EP1306422A1 - Produits solides de lavage, de rincage et de nettoyage - Google Patents

Produits solides de lavage, de rincage et de nettoyage Download PDF

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Publication number
EP1306422A1
EP1306422A1 EP02022837A EP02022837A EP1306422A1 EP 1306422 A1 EP1306422 A1 EP 1306422A1 EP 02022837 A EP02022837 A EP 02022837A EP 02022837 A EP02022837 A EP 02022837A EP 1306422 A1 EP1306422 A1 EP 1306422A1
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Prior art keywords
acid
weight
solid
alcohol
alkali
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German (de)
English (en)
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EP1306422B1 (fr
Inventor
Ditmar Kischkel
Manfred Dr. Weuthen
Michael Elsner
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention is in the field of detergents and relates to solid washing, rinsing and Detergent containing special non-ionic surfactants and inorganic or organic carriers, processes for their preparation and the use of solid preparations from the special non-ionic surfactants and solid carriers for manufacture of means.
  • rinse aids are mixtures e.g. from nonionic surfactants, solubilizers, organic acids and solvents, water and optionally preservatives and fragrances.
  • the task of the surfactants in these agents is that To influence the interfacial tension of the water so that it is as thin as possible coherent film can run off the wash ware, so that during the subsequent drying process no water drops, streaks or films remain (so-called network effect). That is why surfactants in rinse aid must also contain those that occur due to food residues Steam the foam in the dishwasher. Since the rinse aid mostly acids for improvement of the clear drying effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.
  • Rinse aids are used both in the home and in the commercial sector.
  • the rinse aid In household dishwashers the rinse aid is usually after the pre-rinse and cleaning process about 40 to 65 ° C metered.
  • Commercial dishwashers work with just one Cleaning liquor that only by adding the rinse aid solution from the previous one Rinsing process is renewed. So there is no complete one during the entire washing program Water exchange instead. Therefore, the rinse aid must also have a foam-suppressing effect, be stable even when the temperature drops sharply from around 85 to around 35 ° C prove to be inert towards alkali and active chlorine compounds.
  • the object of the present invention was to incorporate nonionic surfactants in solid form for the production of solid washing, rinsing and cleaning agents, especially from solid dishwashing detergents, especially the so-called “2 in 1” or “3 in 1” dishwashing detergents, to provide in the form of tablets or powders, which are characterized by distinguish that they have excellent rinse aid properties, even in the present of protein soiling has a foam-suppressing effect, even when the temperature drops sharply are stable, prove to be inert to alkali and active chlorine compounds when Do not gel dissolve and in particular have a solubility kinetics that carry over the highest possible content of the nonionic surfactant in the rinse of the machine process enables
  • the invention relates to solid washing, rinsing and cleaning agents which are obtained by using gemini surfactants of the formula (I), R 1 CH (OH) CH 2 (OCH 2 CH 2 ) n OCH 2 CH (OH) R 2 (I) in which R 1 and R 2 independently of one another represent linear or branched alkyl and / or alkenyl radicals having 4 to 22 carbon atoms and n represents numbers from 5 to 400, are applied to inorganic or organic supports.
  • nonionic surfactants of the gemini surfactant type fulfill the desired complex requirement profile to full satisfaction.
  • these surfactants are combined with inorganic or organic carriers Process with little effort to solids that do not gel, but the desired one have delayed solubility kinetics. Leave using the granules in particular formulate powders or tablets with a simultaneous rinse aid effect.
  • Nonionic surfactants are preferred those of the type of gemini surfactants with 25 to 40 ethylene oxide units, since these are not only result in particularly good clear drying effects, but also with regard to the Foam attenuation, especially in the presence of proteins, the temperature stability and durability deliver the best results against alkalis and active chlorine compounds.
  • the gemini surfactants according to the invention are usually prepared by reacting 1,2-epoxyalkanes with polyethylene glycols.
  • Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decenepoxide, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-Dodecenepoxid, 3,4-Dodecenepoxid, 4,5-Dodecenepoxid, 5,6-Dodecenepoxid, 1,2-Tetradecenepoxid, 2,3-Tetradecenepoxid , 3,4-Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-
  • those gemini surfactants which have the formula (I) and in which R 1 and R 2 stand for linear alkyl radicals having 10 to 16 carbon atoms and / or which have 25 to 40 ethylene oxide units have proven particularly advantageous.
  • the bisethers can be in a mixture with monoethers. Usually, however, at least 60 mol%, preferably at least 90 mol% and in particular 95 mol% of all free primary hydroxyl groups are blocked.
  • inorganic or organic carriers examples include zeolites, alkali metal phosphates, Alkali carbonates, alkali sulfates, alkali hydrogen carbonates, alkali silicates, alkali citrates, polysaccharides and their derivatives or polymers and their mixtures in question.
  • 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.
  • a cocrystallized sodium / potassiumiumiumium 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.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the sodium salts of the orthophosphates are particularly suitable, the pyrophosphates 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 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 be caused in various ways, for example by surface treatment, compounding, compacting / compression 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 and its degradation products, in particular polyacrylates come as polymeric carriers 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.
