Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—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 agents containing hydroxy mixed ethers and, if appropriate, others Surfactants, polymers and inorganic or organic carriers, a process for their preparation and the use of the solid agent as a precompound for the production of washing, rinsing and Detergents.
• rinse aids are mixtures e.g. from nonionic surfactants, solubilizers, organic acids and solvents, water and possibly preservatives and fragrances
• the task of the surfactants in these agents is to control the interfacial tension of the Influencing water so that it is in the thinnest possible continuous film from Washware can run off, so that no water drops, streaks during the subsequent drying process or films are left behind (so-called network effect). That is why surfactants must be used in rinse aid also dampen the foam from food residues in the dishwasher. Because the rinse aid mostly contain acids for an improvement of the clear drying effect, must be used Surfactants are also comparatively insensitive to hydrolysis against acids.
• Rinse aids are used both in the home and in the commercial sector. In household dishwashers the rinse aid is usually around 40 to 65 after the pre-rinse and cleaning process ° C added. Commercial dishwashers work with just one cleaning fleet, the is only renewed by adding the rinse aid solution from the previous rinsing process. It there is therefore no complete water exchange during the entire washing program. Therefore the rinse aid must also have a foam-suppressing effect, even if the temperature drops sharply from about 85 to about 35 ° C and be inert to alkali and active chlorine compounds.
• the object of the present invention was to provide tensides in solid form (solid agents) for the production of solid detergents, dishwashing detergents and cleaning agents, in particular solid dishwashing agents, for example the so-called "2 in 1" or “3 in 1” dishwashing agents, to provide.
• the solid agents should be characterized by the fact that they have excellent rinse aid properties, have a foam-suppressing effect even in the presence of protein stains, are stable even at high temperature gradients, do not gel when dissolved and, in particular, have a solubility kinetics that carry over the highest possible content of the nonionic surfactant in the rinse cycle of the machine process.
• it should be easier to produce solid detergent formulations.
• the surfaces to be cleaned or rinsed should be equipped in such a way that dirt can be removed more easily during the next cleaning process.
• the object was achieved by the provision of solid agents which contain a combination of hydroxy mixed ether and polymers in the mixing ratio according to the invention .
• these solid agents for example as a precompound in washing, rinsing and cleaning agent formulations, the surfactant content, in particular the hydroxy mixed ether content, can be reduced while maintaining a high cleaning performance. Nevertheless, this results in a very good wetting ability and a spotless shine on the surfaces to be cleaned.
• the addition of polymers to rinse aids means that the next time you clean, you can completely remove otherwise strongly adhering and often critical soiling, such as starchy soiling. This soiling can be removed without additional manual processing of the wash ware.
• the invention relates to solid agents, characterized in that hydroxy mixed ethers (a) and optionally further surfactants (a), polymers (b) and optionally further auxiliaries and additives (c) and carriers (d) typical of detergents, dishwashing detergents and cleaning agents. 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 nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be 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 the subject of, for example, the European patent EP 0693049 B1 and the international patent application WO 94/22800 (Olin) and the documents mentioned therein.
• the hydroxy mixed ethers preferably follow the general formula (I) in which 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 for 0 or numbers from 1 to 60, preferably 2 to 60 and in particular 20 to 40 and m for 0 or numbers from 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.
• R 1 is a linear or branched alkyl radical having 2 to 18, preferably 6 to 16 carbon atoms, in particular 8 to
• the HME ring opening products can be either internal olefins (R 2 not equal to hydrogen) or terminal olefins (R 2 not equal to hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties.
• the polar part of the molecule can be a polyethylene (PE) or a polypropylene (PP) chain; Mixed chains of PE and PP units are also suitable, be it in statistical or block distribution.
• Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-ocetene 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-tetradecene epoxide, 2,3-tetradecene epoxide, 3,4-tetradecene epoxide, 4,5-tetradecenepoxide, 5,6-t
• Capronic 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 their technical Mixtures.
