending on the type of agglomerator used, different press agglomeration processes are distinguished.
  • the four most common and in the present invention preferred press agglomeration processes are the extrusion, the roll pressing or compaction, the hole pressing (pelletizing) and tableting, so that in the present invention preferred press agglomeration processes extrusion, Walzenkompakt réelles-, pelletizing or Tabletting operations are.
  • the premix is compressed under pressure and plasticized and the individual particles are pressed together while reducing the porosity and adhere to each other.
  • the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shearing forces.
  • one or more binders can be used as an aid for compaction.
  • a binder is used which is completely present as a melt at temperatures up to a maximum of 130 ° C., preferably up to a maximum of 100 ° C. and in particular up to 90 ° C.
  • the binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature must - if a particular binder is desired - be adapted to the binder.
  • the actual compression process is preferably carried out at processing temperatures which correspond at least in the compression step at least the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt.
  • the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder.
  • Such a temperature control has the further advantage that even thermally sensitive raw materials, for example peroxy bleaches such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substance.
  • the possibility of precise temperature control of the binder in particular in the decisive step of the compression, ie between the mixing / homogenization of the premix and the shaping, allows an energetically very favorable and extremely gentle for the temperature-sensitive components of the premix process, since the premix for a short time the is exposed to higher temperatures.
  • the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roll compactor and the press roll (s) of the pellet press) have a maximum temperature of 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C and the process temperature is 30 ° C and in particular at most 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the effect of temperature in the compression region of the pressing agglomerators is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. Particularly preferred are combinations of polyethylene glycols with nonionic surfactants, especially of the fatty alcohol polyglycol ether type.
  • the modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also produce C 3 -C 5 glycols and also glycerol and mixtures from these can be used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
  • the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.
  • Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols having a molecular weight of about 4,000 can be used and Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols having a molecular weight between 3,500 and 5,000.
  • polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech.
  • these liquid per se polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must meet the requirements of the invention again, ie must have a melting point or softening point of at least above 45 ° C.
  • suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of not more than 30,000. Preference is given here to molecular weight ranges between 3,000 and 30,000, for example around 10,000.
  • Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others. especially in combination with polyethylene glycols used.
  • the compacted material preferably has temperatures not exceeding 90 ° C. directly after leaving the production apparatus, temperatures between 35 and 85 ° C. being particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the agent according to the invention is produced by means of an extrusion, as used, for example, in US Pat European Patent EP 0486592 B1 or the international patent applications WO 93/02176 and WO 94/09111 respectively.
  • WO 98/12299 to be discribed In this case, a solid premix is extruded under pressure strand and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work.
  • Preferred plasticizing and / or Lubricants are surfactants and / or polymers.
  • the pre-mixture is preferably supplied to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature.
  • the premix under pressure which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally
  • the extrudate is reduced by means of a rotating doctor blade to approximately spherical to cylindrical granules.
  • the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules succeeds a substantially uniformly predictable particle size, wherein in detail the absolute particle sizes can be adapted to the intended use. In general, particle diameters of at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm.
  • the length / diameter ratio of the chopped primary granules is preferably in the range from about 1: 1 to about 3: 1. It is furthermore preferred to supply the still plastic primary granulate to a further shaping processing step; At the same time, edges present on the raw extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • small amounts of dry powder for example, zeolite powder, such as zeolite NaA powder, may be included in this stage. This shaping can be done in commercially available Rondierettin.
  • extrusions can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bexx Bextruder.
  • the temperature control in the transition region of the screw, the predistributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded.
  • the duration of the influence of temperature is in. Compression range of extrusion preferably below 2 minutes and more preferably in a range between 30 seconds and 1 minute.
  • the solid preparations according to the invention can also be prepared by means of roll compaction.
  • the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a sheet-like Kompaktat, the so-called scoop.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rolls smooth, unstructured flake tapes are obtained, while by using structured rolls, correspondingly structured flakes can be produced in which, for example, certain shapes of the later detergent particles can be specified.
  • the sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to granules, which can be refined by further known per se surface treatment method, in particular brought into approximately spherical shape.
  • the temperature of the pressing tools, ie the rolls is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.
  • Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the action of temperature in the compression region of the smooth rolls or rolls provided with depressions of defined shape amounts to a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the agent according to the invention can also be prepared by means of pelleting.
  • the premix is applied to a perforated surface and pressed by means of a pressure-emitting body under plasticization through the holes.
  • the premix is compacted under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted with a knock-off device to granules.
  • pressure roller and perforated die conceivable.
  • flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers.
  • the press rollers may also be conically shaped in the plate devices, in the annular devices can matrices and press roll (s) have co-rotating or opposite sense of rotation.
  • An apparatus suitable for carrying out the method is described, for example, in German Offenlegungsschrift DE 3816842 A1 described.
  • the ring matrix press disclosed in this document consists of a rotating ring die interspersed by press channels and at least one press roller operatively connected to its inner surface, which presses the material supplied to the die space through the press channels into a material discharge.
  • ring matrix and press roller are driven in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized.
  • the temperature of the pressing tools ie the pressure rollers or press rollers, is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.
  • Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the preparation of the solid preparations according to the invention as shaped articles, preferably those in tablet form, is generally carried out by tabletting or press agglomeration.
  • the resulting particulate press agglomerates can be used either directly as detergents, dishwashing detergents or cleaning agents or aftertreated and / or prepared by conventional methods beforehand.
  • the usual post-treatments include, for example, powdering with finely divided ingredients of detergents or cleaners, whereby the bulk density is generally further increased.
  • a preferred aftertreatment is also the procedure according to the German patent applications DE 19524287 A1 and DE 19547457 A1 in which dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate finished products according to the invention, which serve as Kem, and thus arise means which have these so-called fines as an outer shell.
  • this is again done by melt agglomeration.
  • melt agglomeration of the fines on is expressly to the disclosure in the German patent applications DE 19524287 A1 and DE 19547457 A1 directed.
  • the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
  • the base of these tablets may, for example, be circular or rectangular.
  • Multi-layer tablets especially tablets with 2 or 3 layers, which may also be different in color, are especially preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. The tablets can also do this Contain pressed and unpressed portions. Moldings having a particularly advantageous dissolution rate are obtained when the granular constituents before pressing have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
  • aqueous Na-silicate solution, aqueous polymer solution or wax melts and their mixture are sprayed onto the granules produced, and the water is then dried off, thus providing the granules with an outer shell (coating).
  • silicate, wax and polymer solution are to be understood and calculated as carrier material.
  • Another object of the invention relates to the use of the solid compositions as a precompound for the preparation of detergents, dishwashing detergents and cleaning compositions, preferably of automatic dishwasher detergents, characterized in that the solid compositions in amounts of 2 to 80, preferably 7 to 60 and in particular 20 to 50 wt .-% - based on the final preparations - are included.
  • Comparative example 270 g of HME (Dehypon KE 3557®, Cognis) were added to 730 g of STPP in a Lödigemischer at 2000 rev / min and RT within a min. With a temp of 50 ° C and mixed for one min. It was obtained a free-flowing granules.
  • HME hydroxy mixed ether
  • APG alkyl polyglucoside
  • FAS fatty alcohol sulfate
  • STTP sodium tripolyphosphate
  • RT room temperature
  • Formulation I and II contains the solid compositions according to the invention in the form of a pre-compound and further formulation components.
  • V1 describes a comparison formulation containing the same proportions of hydroxy mixed ether and polymer. However, these were not pre-formulated as fixed funds.
  • Example I and Comparative Example C1 The content of hydroxy mixed ethers (HME) and polymer in Example I and Comparative Example C1 was in each case 11.9 g of HME and 0.66 g of polymer, but in Example II only 8.1 g of HME and 0.45 g of polymer. It can be seen that using the solid compositions according to the invention, even with a lower content of nonionic surfactant and polymer, the same clear-drying effect is achieved, whereas in the case of equal weight. Content of HME and polymer prove to be superior to formulation 1 with the solid agents (44%) according to the invention.

