WO2006045453A1 - Unite dosee de lessive ou detergent - Google Patents

Unite dosee de lessive ou detergent Download PDF

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Publication number
WO2006045453A1
WO2006045453A1 PCT/EP2005/011067 EP2005011067W WO2006045453A1 WO 2006045453 A1 WO2006045453 A1 WO 2006045453A1 EP 2005011067 W EP2005011067 W EP 2005011067W WO 2006045453 A1 WO2006045453 A1 WO 2006045453A1
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Prior art keywords
weight
acid
tablet
dosing unit
phase
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PCT/EP2005/011067
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German (de)
English (en)
Inventor
Ulrich Pegelow
Pavel Gentschev
Thomas Holderbaum
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO2006045453A1 publication Critical patent/WO2006045453A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets

Definitions

  • the present invention is in the field of detergents or cleaning agents, in particular the dosage units for detergents or cleaners.
  • Detergents or cleaners are now available to the consumer in a variety of forms.
  • this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions.
  • These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport.
  • the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing.
  • the corresponding means are comprehensively described in the prior art.
  • compacted detergents or cleaners also have a number of disadvantages.
  • Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients.
  • solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years.
  • These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, but on the other hand they also allow the preparation of liquid or powdered detergents or cleaners, which compared to the Kompaktaten characterized by a better resolution and faster effectiveness.
  • EP 1 314 654 A2 (Unilever) discloses a dome-shaped pouch with a receiving chamber containing a liquid.
  • WO 01/83657 A2 Procter & Gamble
  • pouches which contain two particulate solids in a receiving chamber, each of which is present in fixed regions and does not mix with one another.
  • EP 1 256 623 A1 Subject of the European application EP 1 256 623 A1 (Procter & Gambie) is a kit of at least two bags with different composition and optics. The bags are separate and not as a compact single product.
  • the abovementioned detergents or cleaners packaged in water-soluble films or film bags are distinguished from the conventional tablets by increased production costs and lower storage and transport stability. Especially for safe transport, special, cost-intensive outer packaging is required.
  • a first subject of the present application is therefore a multiphase detergent or makeskardosiermati containing at least one enzyme and at least one water-swellable disintegration aid, characterized in that at least one of the phases of the dosing unit has a higher weight fraction of enzyme than the other phases and this phase a smaller proportion by weight of swellable disintegration aid than at least one of the other phases of the dosing unit.
  • compositions according to the invention are washing or cleaning agent dosing units.
  • Dosierüen are in the context of this application such containers or Kon Stammionsformen denotes, which comprise a sufficient amount of a washing or cleaning agent for performing a washing or cleaning cycle, preferably a machine cleaning cycle.
  • the dosing unit does not necessarily have to be a physical unit, ie a single body.
  • the metering unit in the context of the present application may also comprise two or more separate bodies, provided that they are intended for common use in a washing or cleaning cycle, preferably a machine cleaning cycle.
  • the metering units according to the invention are preferably used as mechanical cleaning agents, that is to say for example as machine textile detergents or machine dishwashing detergents.
  • mechanical cleaning agents that is to say for example as machine textile detergents or machine dishwashing detergents.
  • agents according to the invention as machine dishwashing agents is particularly preferred.
  • the weight of metering units according to the invention is preferably between 5 and 40 g, preferably between 7 and 30 g and in particular between 10 and 25 g.
  • the metering units according to the invention are preferably made up in such a way that they can be metered in via the dispensing chambers of textile washing machines or dishwashers.
  • the volume of preferred metering units is therefore preferably between 4 and 50 ml, preferably between 6 and 30 ml and in particular between 8 and 25 ml.
  • phases in the context of this application are designated by a common phase boundary or by a packaging means separate areas of different composition.
  • a "phase” is preferably one by a molding process, such as compaction, tabletting, extrusion or casting , or made-up by a packaging process area. Examples of such phases are, for example, the phases of a tablet or the regions of a multi-chamber bag which are separated from one another by packaging material.
  • the compositions of the invention contain a water-swellable disintegration aid.
  • a water-swellable disintegration aid These substances or mixture of substances, also referred to as tablet disintegrants, increase their volume upon ingress of water, wherein the intrinsic volume increases (swelling) and a pressure can be generated which causes the tablet to disintegrate into smaller particles.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • the weight fraction of the swelling disintegration assistant in the total weight of the metering unit is between 0.5 and 10% by weight, preferably between 3 and 7 Wt .-% and in particular between 4 and 6 wt .-%, each based on the total weight of the dosing unit.
  • Dosing units which are preferred in the context of the present application are characterized in that the swellable disintegration aid is a polymer swellable disintegration aid.
  • Preference according to the invention is given to those metering units in which the swellable disintegration aid has an average particle size of more than 200 ⁇ m, preferably between 300 and 1600 ⁇ m and in particular between 400 and 1200 ⁇ m.
  • Preferred water-swellable disintegrating agents are cellulosic disintegrating agents.