• Cationic polymers are used, for example cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF ), Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid and dimethylaminetetrinoxypropylamine / dimethylamino trietaminopoly
• polymers are included which are selected from the group which is formed from polymers or copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide, dialkyldiallyldiammonium salts, polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, guar, cellulose and Starch derivatives, polyadducts of ethylene oxide with ammonium groups, polyesters and polyamides with quaternary page groups.
• the use of polyacrylic acid copolymers is particularly preferred, e.g. Versicol E11® or Glascol E11® (Allied Colloids), polyacrylamidopropanesulfonic acid e.g.
• Rheothik 80-11® (Cognis), trimethylammonium propyl methacrylamide sodium acrylate ethyl acrylate polymer e.g. Polyquart Ampho 149® Cognis. Also preferred are quaternized protein hydrolyzates e.g. Gluadin WQ ® (Cognis).
• Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked acrylamide acrylamide and non-crosslinked acrylamide acrylamide and polyethylenethacrylate acrylate and with polyesters, uncrosslinked acrylamide acrylamide and non-crosslinked acrylamide acrylamide and with polyesters, non-crosslinked acrylamide and polyammonyl acrylate, with non-crosslinked acrylamide acrylamide and polyamides Copolymers, octylacrylamide / methyl methacrylate / tert-butylamino-eth
• the solid agents contain cationic polymers which have monomer units of the formula ( Ia ) wherein n3 is a number between 2 and 4, preferably 3, R 1a represents hydrogen or a methyl group and R 2a , R 3a and R 4a can be the same or different and represents hydrogen or a C 1-4 alk (en) yl group stand, X - represents an anion from the group of halide anions or a monoalkyl anion of sulfuric acid semiesters.
• the polymers contain the monomer units with the formula ( Ia ) preferably in a proportion of 10 mol% to 80 mol%, particularly preferably 20 mol% to 60 mol%. As a result, the polymers 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, the alcohol components of which have alkyl groups of 1 contain up to 6 carbon atoms, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and their hydroxy derivatives, such as 2-hydroxyethyl methacrylate, with unsaturated groups, optionally further substituted aromatic compounds such as styrene, methyl styrene, vinyl styrene and heterocyclic compounds such as vinyl pyrrolidone.
• Acrylic acid, methacrylic acid and their C 1 -C 6 esters are preferably used as comonomers.
• soil-repellant polymers is also preferred.
• the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10.
• the molecular weight of the linking Polyethylene glycol units are particularly in the range of 750 to 5000, i.e., the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
• the polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block structure, but preferably a random structure.
• Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
• the agents according to the invention contain the components hydroxy mixed ethers and polymers in a weight ratio of 0.1: 1 to 1000: 1, preferably 1: 1 to 100: 1, in particular preferably 5: 1 to 50: 1.
• the solid agents contain inorganic or organic carriers, which are selected from the group consisting of zeolites, alkali sulfates, alkali phosphates, Alkali carbonates, alkali hydrogen carbonates, alkali silicates, alkali citrates, polysaccharides and their derivatives such as celluloses, carboxymethyl celluloses, cyclodextrins, starches, starch degradation products and polyacrylates, and mixtures thereof.
• inorganic or organic carriers which are selected from the group consisting of zeolites, alkali sulfates, alkali phosphates, Alkali carbonates, alkali hydrogen carbonates, alkali silicates, alkali citrates, polysaccharides and their derivatives such as celluloses, carboxymethyl celluloses, cyclodextrins, starches, starch degradation products and polyacrylates, and mixtures thereof.
• the detergent 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 and Y are also suitable.
• zeolite X and mixtures of A, X and / or P and Y are also suitable.
• a cocrystallized sodium / potassium aluminum silicate composed 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 as an undried stabilized suspension that is still moist from its production.
• these small additions of nonionic surfactants can contain as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• the generally known phosphates are used as carrier substances possible.
• the sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.
• Alkali silicates are understood to mean crystalline, layered alkali and especially sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 .
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate 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 .
• Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
• small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
• the layered silicates can also contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
• the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling condition or the type of processing.
• Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1 .
• Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
• the preferred inorganic carrier substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2 , 6, which are delayed release and have secondary washing properties.
• the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / sealing or by overdrying.