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Claims (17)

  1. Composé de base solide pour la fabrication de produits de lavage, de rinçage et de nettoyage,
    caractérisé en ce qu'
    il contient des hydroxyéthers mixtes (a) et, le cas échéant, d'autres tensioactifs (a), des polymères cationiques (b) qui renferment des unités monomères de formule (la)
    Figure imgb0008
     dans laquelle n3 est un nombre compris entre 2 et 4, R1a représente un atome d'hydrogène ou un groupe méthyle, R2a, R3a et R4a peuvent être identiques ou différents et représentent un atome d'hydrogène ou un groupe alkyle (alcényle) en C1-4, et X représente un anion du groupe des anions halogénures ou un anion de monoalkyle des semi-esters de l'acide sulfurique,
    ainsi que, le cas échéant, d'autres excipients et additifs (c) typiques des agents de lavage, de rinçage et de nettoyage, et des supports (d), dans un rapport (a+b+c):(d) de 1:1 à 1:40.
  2. Composé de base solide selon la revendication 1,
    caractérisé en ce que
    les hydroxyéthers mixtes répondent à la formule (I)
    Figure imgb0009
     dans laquelle R1 représente un radical alkyle linéaire ou ramifié comportant de 2 à 18 atomes de carbone, R2 un atome d'hydrogène ou un radical alkyle linéaire ou ramifié comportant de 2 à 18 atomes de carbone, R3 un radical alkyle et/ou alcényle linéaire ou ramifié comportant de 1 à 22 atomes de carbone, n1 et n2 indépendamment l'un de l'autre sont égaux à 0 ou représentent des nombres de 1 à 60, et m est égal à 0 ou représente des nombres de 0,5 à 5, étant précisé que la somme des atomes de carbone dans les radicaux R1 et R2 est au moins égale à 6 et que la somme (n1+m+n2) est différente de O.
  3. Composé de base solide selon la revendication 2,
    caractérisé en ce que
    les hydroxyéthers mixtes répondent à la formule (I) dans laquelle R1 représente un radical alkyle linéaire comportant de 8 à 10 atomes de carbone, R2 un atome d'hydrogène, R3 un radical alkyle linéaire comportant de 8 à 10 atomes de carbone, n1 est égal à 0, m représente des nombres de 0,5 à 2, et n2 des nombres de 20 à 40.
  4. Composé de base solide selon la revendication 2,
    caractérisé en ce que
    les hydroxyéthers mixtes répondent à la formule (I) dans laquelle R1 représente un radical alkyle linéaire comportant de 8 à 10 atomes de carbone, R2 un atome d'hydrogène, R3 un radical alkyle ramifié comportant de 8 à 10 atomes de carbone, n1 et m sont égaux à 0, et n2 représente des nombres de 20 à 40.
  5. Composé de base solide selon la revendication 2,
    caractérisé en ce que
    les hydroxyéthers mixtes répondent à la formule (I) dans laquelle R1 représente un radical alkyle linéaire comportant de 8 à 10 atomes de carbone, R2 un atome d'hydrogène, R3 un radical alkyle linéaire comportant de 8 à 10 atomes de carbone, n1 et m sont égaux à 0, et n2 représente des nombres de 40 à 60.
  6. Composé de base solide selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il contient des polymères (b) choisis dans le groupe constitué de polymérisats de copolymères, monomères comme les alkyl (méth)acrylate de trialkylammonium, ou l'acrylamide, les sels de dialkyldiallylammonium, les produits, de réaction d'éthers ou d'esters de polysaccharides avec des groupes latéraux ammonium, analogues à des polymères, les dérivés de guar, de cellulose et d'amidon, les produits de polyaddition d'oxyde d'éthylène avec des groupes ammonium, les polyesters et les polyamides comportant des groupes latéraux quaternaires.
  7. Composé de base solide selon l'une des revendications 1 à 6,
    caractérisé en ce que
    les hydroxyéthers mixtes et les polymères sont présents dans un rapport de 0,1:1 à 1000:1, de préférence de 1:1 à 100:1, en particulier de 5:1 à 50:1.
  8. Composé de base solide selon l'une des revendications 1 à 7,
    caractérisé en ce qu'
    il contient des supports inorganiques ou organiques choisis dans le groupe formé de zéolithes, de sulfates alcalins, de phosphates alcalins, de carbonates alcalins, d'hydrogénocarbonates alcalins, de silicates alcalins, de citrates alcalins, de polysaccharides et de leurs dérivés comme les celluloses, les carboxyméthylcelluloses, les cyclodextrines, les amidons, les produits de la décomposition de l'amidon et les polyacrylates, ainsi que des mélanges de ces substances.