  • Pure cellulose has the formal gross composition (C 6 H 10 Os) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CWIC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the above and described in more detail in the documents cited coarser disintegration aids are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • microcrystalline cellulose As a further cellulosic disintegrating agent or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and, for example, can be compacted into granules having an average particle size of 200 ⁇ m.
  • Preferred metering units are characterized in that a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, is used as the swelling disintegration assistant.
  • water-swellable disintegration aids are polyvinylpyrrolidones and / or polyacrylates, preferably crosslinked polyvinylpyrrolidones and / or crosslinked polyacrylates. These swellable disintegration aids, as well as the cellulose-based disintegration aids described above, are preferably used in particulate, particularly preferably in granular, co-granulated or compacted form.
  • disintegration aids are the products available under the following trade names: Amberlite ® IRP 88, Disintex ® 75, 100 and 60, Acusol ® 771, Explotab ®, Primogel ®, Polyplasdone ® XL and XL 10, Kollidon ® CL 1 Ac-di- Sol ®, Nymcel ®, Indion ® 234, 294 and 414, Cavamax ®, Alginic Acid ® DC, Kelacid ®, crospovidone ®, VivaSol ®, Emcosoy ®, Solutab ®, Vivastar ®, Primojl ®, Tablo ®, Endurance ® MCC.
  • the dosage units according to the invention may furthermore furthermore comprise gas-evolving effervescent systems as tablet disintegration aids.
  • gas-developing effervescent systems are not swellable disintegration aids in the context of the present invention and are therefore not taken into account in the determination of the proportion by weight of these swellable disintegration aids in the individual phases of metering units according to the invention.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
  • the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an Acidifi ⁇ réellesstoff, which is suitable to release from the alkali metal salts in aqueous solution of carbon dioxide.
  • the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).
  • Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • the compositions of the invention contain enzymes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or Oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.
  • Detergents or detergents contain enzymes preferably in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • agents according to the invention contain proteases, amylases, lipases, hemicellulases, cellulases and / or oxidoreductases as enzymes.
  • the agents according to the invention may contain one, two, three, four or more enzymes.
  • the agents according to the invention may also contain several different proteases or amylases or lipases or hemicellulases or cellulases or oxidoreductases. In the context of the present application, in particular those agents are preferred which contain proteases and amylases but no lipases.
  • subtilisin type those of the subtilisin type are preferable.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvasrd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the .alpha.-amylases from Bacillus licheniformis, S. amyloliquefaciens or B. stearothermophilus and their use in washing and disinfecting Detergents improved developments.
  • the enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase of ⁇ . amyloliquefaciens is sold by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, also from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases which were originally obtainable from Hum / co / a lanuginosa ⁇ Thermomyces lanuginosus) or further developed, in particular those with the amino acid substitution D96L. They are for example marketed by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • useable lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp.
  • Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available.
  • the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • mannanases for example, under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® AB Enzymes B1 from and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • the from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • the enzymes originate, for example, either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the purification of the relevant enzymes is preferably carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example, by applying poly
  • the dosing unit according to the invention contains at least one enzyme in solid form, preferably in encapsulated solid form.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are aminoalcohols, such as up to Ci 2, such as succinic acid, other dicarboxylic acids or salts of said acids, mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.
  • Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • calcium salts such as calcium acetate or calcium formate, and magnesium salts.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance.
  • Crosslinked N-containing compounds also act as enzyme stabilizers.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • peptide-aldehyde stabilizers for example polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is enhanced by the combination with boric acid and / or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.
  • enzymes and / or enzyme preparations Preference is given to one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations.
  • the proportion by weight of enzyme according to the invention of preferred metering units is, based on the total weight of the metering unit, between 0.1 and 5 wt .-%, preferably between 0.2 and 4 wt .-% and in particular between 0.5 and 3 wt .-% ,
  • the object according to the invention could be achieved by the targeted distribution of the enzymes and disintegration aids contained in the dosing unit according to the invention.
  • Particularly advantageous in terms of their storage stability and cleaning performance have such agents of the invention have proven, in which the weight ratio of enzyme to swellable disintegrants in the enzyme-richest phase more than 5: 1, preferably more than 10: 1, more preferably more than 50: 1 and in particular more than 100: 1.
  • Such weight ratios can be realized by raising the enzyme content in one phase of the dosing unit or decreasing the disintegrating agent content in the enzyme-containing phase.
  • agents preferred according to the invention are metering units having an "enzyme phase", ie metering units in which the enzyme-richest phase has an enzyme content above 20% by weight, preferably above 30% by weight, in particular above 40% by weight
  • metering units are also feasible in which the enzyme content is significantly less than 20 wt .-%
  • dosing units in which the enzyme-richest phase has an enzyme content between 2 and 15 wt .-%, preferably between 3 and 12 wt .-% and especially between 4 and 10% by weight are particularly preferred.
  • the disintegrant content in this phase is preferably lowered to low values in accordance with the invention. Preference is given to those metering units in which the enzyme-richest phase, based on the weight of this phase, less than 5 wt .-%, preferably less than 2 wt .-%, preferably less than 1 wt .-%, more preferably less than Contains 0.1 wt .-% and in particular no swellable disintegration aid.