  • Carriers who can also perform a function as builders are, for example low-foaming, preferably nonionic co-surfactants, co-builders, oil and fat dissolving substances, Bleaching agents, bleach activators, graying inhibitors, enzymes, enzyme stabilizers, optical ones Brighteners, polymers, defoamers, disintegrants, fragrances, inorganic salts and the like, as will be explained in more detail below.
  • Solid preparations which, in addition to the gemini surfactants, are particularly preferred further surfactant component non-ionic surfactants, especially addition products of ethylene oxide and / or propylene oxide to contain fatty or oxo alcohols.
  • nonionic co-surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, hydroxy mixed ethers, Alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, protein hydrolyzates (in particular vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, Polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably a narrowed homolog distribution exhibit.
  • Fatty alcohol polyglycol ethers are preferably alkoxylated Fatty acid lower alkyl esters, alkyl oligoglucosides, mixed ethers and especially hydroxy mixed ethers used.
  • 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 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, E-laeostearyl 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 (III) 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, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas.
  • the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (IV), R 9 O- [G] q (IV) 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 preparative organic chemistry methods. 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 oligo glucosides.
  • 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 13 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 13 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.
  • 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 is, for example, the subject of the European patent EP 0693049 B1 as well as the international patent application WO 94/22800 (Olin) and the documents mentioned therein.
  • R 12 represents a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms
  • R 13 represents hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
  • R 14 represents a linear or branched alkyl and / or alkenyl radical with 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 25 and in particular 5 to 15 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 12 to 18 and the sum (n1 + m + n2) is different from 0.
  • 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, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 .
  • Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain 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 methoxyl group content of 15 to 30 % By weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • 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. Substances are suitable 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 known cobalt 19620411 A1, iron-, copper- and ruthenium-ammine complexes, the manganese, copper described in the German patent application DE 4416438 A1 and cobalt complexes , the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese
  • 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 in question. All these Hydrolases help to remove stains, such as protein, fat or in the laundry starchy stains and graying. Cellulases and other glycosyl hydrolases can keep color by removing pilling and microfibrils and contribute to increasing the softness of the textile. For bleaching or for inhibition In the color transfer, oxidoreductases can also be used.
  • Bacillus subtilis Especially are particularly suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active substances obtained.
  • Proteases of the subtilisin type and in particular proteases are preferably which are obtained from Bacillus lentus.
  • 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 acting enzymes or from protease, amylase and lipase or lipolytically acting Enzymes or protease, lipase or lipolytic enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest.
  • lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven 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. Since the distinguish different cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.
  • the enzymes can in turn also be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (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 to keep the fleet suspended and thus prevent the dirt from re-opening.
  • Water-soluble colloids of mostly organic nature are suitable for this, 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. Let continue use soluble starch preparations and starch products other than those mentioned above, e.g. degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose (Na salt) are preferred, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight on the means 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).
  • 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 be.
  • the polymers are characterized by an average molecular weight from about 5000 to 200,000 and can be a block, but preferably a random structure exhibit.
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. 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 of about 10,000 to about 50,000.
  • the products are examples of commercially available polymers Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • Wax-like compounds can be used as defoamers.
  • “waxy” are understood to mean 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 exhibit.
  • the wax-like defoamer substances are practically insoluble in water, i.e. at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water.