  9. Composé de base solide selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il présente une humidité résiduelle d'au maximum 25 % en poids, de préférence d'au maximum 10 % en poids.
  10. Composé de base solide selon l'une des revendications 1 à 9,
    caractérisé en ce qu'
    il contient de 6 à 75 % en poids, de préférence de 10 à 40 % en poids de tensioactifs non ioniques et de 25 à 94 % en poids, de préférence de 50 à 80 % en poids de supports inorganiques ou organiques, étant précisé que les quantités indiquées se complètent le cas échéant avec de l'eau, le cas échéant avec d'autres tensioactifs, excipients et additifs pour donner 100 % en poids.
  11. Procédé de préparation de composés de bases solides selon la revendication 1,
    caractérisé en ce qu'
    on applique des hydroxyéthers mixtes de formule (I) et des polymères, le cas échéant d'autres tensioactifs ainsi que, le cas échéant, d'autres excipients et additifs, sur des supports inorganiques ou organiques.
  12. Procédé selon la revendication 11,
    caractérisé en ce qu'
    on prépare un mélange intime d'hydroxyéthers mixtes, de polymères, le cas échéant d'autres tensioactifs, d'excipients et d'additifs avec des supports.
  13. Procédé selon la revendication 12,
    caractérisé en ce qu'
    on recouvre la surface des supports avec des hydroxyéthers mixtes, des polymères et, le cas échéant, d'autres tensioactifs, excipients et additifs.
  14. Procédé selon l'une des revendications 11 à 13,
    caractérisé en ce qu'
    on prépare des produits solides en mélangeant les composants dans un mélangeur à socs, Lôdige ou Eirich.
  15. Procédé selon l'une des revendications 11 à 14,
    caractérisé en ce qu'
    on prépare les produits solides par séchage par pulvérisation, granulation sur lit fluidisé, agglomération par pressage, extrusion, compactage sur rouleaux, pelletisation ou pastillage.
  16. Utilisation des composés de base solides selon les revendications 1 à 10, pour fabriquer des produits de lavage, de rinçage et de nettoyage,
    caractérisé en ce qu'
    ils contiennent les produits solides en quantité de 2 à 80, de préférence de 7 à 60 et, en particulier, de 20 à 50 % en poids par rapport aux préparations finales.
  17. Utilisation selon la revendication 16,
    caractérisée en ce qu'
    on prépare des produits de lavage pour lave vaisselle.
EP02027904A 2001-12-22 2002-12-13 Hydroxy-ethers mixtes et polymers en forme de pro-produits solides pour produits de lavage, de rinçage et de nettoyage Expired - Lifetime EP1321509B1 (fr)

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DE10163856A DE10163856A1 (de) 2001-12-22 2001-12-22 Hydroxymischether und Polymere in Form von festen Mitteln als Vorcompound für Wasch-, Spül- und Reinigungsmittel
DE10163856 2001-12-22

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EP1321509B1 true EP1321509B1 (fr) 2007-07-18

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US (1) US6897193B2 (fr)
EP (1) EP1321509B1 (fr)
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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19962886A1 (de) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE10153768A1 (de) * 2001-11-02 2003-05-15 Cognis Deutschland Gmbh Hydroxymischether mit Polymeren
DE10163856A1 (de) * 2001-12-22 2003-07-10 Cognis Deutschland Gmbh Hydroxymischether und Polymere in Form von festen Mitteln als Vorcompound für Wasch-, Spül- und Reinigungsmittel