  • the dosing unit according to the invention has two or more phases, of which at least one phase contains enzyme (s), while at least one further phase comprises a swelling disintegrant.
  • Some preferred embodiments for two- or three-phase dosing units are listed in the table below (The term "disintegrants” in the following Table 1 stands for the above-mentioned 2 swellable disintegrants.)
  • the data in% by weight correspond to the proportion by weight of enzyme or swellable disintegrant based on the weight of each phase.)
  • Suitable metering units in the context of the present application are all forms of detergents or cleaners which are known to the person skilled in the art and which can be prepared in a multiphase form. These include, for example, multiphase Kompaktste or extrudates, such as tablets or extruded extrudates, water-soluble dosing units with one or more receiving chambers, such as deep-drawn or injection-molded containers, or combinations of these various forms of offer. Particularly preferred within the scope of the present application are agents according to the invention, characterized in that the dosing unit is a tablet, a filled mortar tablet, a water-soluble container, a combination product of a tablet and a water-soluble container or a combination product of a filled mortar tablet and a water-soluble container.
  • the dosage unit according to the invention is a multiphase tablet.
  • This tablet has at least two phases, but tablets with three, four or more phases are also feasible. Because of the increasing complexity of the production of these tablets with increasing phase number, two, three or four-phase tablets are particularly preferred in the context of the present application.
  • washing or cleaning agent tablets preferably takes place in a manner known to those skilled in the art by compressing particulate starting substances.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process referred to below as tabletting, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and ejection.
  • the tabletting is preferably carried out on so-called rotary presses.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • preferred methods are characterized in that the compression is effected at press pressures of 0.01 to 50 kNcm '2, preferably from 0.1 to 40 kNcm' 2 and in particular 1 to 25 kNcm "2 takes place.
  • the individual phases of the two- or more-phase tablet are preferably arranged in layers.
  • the weight ratio of the phase with the lowest weight fraction of the tablet is preferably at least 50% by weight, preferably at least 10% by weight and in particular at least 20% by weight.
  • the proportion by weight of the phase with the highest proportion by weight of the tablet in the case of biphasic tablets is preferably not more than 90% by weight, preferably not more than 80% by weight and in particular between 55 and 70% by weight.
  • the proportion by weight of the phase with the highest proportion by weight of the tablet is preferably not more than 80% by weight, preferably not more than 70% by weight and in particular between 40 and 60% by weight.
  • the structure of the tablet is onion-like.
  • at least one inner layer is completely surrounded by at least one outer layer.
  • phase 1 corresponds in such an embodiment to a first tablet phase
  • phase 2 corresponds to a second tablet phase
  • phase 3 corresponds to a third tablet phase.
  • a filled mortar tablet is used as a two- or multi-phase dosing unit.
  • the mortar tablet can be configured in one or more phases.
  • the filling of the trough can be designed single or multi-phase.
  • the well can be a cavity (well with a hole on the top of the tablet) or a hole (a well with two holes on the surface of the tablet).
  • the tablet is preferably prepared according to the method described above, wherein for the design of the trough of the or the tablet punches may be provided with a center mandrel.
  • solidifying liquids or gels For example, compacts, extrudates, granules, agglomerates or powders can be used as solids.
  • Suitable liquids are aqueous and nonaqueous solutions, for example surfactant solutions, but also liquid pure substances such as, for example, liquid surfactants.
  • the weight proportions of enzyme and disintegration aid in the previously described container can also vary in the case of the filled well tablets.
  • the weight percentages of the enzymes and disintegration aids of the individual phases are within the limits disclosed in the table above.
  • the phase referred to in the table as "Phase 1" corresponds in such an embodiment, for example, a first tablet phase
  • the phases referred to in the table as "Phase 2" and “Phase 3" then correspond, for example, in each case a second tablet phase or a phase well filling.
  • Preference is given to those forms of offer in which
  • Phase 1 indicates the proportions by weight of enzyme and disintegration aid of a single-phase well tablet, while “Phase 2" indicates the weights of enzyme and disintegration aid of the well fill; “Phase 2” in Table 1 indicates the proportions by weight of enzyme and disintegration aid of a single-phase well tablet, while “Phase 1” indicates the weights of enzyme and disintegration aid of the well fill; “Phase 1” in Table 1 indicates the weight proportions of enzyme and disintegration aid of a first phase of a biphasic well tablet, “Phase 2” indicates the weights of enzyme and disintegration aid of a second phase of a biphasic well tablet, while “Phase 3” indicates the weights of enzyme “Phase 1” in Table 1 indicates the weight percent of enzyme and disintegration aid of a first phase of a biphasic well tablet “Phase 3” indicates the weight percent of enzyme and disintegration aid of a second phase of a biphasic well tablet 2
  • a well tablet having a well or cavity, preferably a well, said well being a filling comprising a) an enzyme-containing powder having a weight fraction of enzyme in the total weight of the powder of between 50 and 100% by weight; preferably of 100% by weight, and b) a liquid, preferably a surfactant-containing liquid, preferably a surfactant-containing liquid packed in a water-soluble material, and the tablet contains no enzyme, but disintegration aid, preferably in amounts between 0.1 and 10 wt .-%, preferably between 0.2 and 8 wt .-% and in particular between 0.4 and 6 wt .-%.