  • all wax-like defoamer substances known from the prior art can be included.
  • Suitable waxy compounds are, for example, bisamides, Fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols as well as paraffin waxes or mixtures thereof. Alternatively you can of course the silicone compounds known for this purpose are 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 that differ from saturated fatty acids 12 to 22, preferably 14 to 18 carbon atoms and alkylenediamines with 2 to 7 carbon atoms derived.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and their mixtures, such as those made 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 their Mixtures 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 monostearate, 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
  • carnauba wax which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, Stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and their Mixtures such as those obtained from natural fats or possibly hardened oils, such as tallow or hydrogenated palm oil are available.
  • Saturated fatty acids with 12 to are preferred 22, in particular 18 to 22 carbon atoms.
  • 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 constructed asymmetrically or symmetrically, i.e. two the same or different Alkyl chains, preferably containing 8 to 18 carbon atoms.
  • typical Examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have 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 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 preferred obtained by basic homogeneously catalyzed addition of ethylene oxide to fatty acids become.
  • the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially Triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, in particular when it comes to producing low ethoxylated compounds.
  • the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
  • the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
  • suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • native starch which is composed of amylose and amylopectin. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
  • Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
  • silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanated.
  • 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 preparations can 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 be used.
  • Fragrance compounds of the ester type are e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g.
  • mixtures are preferred different fragrances, which together have an appealing fragrance produce.
  • perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention but it can also be advantageous to apply the fragrances to the carrier, which have the liability of the perfume on the laundry and by a slower fragrance release ensure long-lasting fragrance of the textiles.
  • carrier materials have become
  • cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.
  • 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
  • Another object of the invention relates to a process for the production of solid washing, rinsing and cleaning agents, preferably dishwashing detergents, in which gemini surfactants of the formula (I) are applied to inorganic or organic carriers.
  • the production can take place in such a way that either a mixture of nonionic Surfactants and carriers manufactured or only the surface of the carrier with the nonionic Surfactants is coated.
  • the agents are preferably produced in that the nonionic surfactants and the carriers and, if appropriate, the further additives, mixed together and agglomerated.
  • the solid preparations can, for example by spray drying or spray mixing, in a ploughshare, Lödige or Eirich mixer or by complex granulation processes, for example fluidized bed granulation become. It is particularly preferred that at least the nonionic surfactant component is produced by fluidized bed granulation.
  • aqueous preparations of the carrier for example the alkali silicate or the alkali carbonate sprayed together with other remaining components in a drying facility be, whereby granulation can take place simultaneously with the drying.
  • the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed to a drying gas stream in 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). This includes is to be understood as a granulation with simultaneous drying, which is preferred is carried out batchwise or continuously.
  • the preliminary products can be dried Condition as well as used as an aqueous preparation.
  • Prefers Fluid bed apparatuses used have base plates with dimensions from 0.4 to 5 m.
  • the granulation is preferably carried out at fluidizing air speeds in the range of 1 to 8 m / s carried out.
  • the granules are preferably discharged from the fluidized bed about a 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), which is regulated so that only particles above a certain particle size removed from the fluidized bed and smaller particles retained in the fluidized bed become.
  • Classifier air which is regulated so that only particles above a certain particle size removed from the fluidized bed and smaller particles retained in the fluidized bed become.
  • the inflowing air usually settles out of the heated one or unheated classifier air and the heated soil air together.
  • the soil air temperature lies between 80 and 400, preferably 90 and 350 and in particular below 70 ° C.
  • a starting mass for example, is advantageously added at the beginning of the granulation a granulate from an earlier experimental approach.
  • the mixtures are then subjected to a compacting step subjected, with further ingredients to the agents only after the compacting step be added.
  • the compacting of the ingredients takes place in a preferred one Embodiment of the invention in a press agglomeration process instead.