KR20050006246A (ko) * 2002-05-14 2005-01-15 이 아이 듀폰 디 네모아 앤드 캄파니 수용성 폴리아미드로 제조된 포장재 및 용기 및 이들의제조 방법
JP3910530B2 (ja) * 2002-12-16 2007-04-25 花王株式会社 汚れ放出剤
GB2404662A (en) * 2003-08-01 2005-02-09 Reckitt Benckiser Cleaning composition
DE102004039921A1 (de) * 2004-08-18 2006-03-02 Henkel Kgaa Klarspülhaltige Wasch- und Reinigungsmittel mit schwefelhaltigen Aminosäuren
US7534381B2 (en) * 2005-09-14 2009-05-19 Isp Investments Inc. Process and apparatus for forming agglomerates of a powder composition of an active and binder
DE102005060431A1 (de) * 2005-12-15 2007-06-21 Henkel Kgaa Maschinelles Geschirrspülmittel
JP5071631B2 (ja) 2006-06-26 2012-11-14 ライオン株式会社 固形洗浄剤組成物
DE102007042859A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsverfahren
ES2702780T3 (es) * 2009-05-12 2019-03-05 Ecolab Usa Inc Auxiliar de enjuague de secado rápido y de drenaje rápido
GB201104244D0 (en) * 2011-03-14 2011-04-27 Reckitt Benckiser Nv Detergent composition with improved drying performance
US9011610B2 (en) 2012-06-22 2015-04-21 Ecolab Usa Inc. Solid fast draining/drying rinse aid for high total dissolved solid water conditions
US9567551B2 (en) 2012-06-22 2017-02-14 Ecolab Usa Inc. Solid rinse aid composition and method of making same
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9982220B2 (en) 2015-05-19 2018-05-29 Ecolab Usa Inc. Efficient surfactant system on plastic and all types of ware
AU2017272086B2 (en) 2016-05-23 2019-06-27 Ecolab Usa Inc. Reduced misting alkaline and neutral cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers
EP3464542B1 (fr) 2016-05-23 2020-04-29 Ecolab USA Inc. Compositions acides de nettoyage, d'aseptisation et de désinfection à faible embuage par l'utilisation de polymères en émulsion d'eau dans l'huile à masse moléculaire élevée
JP2020510729A (ja) 2017-03-01 2020-04-09 エコラボ ユーエスエー インコーポレイティド 高分子量ポリマーによって低減した吸入ハザードの消毒剤および殺菌剤
US11155769B2 (en) 2018-07-25 2021-10-26 Ecolab Usa Inc. Rinse aid formulation for cleaning automotive parts
BR112022000446A2 (pt) 2019-07-12 2022-03-03 Ecolab Usa Inc Composição de limpeza passível de aspersão, sistema para aplicar composição de limpeza passível de aspersão com produção de névoa reduzida, e, método para limpar uma superfície dura com o uso de uma composição de limpeza aspergida com produção de névoa reduzida

Family Cites Families (92)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
GB1455873A (en) * 1973-08-24 1976-11-17 Procter & Gamble Textile-softening detergent compositions
US4172887A (en) * 1973-11-30 1979-10-30 L'oreal Hair conditioning compositions containing crosslinked polyaminopolyamides
LU68901A1 (fr) 1973-11-30 1975-08-20
DE2432757C2 (de) * 1974-07-08 1984-02-16 Henkel KGaA, 4000 Düsseldorf Als Schauminhibitoren geeignete, Hydroxylgruppen enthaltende Polyäthylenglykol-diäther sowie deren Herstellung
DE2553900A1 (de) 1975-12-01 1977-06-08 Konrad Ruckstuhl Verfahren und vorrichtungen zur aufbereitung von gepressten zuckerrohrbagasse-ballen
EP0026529B2 (fr) 1979-09-29 1992-08-19 THE PROCTER & GAMBLE COMPANY Compositions détergentes
ATE5896T1 (de) 1979-11-03 1984-02-15 The Procter & Gamble Company Granulare waschmittelzusammensetzungen.
NL8004703A (nl) * 1980-08-20 1982-03-16 Nl Bank Nv Drukwerk met elementen die namaak zichtbaar kunnen maken, en werkwijze voor het vervaardigen van dergelijk drukwerk.