• the term “amorphous” also means “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 .
• Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• polysaccharides are cellulose, carboxymethyl cellulose, cyclodextrin or starch as well their degradation products, as polymeric carrier (d) come in particular polyacrylates with molecular weights in the range of 1,000 to 50,000 in question.
• the solid agents can be used for Detergents, dishwashing detergents and cleaning agents contain typical additives and additives, as well as other surfactants.
• these are, for example low-foaming, preferably nonionic co-surfactants, anionic co-surfactants, co-builders, oil and fat-dissolving substances, bleaching agents, bleach activators, graying inhibitors, enzymes, enzyme stabilizers, optical brighteners, defoamers, disintegrants, fragrances, inorganic salts and the like, as they are explained in more detail below.
• Solid agents are particularly preferred which, in addition to the hydroxy mixed ethers, contain nonionic surfactants as a further surfactant component, especially addition products of ethylene oxide and / or propylene oxide onto fatty or oxo alcohols.
• 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 or mixed formals, alk (en) yl-oligoglycosides, fatty acid-N-hydrolysate-based products, especially vegetable hydrolysis fatty acids (polyglycolic acid products), polyhydric acid-based polyglycolic acid products, vegetable-based polyglycolic acid fatty acids, vegetable-based polyglycolic acid fatty acids, and vegetable-based polyglycolic acid fatty acids ,
• nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
• Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters, alkyl oligoglucosides or mixed ethers are preferably used.
• the preferred fatty alcohol polyglycol ethers follow the formula (II) R 4 O (CH 2 CHR 5 O) p1 H in which R 4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 5 represents hydrogen or methyl and p1 represents numbers from 1 to 20.
• Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.
• Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula ( III ) R 6 CO- (OCH 2 CHR 7 ) p2 OR 8 in which R 6 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 7 is hydrogen or methyl, R 8 is a linear or branched alkyl radical having 1 to 4 carbon atoms and p2 is a number from 1 to 20 stands.
• Typical examples are the formal insert products of on average 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2-ethylhexanoic acid , Capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
• the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
• Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula ( IV ), R 9 O- [G] q in which R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and q represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977 .
• the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
• the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
• Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
• the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
• Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
• the alkyl or alkenyl radical R 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 their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
• Typical examples are coconut oil alcohol + 10EO-butyl ether, coconut oil alcohol + 5PO + 4EO-butyl ether or coconut oil alcohol + 10EO-benzyl ether.
• anionic co-surfactants are soaps, alkylbenzenesulfonates, secondary alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, hydroxymethane sulfate ethers, fatty acid mono ether sulfate, hydroxymethane sulfate ether, sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid
• anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
• the surfactant mixtures can particularly preferably contain anionic surfactants which are selected from the group formed by alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates sulfonates and linear alkyl benzene sulfonates and linear alkyl benzene sulfonates.
• Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (VIII) R 16 O-SO 3 X in which R 16 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol as well as their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
• the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
• Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
• ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
• SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
• ether sulfates are suitable which follow the formula (IX) R 17 O- (CH 2 CH 2 O) a SO 3 X in which R 17 represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol,
• the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
• Usable organic builders that are suitable as co-builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is used for ecological reasons is not objectionable, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Other 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. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used.
• a preferred dextrin is described in British patent application GB 9419091 A1 ,
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
• An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable .
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
• Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , such as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 .
• Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• Such cobuilders are described, for example, in international patent application WO 95/20029 .
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid).
• Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
• Granular polymers are usually subsequently mixed into one or more basic granules.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or, according to DE 4221381 C2, are monomers salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids are also to be mentioned as further preferred builder substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1 .
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• the agents can also contain components that make the oil and fat washable made of textiles.
• the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
• the sulfonated derivatives of phthalic acid and the terephthalic acid polymers include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt
• bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
• the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (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 acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from
• hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
• the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
• the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts.
