EP1802736A1 - Agents de lavage ou de nettoyage - Google Patents

Agents de lavage ou de nettoyage

Info

Publication number
EP1802736A1
EP1802736A1 EP05803738A EP05803738A EP1802736A1 EP 1802736 A1 EP1802736 A1 EP 1802736A1 EP 05803738 A EP05803738 A EP 05803738A EP 05803738 A EP05803738 A EP 05803738A EP 1802736 A1 EP1802736 A1 EP 1802736A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
preferred
cavity
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05803738A
Other languages
German (de)
English (en)
Inventor
Ulf Arno Timmann
Salvatore Fileccia
Wolfgang Barthel
Arno DÜFFELS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1802736A1 publication Critical patent/EP1802736A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 cleaners.
  • the present invention relates to a process for the preparation of detergents or cleaners, in particular of metering units of 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, on the other hand, but at the same time they also allow the preparation of liquid or powder detergents or cleaning agents Compared to the compact data 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 & Gamble) 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 object of the present application was to provide a process for the preparation of detergents or cleaners, which enables the joint preparation of solid and liquid or flowable detergent or cleaner compositions in separate areas of a compact dosing unit.
  • the final process product should be characterized by an attractive appearance.
  • washing or cleaning agent tablets comprising a cavity which has at least two openings on the surface of the tablet, characterized in that the openings of the cavity are closed by two separate sealing elements.
  • compositions according to the invention not only solve the object of the invention mentioned above, but also have an improved washing and cleaning performance compared with conventional detergents or cleaners.
  • moldings preferably compacted, preferably tabletted, or extruded or cast molded bodies are used in the compositions according to the invention. In the context of the present application, however, tableted shaped bodies are particularly preferred.
  • 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 hereinafter referred to as tabletting, is divided into four sections: dosing, 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 pressing takes place at pressing pressures of 0.01 to 50 kNcm “2 , preferably 0.1 to 40 kNcm “ 2 and especially 1 to 25 kNcm "2 .
  • the individual phases of 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 wt .-%, preferably at least 10 wt .-% 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.
  • cavity in the context of the present invention, both troughs and through the molding through holes or holes, which connect two sides of the molding, preferably opposite sides of the molding, for example, the bottom and roof surface of the molding together.
  • the shape of the cavity which is preferably a well, may be chosen freely, with tablets being preferred in which at least one well is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral , conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal, prismatic and rhombohedral forms.
  • Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized.
  • wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • the bottom surface of the trough can be flat or inclined.
  • the cavity is an opening, which connects two opposite sides of the molding together.
  • a corresponding shaped body can be referred to as a ring body.
  • the aperture areas of the aperture in the surface of this annular body may be the same size but may differ in size. If a tablet is used as the shaped body, then the shaped body with such a breakthrough corresponds to a so-called ring tablet.
  • Breakthrough shaped moldings are particularly preferably used in which the opening areas of the opening on the opposite sides of the molded body are less than 80%, preferably less than 60%, preferably less than 40%, based on the larger of the two opening areas. more preferably differ by less than 20% and in particular by less than 10%.
  • ring tablets are used in which the opening areas of the opening are the same size.
  • the cross-section of the aperture may be angular or round.
  • Cross sections with one, two, three, four, five, six or more corners can be realized, however, such shaped bodies are particularly preferred in the context of the present application, which have a breakthrough without corners, preferably a breakthrough with a round or oval cross-section.
  • a "cross section" refers to a surface which is perpendicular to a straight connecting line between the center points of the two opposite opening surfaces of the shaped body.
  • the molding may have more than one cavity. Moldings having two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more cavities are particularly preferred in the present application. If the shaped body has more than one cavity, these cavities can be both the wells described above and the breakthroughs described above. Shaped bodies which have more than one cavity, wherein at least one of the cavities is a depression and at least one further one of the cavities is an opening, are particularly preferred in the context of the present application.
  • the volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.
  • Detergents or cleaning agent shaped bodies characterized in that the cavity has two openings which are located on opposite sides of the shaped body, are preferred according to the invention.
  • the detergent tablets according to the invention are characterized by the two separate sealing elements on the openings of the cavity of the shaped body.
  • a multiplicity of different agents can be used as sealing elements, wherein washing or cleaning agent shaped bodies, characterized in that the sealing element is a foil, a filled water-soluble container or a second shaped body, are preferred according to the invention.