WO1985000944A1 (fr) * 1983-08-16 1985-02-28 The Variable Speech Control Company ("Vsc") Empilage de canaux audio avec compression de signaux vocaux pour la transmission en bandes etroites et possibilite d'appels composes
GB8324276D0 (en) * 1983-09-10 1983-10-12 Univ Strathclyde Biocompatible glasses
SE438113B (sv) * 1983-09-12 1985-04-01 Rovac Ab Distansmaterial och forfarande att framstella detsamma
US4524009A (en) * 1984-01-31 1985-06-18 A. E. Staley Manufacturing Company Detergent builder
CA1238917A (fr) 1984-01-31 1988-07-05 Vivian B. Valenty Adjuvant pour detergent
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
US4639325A (en) * 1984-10-24 1987-01-27 A. E. Staley Manufacturing Company Detergent builder
DE3526405A1 (de) * 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
FR2597473B1 (fr) 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
DE3706036A1 (de) 1987-02-25 1988-09-08 Basf Ag Polyacetale, verfahren zu deren herstellung aus dialdehyden und polyolcarbonsaeuren und verwendung der polyacetale
DE3723826A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verfahren zur herstellung von alkylglykosiden
DE3732947A1 (de) * 1987-09-30 1989-04-13 Henkel Kgaa Zur verwendung in wasch- und reinigungsmitteln geeignetes schaumregulierungsmittel
DE3816842A1 (de) 1988-05-18 1989-11-23 Schlueter Gmbh U Co Kg H Ringmatrizenpresse
DE3833780A1 (de) 1988-10-05 1990-04-12 Henkel Kgaa Verfahren zur direkten herstellung von alkylglykosiden
US5576425A (en) * 1988-10-05 1996-11-19 Henkel Kommanditgesellschaft Auf Aktien Process for the direct production of alkyl glycosides
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
KR927003783A (ko) 1989-08-09 1992-12-18 게오르그 차이트 세제용 압축과립의 제조방법
ATE124960T1 (de) 1989-11-10 1995-07-15 Tno Verfahren zur herstellung von polydicarboxysacchariden.
YU221490A (sh) * 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
EP0458397B1 (fr) 1990-05-21 1997-03-26 Unilever N.V. Activation du blanchiment
IT1249883B (it) 1990-08-13 1995-03-30 Ferruzzi Ricerca & Tec Agenti sequestranti del calcio a base di carboidrati ossidati e loro impiego come builder per detergenti
DE4030688A1 (de) * 1990-09-28 1992-04-02 Henkel Kgaa Verfahren zur spruehtrocknung von wertstoffen und wertstoffgemischen unter verwendung von ueberhitztem wasserdampf
GB9101606D0 (en) 1991-01-24 1991-03-06 Dow Corning Sa Detergent foam control agents
EP0525239B1 (fr) 1991-07-31 1997-07-09 AUSIMONT S.p.A. Procédé pour augmenter l'efficacité de blanchiment d'un persel inorganique
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
EP0542496B1 (fr) 1991-11-14 1998-05-20 The Procter & Gamble Company Amidon oxydé à C6/C2-C3 utilisé comme ingrédient pour détergent
CA2083661A1 (fr) 1991-11-26 1993-05-27 Rudolf J. Martens Compositions pour detersif
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) * 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
US5637560A (en) * 1992-02-12 1997-06-10 Henkel Kommanditgesellschaft Auf Aktien Process for the production of surface-active anionic surfactant salts using superheated steam
DE4206521A1 (de) 1992-03-02 1993-09-09 Cognis Bio Umwelt Verfahren zur herstellung von granulaten, die als netz-, wasch- und/oder reinigungsmittel geeignet sind
DE4204090A1 (de) 1992-02-12 1993-08-19 Cognis Bio Umwelt Vereinfachtes trocknungsverfahren fuer wertstoffe und wertstoffgemische aus dem bereich der wasch- und reinigungsmittel mit ueberhitztem wasserdampf
DE4206495A1 (de) 1992-03-02 1993-09-09 Cognis Bio Umwelt Verfahren zum herstellen von granulaten, die als netz-, wasch und/oder reinigungsmittel geeignet sind
EP0626005B1 (fr) * 1992-02-12 1997-12-10 Henkel Kommanditgesellschaft auf Aktien Concentres pulverulents ou granules, sans poussiere, de tensioactifs anioniques a solubilite amelioree
DE4206050A1 (de) 1992-02-27 1993-09-02 Cognis Bio Umwelt Neuartige staubarme aniontensidkonzentrate in pulver- beziehungsweise granulatform mit verbessertem aufloesevermoegen in waessrigen medien