  • a well tablet having a well or cavity, preferably a well, said well being a filling comprising a) an enzyme-containing powder having a weight fraction of enzyme in the total weight of the powder of between 50 and 100% by weight; and b) a liquid, preferably a surfactant-containing liquid, preferably a surfactant-containing liquid packed in a water-soluble material, and the well tablet, based on the weight of the well tablet, between 0.1 and 5 wt .-% enzyme, preferably between 0.2 and 4 wt .-% enzyme and in particular between 0.4 and 3 wt .-% enzyme and further Disintegrationstosmittel, preferably in amounts between 0.1 and 10 wt .-%, preferably between 0.2 and 8 wt. % and in particular between 0.4 and 6 wt .-%, each based on the weight of the well tablet contains.
  • a water-soluble container is used as a two- or multi-phase dosing unit.
  • This container may have one, two, three, four or more compartments.
  • the two or more phases can therefore be present side by side in a common compartment or separately in different compartments.
  • the water-soluble containers contain the detergents or cleaners in different clothing forms and / or physical states.
  • Particularly preferred are such forms in water-soluble containers containing as individual phases a tablet and a liquid; a particulate composition, and a liquid; a tablet and a particulate composition; a tablet, a particulate composition and a liquid.
  • the water-soluble or water-dispersible container is a thermoformed body.
  • "deep-drawing body” refers to those containers which are obtained by deep-drawing a first film-like wrapping material, preferably by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing mold and molding the wrapping material into it
  • the enveloping material may be pretreated before or during shaping by the action of heat and / or solvent and / or conditioning by relative humidity changes and / or temperatures to environmental conditions two parts of a tool, which behave as positive and negative to each other and deform a film placed between these tools when compressed the weight of the film and / or the weight of a spent on the top of the film active substance.
  • the deep-drawn shell materials are preferably fixed after deep drawing by using a vacuum within the receiving wells and in their achieved by the deep-drawing process space shape.
  • the vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers.
  • a discontinuous vacuum for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible.
  • the continuous or discontinuous vacuum can vary in its thickness and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (during filling or sealing or singulation).
  • the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices.
  • the shell material preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 6O 0 C for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 8O 0 C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.
  • the dies used and the receiving troughs located in these dies are preferably carried out at temperatures below 2O 0 C, preferably below 15 0 C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C.
  • the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling fluids, preferably water, which are circulated in special cooling lines within the matrix, are particularly suitable for cooling.
  • This cooling as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, whereby not only the appearance of the process product is improved, but also at the same time the discharge of the filled into the receiving chambers means the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.
  • the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material over a continuously rotating Matrizenformwalze (optionally optionally with a counter-guided Patrizenformwalze, which lead the forming upper punch to the cavities of the Matrizenformwalze) differ.
  • the first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means.
  • the receiving troughs located in the matrices can be arranged "in series" or staggered.
  • the thermoforming bodies can have one, two, three or more receiving chambers. These receiving chambers can be arranged side by side and / or one above the other in the deep-drawn part.
  • the individual receiving chambers of the thermoforming bodies are filled with different agents. It is preferred in particular to fill at least one receiving chamber of a thermoformed body with a liquid, while at least one further receiving chamber of this thermoformed body is filled with a solid.
  • the water-soluble container is an injection-molded part.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling. Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 0 C) and injected under high pressure (up to 140 MPa) in closed, two-part, ie from Gesenk (formerly Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify.
  • Suitable molding compositions are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • the information in Table 1 can also be applied to the supply form of the water-soluble containers. From the combination of the data in Table 1 with this preferred form of supply, the following particularly preferred metering units according to the invention result:
  • a multiphase washing or cleaning agent dosing unit containing at least one enzyme and at least one water-swellable disintegration aid wherein the Dosage unit comprises a tablet and a liquid, which are present together in the same compartment or in separate compartments of a water-soluble container, characterized in that the liquid has a higher proportion by weight of enzyme than the tablet and the liquid at the same time a smaller proportion by weight of swellable disintegration aid than the pill.
  • a multi-phase detergent or dosing unit containing at least one enzyme and at least one water-swellable disintegration aid comprising a particulate composition and a liquid which are present together in the same compartment or in separate compartments of a water-soluble container, characterized in that the liquid has a higher weight fraction of enzyme than the particulate composition and at the same time has a lower weight fraction of swellable disintegration aid than the particulate composition.
  • a multi-phase detergent or dosing unit containing at least one enzyme and at least one water-swellable disintegration aid comprising a tablet and a particulate composition which are present together in the same compartment or in separate compartments of a water-soluble container, characterized in that the particulate Composition has a higher weight fraction of enzyme than the tablet and the particulate composition at the same time has a lower weight content of swellable disintegration aid, as the tablet.