• the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, described in German patent application DE 19605688 A1 and copper complexes with nitrogen-containing tripod ligands that from German patent application DE 19620411 A1 known cobalt-, iron-, copper- and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes cobalt complexes described in the European patent application EP 0272030 A1 , the manganese-K known from the European patent application EP 0693550
• Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
• enzymes from the hydrolase class such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases carry in the Laundry for removing stains such as stains containing protein, fat or starch, and graying. Cellulases and other glycosyl hydrolases can be removed by removing of pilling and microfibrils help to maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer become.
• Bacillus subtilis From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Agents. Proteases of the subtilisin type and in particular proteases which are preferred obtained from Bacillus lentus.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or Protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases too or oxidases have been found to be suitable in some cases.
• Amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• Cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases that also called cellobiases, or mixtures of these are used. Because the different Differentiate cellulase types by their CMCase and avicelase activities the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes can in turn also be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
• the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to be about 2% by weight.
• the agents can contain further enzyme stabilizers.
• enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
• calcium salts magnesium salts also serve as stabilizers.
• boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
• Graying inhibitors have the task of removing the dirt detached from the fiber in the liquor to keep suspended and thus prevent the dirt from re-opening.
• Suitable water-soluble colloids mostly organic, for example the water-soluble Salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or cellulose or salts of acidic sulfuric acid esters of cellulose or strength.
• Water-soluble polyamides containing acidic groups are also for this Suitable purpose.
• Soluble starch preparations and others other than those mentioned above can also be used Use starch products, e.g. degraded starch, aldehyde starches, etc. Also polyvinyl pyrrolidone is useful.
• cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, based on the agent used.
• the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.
• Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are also present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
• a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
• Wax-like compounds can be used as defoamers.
• waxy understood such compounds that 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.e. at 20 ° C they show in 100 g of water have a solubility below 0.1% by weight.
• Suitable waxy Compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters from one and polyhydric alcohols and paraffin waxes or mixtures thereof. Alternatively, you can of course, the silicone compounds known for this purpose can also be used.
• Suitable paraffin waxes are generally a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420 , and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention.
• the soft waxes which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products.
• the solid hydrocarbons with melting points between 63 and 79 ° C which are separated from the highly viscous, paraffin-containing lubricating oil distillates during dewaxing are also suitable.
• These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins.
• the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin can be used with a solidification point from 42 ° C to 56 ° C and 2% by weight to 25% by weight soft paraffin with a solidification point from 35 ° C to 40 ° C.
• Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
• Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C.
• the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
• the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
• Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms.
• suitable Fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil, are available.
• 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 bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
• Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
• these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
• the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
• suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
• Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
• Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters.
• Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
• Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
• suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long chain acids, high molecular weight alcohols and hydrocarbons.
• Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stearic acid, Oleic acid, palmitic acid, myristic acid and lauric acid and their mixtures, as made up natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are.
• Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
• the corresponding fatty alcohols of the same C chain length can be used.
• Dialkyl ethers may also be present as defoamers.
• the ethers can be asymmetric or be symmetrical, i.e. two identical or different alkyl chains, preferably contain from 8 to 18 carbon atoms.
• Typical examples are di-n-octyl ether and di-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point have 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 from, for example, carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example in accordance with German published patent application DE 2553900 OS.
• Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid.
• Suitable defoamers are fatty acid polyethylene glycol esters, which are preferably basic homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained.
• ethylene oxide to the fatty acids takes place in the presence of alkanolamines Catalysts.
• alkanolamines especially triethanolamine, leads to an extremely selective one Ethoxylation of fatty acids, especially when it comes to low ethoxylation Make connections.
• fatty acid polyethylene glycol esters such preferred, which have a melting point above 25 ° C, in particular above 40 ° C.
• the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in mixtures with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
• the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
• the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
• the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
• the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
• the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
• suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
• Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
• Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
• the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
• native starch which is composed of amylose and amylopectin. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
• Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
• alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
• Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
• silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanated.
• Silica-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
• the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C.
• silicones in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
• the silicones are preferably used in the form of their aqueous emulsions. As a rule, the silicone is added to the water provided with stirring. If desired, thickeners, as are known from the prior art, can be added to increase the viscosity of the aqueous silicone emulsions.
• nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyoxy cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC) are particularly preferred.
• Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
• aqueous silicone solutions are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat.