DE4234376A1 (de) 1992-10-12 1994-04-14 Henkel Kgaa Wertstoffe und Wertstoffgemische für Netz-, Wasch- und/oder Reinigungsmittel in neuer Zubereitungsform
DE4204035A1 (de) 1992-02-12 1993-08-19 Cognis Bio Umwelt Verbessertes verfahren zur trocknung von wertstoffen fuer wasch- und reinigungsmittel mit ueberhitztem wasserdampf
DE4208773A1 (de) 1992-03-19 1993-09-23 Cognis Bio Umwelt Verfahren zur trocknung von wertstoffen oder deren gemischen, die als netz-, wasch- und/oder reinigungsmittel geeignet sind
DE4209432A1 (de) 1992-03-24 1993-09-30 Henkel Kgaa Verfahren zur verbesserten Brüdenentsorgung bei der Heißdampftrocknung
JPH05339896A (ja) 1992-06-03 1993-12-21 Arakawa Chem Ind Co Ltd 紙用サイズ剤および紙サイジング方法
DE4300772C2 (de) * 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) * 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
US5576281A (en) 1993-04-05 1996-11-19 Olin Corporation Biogradable low foaming surfactants as a rinse aid for autodish applications
DE4317519A1 (de) * 1993-05-26 1994-12-01 Henkel Kgaa Herstellung von Polycarboxylaten auf Polysaccharid-Basis
DE4400024A1 (de) 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE4402851A1 (de) * 1994-01-31 1995-08-03 Henkel Kgaa Wirbelschicht-Oxidationsverfahren zur Herstellung von Polycarboxylaten auf Polysaccharid-Basis
DE4415804A1 (de) * 1994-05-05 1995-11-09 Henkel Kgaa Klarspülmittel mit biologisch abbaubaren Polymeren
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
DE4417734A1 (de) 1994-05-20 1995-11-23 Degussa Polycarboxylate
ATE269392T1 (de) 1994-07-21 2004-07-15 Ciba Sc Holding Ag Bleichmittelzusammensetzung für gewebe
GB9419091D0 (en) 1994-09-22 1994-11-09 Cerestar Holding Bv Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
DE19547457A1 (de) 1995-12-19 1997-06-26 Henkel Kgaa Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte
DE19524287A1 (de) 1995-07-06 1997-01-09 Henkel Kgaa Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte
DE19529905A1 (de) 1995-08-15 1997-02-20 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19536082A1 (de) 1995-09-28 1997-04-03 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19600018A1 (de) * 1996-01-03 1997-07-10 Henkel Kgaa Waschmittel mit bestimmten oxidierten Oligosacchariden
DE19605688A1 (de) 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19613103A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
US5967157A (en) * 1996-09-11 1999-10-19 The Procter & Gamble Company Automatic dishwashing compositions containing low foaming nonionic surfactants in conjunction with enzymes
DE19758811B4 (de) 1997-03-11 2008-12-18 Henkel Ag & Co. Kgaa Waschmittelpressling
DE19710254A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
DE19738866A1 (de) 1997-09-05 1999-03-11 Henkel Kgaa Schaumarme Tensidmischungen mit Hydroxymischethern
DE19751859A1 (de) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
WO2000027903A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
AU2456699A (en) * 1999-01-14 2000-08-01 Procter & Gamble Company, The Detergent compositions comprising a pectate lyase and a low foaming nonionic surfactant
DE19962885A1 (de) * 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
DE10019344A1 (de) * 2000-04-18 2001-11-08 Cognis Deutschland Gmbh Wasch- und Reinigungsmittel
DE10153768A1 (de) * 2001-11-02 2003-05-15 Cognis Deutschland Gmbh Hydroxymischether mit Polymeren
DE10163856A1 (de) * 2001-12-22 2003-07-10 Cognis Deutschland Gmbh Hydroxymischether und Polymere in Form von festen Mitteln als Vorcompound für Wasch-, Spül- und Reinigungsmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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DE10163856A1 (de) 2003-07-10
ATE367428T1 (de) 2007-08-15
DE50210492D1 (de) 2007-08-30
US20030171243A1 (en) 2003-09-11
EP1321509A1 (fr) 2003-06-25
US6897193B2 (en) 2005-05-24

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