  • Weight proportions according to Phase 2 of Table 1 corresponds to the respective proportions by weight of the tablet.
  • a multi-phase detergent or dosing unit containing at least one enzyme and at least one water-swellable disintegration aid comprising a tablet, a particulate composition and a liquid which are present together in the same compartment or in separate compartments of a water-soluble container, characterized the liquid has a higher proportion by weight of enzyme than the tablet and the liquid at the same time has a smaller proportion by weight of swellable disintegration aid than the tablet.
  • a multi-phase detergent or dosing unit containing at least one enzyme and at least one water-swellable disintegration aid comprising a tablet, a particulate composition and a liquid which are present together in the same compartment or in separate compartments of a water-soluble container, characterized in that the particulate composition has a higher proportion by weight of enzyme than the tablet and the particulate composition at the same time has a lower proportion by weight of swellable disintegration aid than the tablet.
  • a combination product of a tablet and a water-soluble container is used as a two- or multi-phase dosing unit.
  • the tablet and the water-soluble container may be present separately from each other, but the tablet and water-soluble container may also be interconnected, in which case adhesive, latching, plugging or snap connections, but in particular adhesive or plug connections are preferred .
  • the tablet may be the (teat) tablets described above.
  • well tablets, in particular well tablets with a hole / breakthrough in a combination product with a water-soluble container are particularly preferred.
  • the well tablet preferably has an enzyme content and disintegration assistant content as indicated for Phase 2 in Table 1, while at least one of the phases contained in the water-soluble container has an enzyme content and disintegration aid content as indicated for Phase 1 of Table 1 ,
  • the preferred subject of the present application are thus furthermore:
  • a multi-phase detergent or dosing unit containing at least one enzyme and at least one water-swellable disintegration aid comprising a tablet and a water-soluble container filled with a particulate composition, characterized in that the particulate composition has a higher weight fraction of enzyme than the tablet and at the same time the particulate composition has a lower weight fraction of swellable disintegration aid than the tablet.
  • a multiphase washing or cleaning agent dosing unit comprising at least one enzyme and at least one water-swellable disintegration aid, the dosing unit comprising a tablet and a water-soluble container filled with a liquid, characterized in that the liquid has a higher proportion by weight of enzyme than the tablet and the Liquid at the same time has a lower weight fraction of swellable disintegration aid, as the tablet.
  • dosage units according to the invention which comprise at least one (well) tablet, wherein the (tablets) tablet has a surfactant content below 8% by weight, preferably below 6% by weight, particularly preferably below 4% by weight. and in particular below 2 wt .-% have.
  • Particularly preferred dosage units comprise a (well) tablet which contains less than 4% by weight, preferably less than 2% by weight, more preferably less than 1% by weight, most preferably less than 0.2% by weight. % and in particular contains no anionic surfactants.
  • the metering unit is a tablet, a filled mortar tablet, a combination product of a tablet and a water-soluble container or a combination product of a filled tablet and a water-soluble container, Trough) tablet has a surfactant content below 4 wt .-%, preferably below 2 wt .-%, more preferably below 1 wt .-% and in particular below 0.2 wt .-%.
  • a very particularly preferred agent according to the invention is a multiphase washing or cleaning agent dosing unit containing at least one enzyme and at least one water-swellable disintegration aid, wherein the dosing unit comprises a single-phase well tablet having a cavity or an opening and the cavity is a single- or multi-phase filling, preferably a filling of a powder and a liquid-filled water-soluble container, wherein at least one of the phases of the filling has a higher proportion by weight of enzyme than the well tablet and this phase has a lower weight content of swellable disintegration aid, as the well tablet.
  • Another very particularly preferred agent according to the invention is a multiphase washing or cleaning agent dosing unit containing at least one enzyme and at least one water-swellable disintegration aid, the dosing unit comprising a biphasic well tablet having a cavity or an opening and the well a single- or multi-phase filling, preferably comprises a filling of a powder and a liquid-filled water-soluble container, wherein at least a first phase of the tablet has a higher weight fraction of enzyme than a second phase of the tablet and this first phase has a lower weight fraction of swellable disintegration aid, as the second phase the tablet.
  • a third very particularly preferred agent according to the invention is a multiphase washing or cleaning agent dosing unit containing at least one enzyme and at least one water-swellable disintegration aid, the dosing unit comprising a biphasic well tablet having a cavity or an opening and the well a single- or multi-phase filling, preferably comprises a filling of a powder and a liquid-filled water-soluble container, wherein at least one of the phases of the filling, preferably the powder, a higher weight fraction of enzyme than at least one of the tablet phases and this tablet phase has a lower weight fraction of swellable disintegration aid than the phase of filling.
  • compositions according to the invention or the compositions prepared by the process according to the invention described above contain further washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaching agents, bleach activators, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + I
  • 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.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • crystalline layer-form silicates of the general formula NaMSi x O 2x + I • y H 2 O are used, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1 , 9 to 4, and y is a number from 0 to 33.