  • the press agglomeration process to which the solid premix (dried basic detergent) subject can be realized in various devices. ever Depending on the type of agglomerator used, there are different press agglomeration processes distinguished.
  • the four most common and within the scope of the present invention The preferred press agglomeration processes are extrusion, roller pressing or compacting, hole pressing (pelleting) and tableting, so that preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting processes are.
  • binders can be used as an aid to compaction become.
  • a binder used that at temperatures up to a maximum of 130 ° C, preferably up to a maximum 100 ° C and in particular up to 90 ° C is already completely present as a melt.
  • 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 certain binder is desired - be adapted to the binder.
  • the actual compression process is preferably carried out at processing temperatures, at least in the compression step at least the temperature of the softening point, if not the temperature of the melting point of the binder correspond.
  • 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 not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. It is technically quite possible to set even higher temperatures; but it has shown that a temperature difference to the melting temperature or the softening temperature the binder of 20 ° C is generally sufficient is and even higher temperatures have no additional advantages.
  • Such a temperature control has the further advantage that also thermally sensitive raw materials, for example peroxy bleach like perborate and / or percarbonate, but also enzymes, increasingly without serious losses of active substance can be processed.
  • thermally sensitive raw materials for example peroxy bleach like perborate and / or percarbonate, but also enzymes, increasingly without serious losses of active substance can be processed.
  • a temperature of maximum 150 ° C preferably maximum 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit the melting range of the binder.
  • the duration is preferably The maximum temperature impact in the compression area of the press agglomerators is 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. 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 are 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, especially are 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 plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers.
  • the premix is preferably fed to a planetary roller extruder or a 2-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.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
  • the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
  • the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the solid preparations according to the invention can also be roll compacted getting produced.
  • the premix is targeted between two smooth or Rollers provided with depressions of a defined shape are metered in and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers one obtains smooth, unstructured sash bands, while through the Structured slugs are generated using structured rollers can, in which, for example, certain forms of the later detergent particles can be specified.
  • the cuff band is subsequently knocked off Crushing process broken into smaller pieces and can be done in this way Granules are processed by further known surface treatment processes refined, in particular brought into an approximately spherical shape can be.
  • the temperature of the pressing is also in the roller compacting Tools, i.e. the rollers, preferably at a maximum of 150 ° C., preferably at a maximum 100 ° C and especially at a maximum of 75 ° C.
  • Particularly preferred manufacturing processes work in roller compacting with process temperatures that are 10 ° C, in particular maximum 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of exposure to temperature in the compression area of the smooth or with depressions rollers of a defined shape is a maximum of 2 minutes and in particular is 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 ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools is preferably at a maximum of 150 ° C., preferably at a maximum of 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the 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 , where dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to means , which have these so-called fines as an outer shell.
  • this advantageously takes place by melting agglomeration.
  • the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
  • the base of these tablets can be circular or rectangular, for example.
  • Multi-layer tablets in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
  • the tablets can also contain pressed and unpressed parts. Shaped articles with a particularly advantageous dissolution rate are obtained if the granular constituents, prior to pressing, have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
  • Another object of the invention relates to the use of the solid means for production detergents, detergents and cleaning agents, preferably machine dishwashing detergents, in which they e.g. in amounts of 2 to 100, preferably 7 to 60 and in particular 20 to 50 wt .-% - based on the final preparations - may be included.
  • Example 6 and Comparative Example V1 The content of gemini surfactants in Example 6 and Comparative Example V1 was in each case 12 g, in Example 7, however, only 8 g. It can be seen that using the granules according to the invention the same clear drying effect is achieved with a lower content of nonionic surfactant, while when the gemini surfactant content is equal in weight, the granules prove to be superior.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP02022837A 2001-10-23 2002-10-12 Produits solides de lavage, de rincage et de nettoyage Expired - Lifetime EP1306422B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10152142A DE10152142A1 (de) 2001-10-23 2001-10-23 Feste Wasch-, Spül- und Reinigungsmittel
DE10152142 2001-10-23