• the starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
• the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added.
• the silicones are expediently incorporated with the aid of effective stirring and mixing devices.
• the solid agents may further contain disintegrants or disintegrants.
• 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 cross-linked polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention. Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
• Such chemically modified celluloses include, for example, products from 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 bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
• the cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant.
• Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
• Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
• microcrystalline celluloses which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
• the disintegrants can be homogeneously distributed in the molded body from a macroscopic point of view, but from a microscopic point of view they form zones of increased concentration due to the manufacturing process.
• Disintegrants which may be present in the context of the invention, such as, for example, collidone, alginic acid and its alkali metal salts, amorphous or also partially crystalline sheet 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) can be found. Reference is expressly made to the teaching of these writings.
• the moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.
• fragrance compounds e.g. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used become.
• Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
• the ethers include, for example, benzyl ethyl ether and the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g.
• the hydrocarbons mainly include the terpenes like limes and pinene.
• perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources are, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
• Muscatel are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.
• the fragrances can be incorporated directly into the agents according to the invention, but they can it may also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume reinforce the laundry and by a slower fragrance release for long-lasting fragrance the Take care of textiles.
• Cyclodextrins for example, have proven useful as such carrier materials, the cyclodextrin-perfume complexes additionally coated with other auxiliaries can be.
• Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used.
• the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
• the content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
• Sodium sulfate for example, may also be present as a filler or filler in amounts of 0 to 10, in particular 1 to 5,% by weight, based on the agent
• the solid agents according to the invention can have a residual moisture content of at most 25, preferably at most 10, and in particular at most 8 and very particularly preferably below 5% by weight exhibit.
• the water content of the zeolites is not included in the calculation.
• Such agents are preferably used which are 6 to 75, preferably 10 to 40,% by weight nonionic Surfactants and 25 to 94, preferably 50 to 80 wt .-% inorganic or organic carriers contain, with the proviso that the amounts indicated with the polymers, optionally other Surfactants, other auxiliaries and additives and optionally with water and at 100% by weight complete.
• the solid agents according to the invention consist of hydroxy mixed ethers in combination with polymers on supports the desired complex requirement profile to complete satisfaction.
• these surfactants combine with inorganic or have organic carriers processed into solids with little effort, which are not gel, but have the desired delayed solubility kinetics.
• Using the fixed Means e.g. in the form of granules, powders or tablets in particular Formulate a rinse effect at the same time.
• cleaners or regeneration agents for the ion exchanger can be implemented as so-called "3 in 1" systems.
• the invention includes the knowledge that the use of the agents according to the invention is not only particularly good Clear drying effects results, but also with regard to foam damping, especially in the presence of proteins and the temperature stability provides the best results.
• Another object of the invention relates to a method for producing the invention solid agents as a pre-compound in washing, rinsing and cleaning agents, preferably dishwashing agents, characterized in that hydroxy mixed ethers of the formula (I) and polymers, if appropriate further surfactants and optionally further auxiliaries and additives on inorganic or applies organic carriers.
• the production can take place in such a way that intimate mixing of hydroxy mixed ethers, polymers, optionally further surfactants and auxiliaries and additives takes place with carriers. It is further preferred that only the surface of the carrier 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, if appropriate, further surfactants and the carriers, and, if appropriate, the further additives.
• the solid agents can be mixed by mixing the components in the Ploughshare, Lödige or Eirich mixers can be manufactured.
• hydroxy mixed ether component with the polymers is produced by fluidized bed granulation.
• aqueous preparations of the carrier the alkali silicate or the alkali carbonate together with other other components in one Drying device are sprayed, granulation taking place simultaneously with the drying can.
• the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
• the drying is carried out as spray drying in a drying tower.
• the aqueous preparations are exposed to a drying gas stream in a finely divided form in a known manner.
• Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
• a particularly preferred way of producing the agents is to use the precursors to subject fluidized bed granulation ("SKET" granulation).
• SKET fluidized bed granulation
• the preliminary products can be used both in the dried state and as an aqueous preparation be used.
• Fluidized bed apparatuses which are preferably used have base plates with dimensions from 0.4 to 5 m.