  • the crystalline layered silicates of the formula NaMSi x O 2x + I • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 • x H 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 • x H 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 Oi ⁇ x 7 H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9
  • crystalline phyllosilicates of the formula NaMSi x O 2x + I • y H 2 O in which x is 2.
  • Na-SKS-5 OC-Na 2 Si 2 O 5
  • Na-SKS-7 U-Na 2 Si 2 O 5 , Natrosilit
  • Na-SKS-9 NaHSi 2 O 5 • H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3 H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 0 5
  • Na-SKS-13 Na-SKS-13
  • Na-SKS-6 5-Na 2 Si 2 O 5 ).
  • these compositions preferably comprise a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x + 1 • y H 2 O from 0.1 to 20 wt .-%, from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • Such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% of silicate of the general formula NaMSi x O 2x + I ⁇ y H 2 O is.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • compositions according to the invention or agents prepared by the process according to the invention as automatic dishwasher detergents which is particularly preferred in the context of the present application.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric (HPO 3 ) ⁇ and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Suitable phosphates are for example the sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1.91 like “3 , melting point 60 °) or in the form of the monohydrate (density 2.04 like '3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na 2 HPO 4 , which is anhydrous or 11067
  • the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) is marketed, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O).
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, based in each case on the weight of the washing or cleaning agent.
  • potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, especially preferably more than 10: 1 and in particular more than 20: 1 use. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of detergents or cleaners to (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%. 5 011067
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • 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.
  • 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.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • 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.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • the nonionic surfactants used are preferably alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical branches linearly or preferably methyl in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols having 3 EO or 4 EO, C g . ir alcohol containing 7 EO, C. 13 1s- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 - 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 - alcohol with 3 EO and C 12 . 18- alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • R is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • Nonionic surfactants which have a melting point above room temperature.
  • surfactants which are solid at room temperature, come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol having from 6 to 20 carbon atoms, preferably at least 12 Mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 mole percent of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • end-capped poly (oxyalkylated) nonionic surfactants are of the formula
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x are values between 1 and 30
  • k and j are values between 1 and 12, preferably between 1 and 5, preference being given to surfactants of the type
  • x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the The above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • nonionic surfactants which have a C 9 . 15 alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms
  • R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.
  • radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms adjacent to a monohydroxylated intermediate group -CH 2 CH (OH) -.
  • x in this formula stands for values between 1 and 90.
  • R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably -CH 3
  • x and y are independently of one another values between 1 and 32, nonionic surfactants having values for x of 15 to 32 and y of 0, 5 and 1, 5 are very particularly preferred.
  • R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably represents -CH 3
  • x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein nonionic surfactants with values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not referred to as mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather those mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • surfactants of the sulfonate type preferably come C 9 - 13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from Ci 2 -i 8 monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettcicren are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelklareschester the C 12 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • 21 -alcohols such as 2-methyl-branched C 9 . ir alcohols containing on average 3.5 mol ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO, are also suitable. You will be in cleaning mittein due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%, used.
  • the anionic surfactants including the soaps, may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • anionic surfactants are part of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • cationic active substances for example, cationic compounds of the following formulas can be used:
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
  • “Cationic polymers” for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and Methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, the quaternized polyvinyl alcohols or under the INCI names Polyquatemium 2, Polyquatemium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms;
  • R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group;
  • x and y independently represent integers between 1 and 3.
  • X ⁇ represents a counterion, preferably a counterion selected from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, Methosuifat, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • a counterion selected from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, Methosuifat, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, -CH 2 - CH 2 -CH 3, -CH (CHs) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • cationic or amphoteric polymers contain a monomer unit of the general formula
  • Ri HC C-R2 C (O) -NH- (CH 2) -N + R3R4R5
  • X " in the R 1 , R 2 , R 3 , R 4 and R 5 are independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6.
  • H 2 C C (CH 3 ) -C (O) -NH- (CH 2 ) x - N + (CH 3 ) 3
  • X " chloride also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).
  • MAPTAC Metalacrylamidopropyl trimethylammonium chloride
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred useful amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) - acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonion
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers are selected from the group of methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethylcyclodially ammonium chloride / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyldiallylammonium chloride / acrylic acid copolymers, IVIethacrylamidopropyltrimethylammonium chloride / DirnetriyKdiallyOammonium- chloride / acrylic acid copolymers and Methacrylamidopropyltrimethylarnmoniurn- chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their Alkali and ammonium salts.
  • the polymers are present in prefabricated form.
  • Coating compositions preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or
  • Paraffins having a melting point above 3O 0 C Paraffins having a melting point above 3O 0 C; the co-granulation of the polymers with inert support materials, preferably with
  • Support materials from the group of washing or cleaning-active substances particularly preferably from the group of builders (builders) or cobuilders.
  • Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) COOH in which R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 methacrylamido-2-hydroxy-propane sulfonic acid, Allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of mentioned
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • copolymers which are structural units of the formula are preferred.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative.
  • acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
  • the corresponding copolymers contain the structural units of the formula
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred detergents or cleaners are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 have.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid
  • washing or cleaning agents in particular automatic dishwashing agents, are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight % Bleach, preferably sodium percarbonate.
  • the active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing detergents in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%.
  • Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.
  • R 1 for -H, -CH 3 a C 2 . 24 alkyl or alkenyl, a substituted C 2-24 -AIKyI- or alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or Alkenylarylrest with one Ci -24- alkyl group, or for a substituted alkyl or Alkenylarylrest with a Ci.
  • bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • bleach activators preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • acylated phenolsulfonates in particular n-nonanoyl or isononanoyloxybenzenesulfonate
  • n- or iso-NOBS n- or iso-NOBS
  • n-methyl-morpholinium-acetonitrile-methyl sulfate MMA
  • up to 10% by weight in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the bleach activator-containing agents.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing agents used. But in special cases, more bleach activator can be used.
  • a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
  • the zinc compounds mentioned are preferably used in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 % By weight, based in each case on the entire glass corrosion inhibitor-containing agent.
  • the exact content of the agent on the zinc salt or the Zinc salts are naturally dependent on the type of zinc salts - the less soluble the zinc salt used is, the higher its concentration in the compositions should be.
  • the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 ⁇ m. Again, this is even more true the less the zinc salt is soluble.
  • the glass corrosion inhibiting effectiveness increases with decreasing particle size.
  • the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 60 ⁇ m are preferred for the very poorly soluble zinc oxide.
  • Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that, even with repeated use, the surfaces of glassware do not undergo corrosive changes, in particular no clouding, streaks or scratches, but also no iridescence of the glass surfaces.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, yet the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the spectrum of the inventively preferred zinc salts of organic acids ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l have, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C water temperature).
  • the group of soluble zinc salts include, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • At least one zinc salt of an organic carboxylic acid more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or Zinkeitrat used.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.
  • 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention which may be mentioned are: propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl -, undecyl, - dodecyl, - isononyl, -Versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, 3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, -3 amino-1, 2,4-triazole.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds used.
  • organic redox-active compounds such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds used.
  • salt and complex inorganic compounds such as salts of the metals Mn 1 Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. Oxide, sulfate, nitrate, fluoride, but also organic anions such as e.g. Stearate.
  • Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned.
  • Anions exist.
  • the central atom is one of the o.g. Metals in one of the above Oxidation states.
  • the ligands are neutral molecules or anions that are mono- or polydentate;
  • the term "ligand" within the meaning of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail.
  • the charge of the central atom and the charge of the ligand (s) do not add up to zero, either one or more of the above may be provided, depending on whether there is cationic or anionic charge excess.
  • Anions or one or more cations e.g. Sodium, potassium, ammonium ions, for the charge balance.
  • Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1-diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , M
  • metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners.
  • the mixture of pentavalent and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from the SO 3 preparation (contact method) is suitable, as is the case by diluting a Ti (SO 4 ) 2 - Solution resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, ie completely coated with a water-tight material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a likewise continuously produced spray zone of the molten coating material.
  • the melting point must be selected so that the coating material easily dissolves or melts rapidly during silver treatment.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 0 C lie ⁇ gene.
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing agent.
  • fragrance compounds for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, oc-lsomethylionon and methyl cedrylketone , to the Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance To be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role plays. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “body note” ) and “base note” (end note or dry out).
  • the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • fixatives preventing them from evaporating too quickly.
  • Adhesion-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edel fir oil, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copa ⁇ va balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil
  • fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bomyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol,
  • Methyl anthranilate p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, ⁇ -naphtholethyl ether, ⁇ -naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, ⁇ -phenylethyi alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, cyclohexyl sal
  • the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.
  • the colorant it must be taken into account that in the case of textile detergents, the colorants do not have too high an affinity for textile surfaces and, in particular, for synthetic fibers, whereas in the case of detergents an excessive affinity for glass, ceramic or plasticware must be avoided. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation.
  • water-insoluble colorants are more stable to oxidation than water-soluble colorants.
  • concentration of the colorant in the detergents or cleaners varies.
  • highly soluble dyes for example, the above-mentioned Basacid ® Green or the above-mentioned Sandolan Blue ® are typically chosen dyestuff concentrations in the range of some 10 '2 to 10 "3 wt .-%.
  • the suitable concentration of the colorant in detergents or cleaning agents is typically some 10 '3 to 10 "4 wt .-%.
  • Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
  • Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.
  • the detergents and cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
  • Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
  • pH adjusters In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.
  • Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) X and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa.s.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners may be added to laundry detergents or cleaners to remove graying and yellowing of the treated fabrics which will attract the fiber and cause lightening and fake bleaching by exposing invisible ultraviolet radiation to visible, longer wavelength light where the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and gives the whiteness of the bruised or yellowed wash pure white ..