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EP1306422A1 true EP1306422A1 (fr) 2003-05-02
EP1306422B1 EP1306422B1 (fr) 2005-08-17

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US (2) US20030114348A1 (fr)
EP (1) EP1306422B1 (fr)
AT (1) ATE302259T1 (fr)
DE (2) DE10152142A1 (fr)
ES (1) ES2248471T3 (fr)

Cited By (2)

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EP1607468A2 (fr) * 2004-06-16 2005-12-21 Cognis IP Management GmbH Agent de rinçage contenant d'éthers alkyliques de polyols
WO2017071984A1 (fr) * 2015-10-26 2017-05-04 Basf Se Granulats, procédé pour leur fabrication et leur utilisation

Families Citing this family (10)

* Cited by examiner, † Cited by third party
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DE10121724A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside
DE10121723A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside
DE10121722A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside in Klarspülmitteln
DE10137925A1 (de) * 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Geminitenside und Polyethylenglycol
DE10162023A1 (de) * 2001-12-18 2003-07-03 Cognis Deutschland Gmbh Mischungen aus Geminitensiden und Fettalkoholalkoxylaten in Klarspülmitteln
DE102004005344A1 (de) * 2004-02-04 2005-09-01 Henkel Kgaa Maschinelles Geschirrspülmittel ####
DE102004048779A1 (de) 2004-10-07 2006-04-13 Cognis Ip Management Gmbh Reinigungsmittel, enthaltend Polyolhydroxyalkylether
DE602005026303D1 (de) * 2004-10-14 2011-03-24 Asahi Kasei Chemicals Corp Harzzusammensetzung
US10351803B2 (en) * 2016-02-01 2019-07-16 Ecolab Usa Inc. Solid laundry detergent for restaurant soils
CN109835909B (zh) * 2017-11-28 2022-12-02 中国石油天然气股份有限公司 一种改性硅胶载体的制备方法

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US4898621A (en) * 1987-07-18 1990-02-06 Henkel Kommanditgesellschaft Auf Aktien Use of hydroxyalkyl polyethylene glycol ethers as surfactants in rinse aids for dishwashing machines
US5160450A (en) * 1990-12-05 1992-11-03 Lion Corporation Surface-active agents having two hydrophobic chains and two hydrophilic groups
EP1254948A1 (fr) * 2001-05-04 2002-11-06 Cognis Deutschland GmbH & Co. KG Tensioactifs gemini
EP1254947A1 (fr) * 2001-05-04 2002-11-06 Cognis Deutschland GmbH & Co. KG Tensioactifs gemini

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DE4323252C2 (de) * 1993-07-12 1995-09-14 Henkel Kgaa Klarspüler für die maschinelle Reinigung harter Oberflächen
DE10121722A1 (de) * 2001-05-04 2002-11-07 Cognis Deutschland Gmbh Geminitenside in Klarspülmitteln

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US4898621A (en) * 1987-07-18 1990-02-06 Henkel Kommanditgesellschaft Auf Aktien Use of hydroxyalkyl polyethylene glycol ethers as surfactants in rinse aids for dishwashing machines
US5160450A (en) * 1990-12-05 1992-11-03 Lion Corporation Surface-active agents having two hydrophobic chains and two hydrophilic groups
EP1254948A1 (fr) * 2001-05-04 2002-11-06 Cognis Deutschland GmbH & Co. KG Tensioactifs gemini
EP1254947A1 (fr) * 2001-05-04 2002-11-06 Cognis Deutschland GmbH & Co. KG Tensioactifs gemini

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1607468A2 (fr) * 2004-06-16 2005-12-21 Cognis IP Management GmbH Agent de rinçage contenant d'éthers alkyliques de polyols
EP1607468A3 (fr) * 2004-06-16 2006-02-08 Cognis IP Management GmbH Agent de rinçage contenant d'éthers alkyliques de polyols
WO2017071984A1 (fr) * 2015-10-26 2017-05-04 Basf Se Granulats, procédé pour leur fabrication et leur utilisation
CN108350397A (zh) * 2015-10-26 2018-07-31 巴斯夫欧洲公司 颗粒、其生产方法和用途
US10717952B2 (en) 2015-10-26 2020-07-21 Basf Se Granulates, method for the production and use thereof
RU2736331C2 (ru) * 2015-10-26 2020-11-13 Басф Се Грануляты, способ их получения и их применение
CN108350397B (zh) * 2015-10-26 2021-02-26 巴斯夫欧洲公司 颗粒、其生产方法和用途

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DE10152142A1 (de) 2003-04-30
ATE302259T1 (de) 2005-09-15
US20030114348A1 (en) 2003-06-19
US6919305B2 (en) 2005-07-19
ES2248471T3 (es) 2006-03-16
DE50203939D1 (de) 2005-09-22
EP1306422B1 (fr) 2005-08-17
US20040186038A1 (en) 2004-09-23

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