• the granulation is preferably carried out at fluidizing air speeds carried out in the range of 1 to 8 m / s.
• the discharge of the granules from the fluidized bed is preferably done by size classification of the granules.
• the classification can for example by means of a screening device or by means of an opposed air flow (classifier air) take place, which is regulated so that only particles from a certain particle size out the fluidized bed is removed and smaller particles are retained in the fluidized bed.
• the inflowing air consists of the heated or unheated classifier air and the heated soil air together.
• the soil air temperature is between 80 and 400, preferably 90 and 350 and especially below 70 ° C. It is advantageous at the beginning of the granulation a starting mass, for example a granulate from an earlier experiment, submitted.
• the mixtures are then subjected to a compacting step, where other ingredients are only added to the agents after the compacting step.
• the Compacting the ingredients takes place in one preferred embodiment of the invention Press agglomeration process instead.
• the press agglomeration process which the solid premix (dried basic detergent) is subjected to different apparatus will be realized. Depending on the type of agglomerator used, there will be different ones A distinction is made between press agglomeration processes.
• the four most common and within the scope of the present invention The preferred press agglomeration processes are extrusion, roll pressing or compacting, punching (pelleting) and tableting, so that in In the context of the present invention, preferred press agglomeration processes, extrusion, roll compaction, Pelleting or tableting processes are.
• binders can be used as an aid to compaction become.
• a binder is used that at temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C is completely in the form of a melt.
• the binder must therefore depend on the process and process conditions be selected or the process conditions, in particular the process temperature, must - if a certain binder is desired - to the binder be adjusted.
• the actual compression process is preferably carried out at processing temperatures, which, at least in the compression step, at least the temperature of the softening point, if do not even correspond to the temperature of the melting point of the binder.
• the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
• the process temperature in the compression step is not more than 20 ° C is above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; it has but showed that a temperature difference to the melting temperature or to the softening temperature the binder of 20 ° C is generally quite sufficient and even higher temperatures have no additional advantages.
• Such a temperature control has the further advantage that it is also thermal sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can.
• peroxy bleaching agents such as perborate and / or percarbonate
• enzymes increasingly processed without serious loss of active substance can.
• the possibility of precise temperature control of the binder, especially in the crucial Compaction step, i.e. between the mixing / homogenization of the premix and the shape, allows an energetically very favorable and for the temperature sensitive Components of the premix extremely gentle process management, because the premix is only exposed to the higher temperatures for a short time.
• press agglomeration processes show the working tools of the press agglomerator (the screw (s) of the Extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) one Temperature of at most 150 ° C, preferably at most 100 ° C and in particular at most 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above Melting temperature or the upper temperature limit of the melting range of the binder.
• the duration of the temperature influence in the compression range of the press agglomerators is preferably maximum 2 minutes and is in particular in a range between 30 seconds and 1 minute.
• Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. Combinations of polyethylene glycols with nonionic surfactants, especially of the fatty alcohol polyglycol ether type, are particularly preferred.
• the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
• polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Furthermore, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
• the preferably used polyethylene glycols can have a linear or branched structure, linear polyethylene glycols being preferred in particular.
• the particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight of between 3,500 and 5,000.
• polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
• these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
• suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred.
• Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.
• the compressed material preferably points directly after it leaves the production apparatus Temperatures do not exceed 90 ° C, with temperatures between 35 and 85 ° C especially are 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 described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 and WO 98/12299 .
• a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate by means of a cutting device after it has emerged from the hole shape.
• the homogeneous and solid premix contains a plasticizing and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
• Preferred plasticizers and / or lubricants are surfactants and / or polymers.
• the premix is preferably fed to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
• the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally under pressure, which is preferably at least 25 bar, but can also be below this at extremely high throughputs depending on the apparatus used
• the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
• the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this way, granules of an essentially uniformly predeterminable particle size can be produced, the absolute particle sizes in particular being able to be adapted to the intended use.
• particle diameters up to at most 0.8 cm are preferred.
• Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
• the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
• small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
• extrusion pressing can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
• the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
• the duration of the temperature influence is. Compression range of the extrusion preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
• the solid preparations according to the invention can also be roll compacted getting produced.
• the premix is targeted between two smooth or with depressions rollers of a defined shape are metered in and between the two rollers below Rolled out to a sheet-shaped compact, the so-called Schülpe.
• the reels a high line pressure on the premix and can also be heated as required or cooled.
• smooth rollers you get smooth, unstructured Belt bands, while structured using the use of structured rollers Schülpen can be generated, in which, for example, certain forms of the later Detergent particles can be specified.
• the cuff band is subsequently replaced by a Teeing and crushing process broken into smaller pieces and can be done this way processed into granules by further known surface treatment methods refined, especially brought into an approximately spherical shape can.
• the temperature of the pressing tools is also in the case of roller compacting the rollers, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C.
• Particularly preferred manufacturing processes work in roller compaction with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above Melting temperature or the upper temperature limit of the melting range of the binder lie.
• the duration of the temperature influence in the compression range no more than 2 smooth rollers or those with a defined shape Minutes and is in particular in a range between 30 seconds and 1 minute.
• the agent according to the invention can also be produced by means of pelleting.
• the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
• the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
• the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
• the press rollers can also be conical in the plate devices, in the ring-shaped devices dies and press roller (s) can have the same or opposite direction of rotation.
• An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 .
• the ring die press disclosed in this document consists of a rotating press channel penetrated ring die and at least one with its inner surface in operative connection standing press roller, which the material supplied to the die space through the press channels into one Presses material discharge.
• ring die and press roller can be driven in the same direction, whereby a reduced shear stress and thus a lower temperature increase in the premix is feasible.
• it can also be used for pelleting with heatable or coolable ones Rollers are worked to set a desired temperature of the premix.
• the pelleting temperature is also the temperature of the pressing tools, i.e. the pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C.
• Particularly preferred manufacturing processes work in roller compaction with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above Melting temperature or the upper temperature limit of the melting range of the binder lie.
• the solid preparations according to the invention are produced as tablets, preferably those in tablet form, as a rule by tableting or press agglomeration.
• the particulate press agglomerates obtained can either be used directly as detergents, dishwashing detergents or cleaning agents, or they can be aftertreated and / or prepared beforehand by customary methods.
• the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density.
• a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , dusty or at least finely divided ingredients (the so-called fine fractions) being adhered to the particulate end products of the process, which serve as a core, and thus give rise to agents which have these so-called fines as an outer shell.
• the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
• the base of these tablets can be circular or rectangular, for example.
• Multi-layer tablets in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
• the tablets can also contain pressed and unpressed parts. Shaped articles with a particularly advantageous dissolution rate are obtained if the granular constituents, prior to pressing, have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
• aqueous sodium silicate solution, aqueous polymer solution or Wax melts and their mixtures are sprayed onto the granules produced and then the water is dried, and the granules are thus provided with an outer coating (coating).
• Either 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 agent as a precompound Manufacture of detergents, dishwashing detergents and cleaning agents, preferably machine dishwashing detergents, characterized in that the solid agents 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 Lödige mixer at 2000 rpm and RT within one minute and at a temperature of 50 ° C. and mixed for one minute. Free-flowing granules were obtained.
• HME hydroxy mixed ether
• APG alkyl polyglucoside
• FAS fatty alcohol sulfate
• STTP sodium tripolyphosphate
• RT room temperature
• Recipe I and II contains the solid agents according to the invention in the form of a Pre-compounds and other recipe components.
• V1 describes a comparison recipe that the contains equal proportions of hydroxy mixed ether and polymer. However, these were not considered to be a fixed means pre-formulated.
• Example II The content of hydroxy mixed ethers (HME) and polymer in Example I and Comparative Example V1 was each 11.9g HME and 0.66g polymer, but in Example II only 8.1g HME and 0.45g polymer. It can be seen that using the solid agents according to the invention even with a lower one Content of nonionic surfactant and polymer the same clear drying effect is achieved, while at the same weight
• the HME and polymer content were recipe 1 with the solid agents according to the invention (44%) prove superior.

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