  • Suitable compounds are derived, for example, from the substance classes of the 4,4 "diamino-2,2 ' stilbenedisulfonic (Flvonäuren), 4,4'-distyryl-biphenyls, Methylumbelliferone, coumarins, Dihydrochinolinone, 1,3-Diarylpyrazoline, Naphthal Acidimide, Benzoxazol-, Benzisoxazol- and benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • 4,4 "diamino-2,2 ' stilbenedisulfonic (Flvonäuren) 4,4'-distyryl-biphenyls, Methylumbelliferone, coumarins, Dihydrochinolinone, 1,3-Diarylpyrazoline, Naphthal Acidimide, Benzoxazol-, Benzisoxazol- and benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • Cellulosic ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof can furthermore be used as graying inhibitors.
  • synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability.
  • Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled, polymerizable compounds.
  • Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish.
  • a further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing).
  • the water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc.
  • hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening.
  • silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.
  • compositions may contain anti-oxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.
  • Softeners can be used to care for textiles and to improve the textile properties such as a softer "avivage” and reduced electrostatic charge (increased wearing comfort.)
  • the active ingredients in fabric softening formulations are "esterquats", quaternary ammonium compounds with two hydrophobic radicals, such as Disteraryldimethylammoniumchlorid, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
  • esters with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Further suitable as a finish is dimethylolethyleneurea.
  • Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and also the polyalkylene oxide-modified dimetylpolysiloxanes.
  • UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds having these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic nitium complexes and natural substances such as umbelliferone and the endogenous urocanic acid.
  • Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners.
  • Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
  • protein hydrolysates of both vegetable and animal origin can be used.
  • Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein hydrolysates, which may also be present in the form of salts.
  • Preferred according to the invention is the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates.
  • amino acid mixtures or individual amino acids obtained otherwise such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. It is likewise possible to use derivatives of the protein tetrolyzates, for example in the form of their fatty acid condensation products.
  • the nonaqueous solvents which can be used according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (acetic esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, Pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), halogenated hydrocarbons (d
  • a solvent mixture which is particularly preferred in the context of the present application is, for example, benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90 wt .-%, each based on the total weight of the mixture, preferably having a boiling range of 81 to 110 0 C.

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Abstract

L'invention concerne une unité dosée de lessive ou détergent à plusieurs phases, qui contient au moins une enzyme et au moins un agent désintégrant pouvant gonfler dans l'eau. Cette invention se caractérise en ce qu'au moins une des phases de l'unité dosée présente un pourcentage en poids d'enzyme supérieur à celui des autres phases et cette phase présente un pourcentage en poids d'agent désintégrant pouvant gonfler dans l'eau inférieur à celui d'au moins une des autres phases de l'unité dosée. Cette unité dosée se distingue des lessives et détergents classiques par une meilleure efficacité de nettoyage.
PCT/EP2005/011067 2004-10-22 2005-10-14 Unite dosee de lessive ou detergent WO2006045453A1 (fr)

Applications Claiming Priority (2)

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DE200410051557 DE102004051557A1 (de) 2004-10-22 2004-10-22 Wasch- oder Reinigungsmitteldosiereinheit
DE102004051557.3 2004-10-22

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0976820A1 (fr) * 1998-07-31 2000-02-02 Chimiotechnic Tablette détergente multicouches pour le lavage du linge et procédé de fabrication
DE19903288A1 (de) * 1999-01-28 2000-08-03 Henkel Kgaa Mehrphasige Waschmitteltabletten
WO2000070008A1 (fr) * 1999-05-17 2000-11-23 Reckitt Benckiser N.V. Procede de production d'une pastille de detergent a plusieurs couches
US6313080B1 (en) * 1998-02-04 2001-11-06 Unilever Home & Personal Care, Usa Division Of Conopco, Inc. Detergent compositions
US6548473B1 (en) * 1997-11-26 2003-04-15 The Procter & Gamble Company Multi-layer detergent tablet having both compressed and non-compressed portions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19851426A1 (de) * 1998-07-15 2000-01-20 Henkel Kgaa Verfahren zur Herstellung mehrphasiger Wasch- und Reinigungsmittelformkörper
DE19856213A1 (de) * 1998-12-05 2000-06-08 Henkel Kgaa Punkttabelle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6548473B1 (en) * 1997-11-26 2003-04-15 The Procter & Gamble Company Multi-layer detergent tablet having both compressed and non-compressed portions
US6313080B1 (en) * 1998-02-04 2001-11-06 Unilever Home & Personal Care, Usa Division Of Conopco, Inc. Detergent compositions
EP0976820A1 (fr) * 1998-07-31 2000-02-02 Chimiotechnic Tablette détergente multicouches pour le lavage du linge et procédé de fabrication
DE19903288A1 (de) * 1999-01-28 2000-08-03 Henkel Kgaa Mehrphasige Waschmitteltabletten
WO2000070008A1 (fr) * 1999-05-17 2000-11-23 Reckitt Benckiser N.V. Procede de production d'une pastille de detergent a plusieurs couches

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