  • the sealing element used is a film material, preferably a film material comprising one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVOH polyvinylpyrrolidone
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the film material used in the process according to the invention at least partially comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and in particular 82 to 88 mol%.
  • the first film material used in the process according to the invention is at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably comprises at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82nd to 88 mol%.
  • Polyvinyl alcohols having a specific molecular weight range are preferably used as the film material, wherein the film material preferably comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 1,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol '1 and in particular from 13,000 to 70,000 gmol "1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • polyvinyl alcohols are as the film material ® ELVANOL 51-05, 52-22, 50-42, 85- 82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • To use extremely advantageous are the reaction products of PVAL and starch.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples are those available under the name "SOLUBLON® ®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • ethylene oxide oxirane
  • ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to polymeriza- grades of about 5 to> 100,000.
  • Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and only show weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the gelatin corresponds largely to that of the collagen from which it was obtained, and varies depending on its provenance.
  • film materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight-chain amylose (MW 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included.
  • the amylose forms long, helical, entangled chains with approximately 300 to 1,200 glucose molecules as a result of the 1, 4-position bond
  • the amylopectin branch branches off into a branch-like structure after an average of 25 glucose building blocks by 1,6-bonding with about 1,500 to 12,000 molecules of glucose.
  • starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C 6 Hio0 5 ) ⁇ and formally represents a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 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 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, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • HPMC hydroxypropyl methylcellulose
  • degree of substitution average number of methoxy groups per unit of anhydroglucose cellulose
  • molar substitution average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose
  • the film material used is preferably transparent.
  • transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
  • Preparations made according to the invention, for the production of which transparent film material has been used, may contain a stabilizing agent.
  • Stabilizing agents in the context of the invention are materials which protect the ingredients at least partially enclosed by the film material from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • antioxidants are particularly suitable stabilizing agents in the context of the invention.
  • the formulations may contain antioxidants.
  • antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • aromatic amines preferably secondary aromatic amines and substituted p-phenylenediamines
  • phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites
  • citric acids and citric acid derivatives such as Isopropyl citrate
  • endiol group-containing compounds so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate
  • organosulfur compounds such as the esters of 3,3 ' -Thiodipropionklare with d - ⁇ - alkanols, especially Ci 0 .
  • metal ion deactivators capable of complexing autooxidation catalyzing metal ions, such as copper, such as nitrilotriacetic acid and its derivatives and mixtures thereof.
  • Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
  • UV absorbers can improve the light stability of the formulation components. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) - 4-hydroxy-5- (methylpro-pyl) -mononathumsalz (Cibafast ® H), 3-phenyl-substituted acrylates ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the biphenyl and especially stilbene derivatives which are available as Tinosorb ® FD or Tinosorb ® FR ex Ciba commercial.
  • UV-B absorber are 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably A-
  • Esters of cinnamic acid preferably 2-ethylhexyl A-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
  • Esters of salicylic acid preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;
  • Derivatives of benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenz
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-borny! Iden) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface treated, i. hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones.
  • micronized zinc oxide is used.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • Preferred agents have a sealing material with a thickness of between 5 and 2000 .mu.m, preferably between 10 and 1000 .mu.m, particularly preferably between 15 and 500 .mu.m, very particularly preferably between 20 and 200 .mu.m and in particular between 25 and 100 .mu.m as a sealing element.
  • the films used may be single-layer or multi-layer films (laminate films). Regardless of their chemical or physical structure, the water content of the film materials is preferably below 10 wt .-%, more preferably below 7 wt .-%, most preferably below 5 wt .-% and in particular below 4 wt .-%.
  • the adhesive connection is in spatial proximity to the opening of the cavity.
  • the adhesive compounds along a circumferential sealed seam can be realized by a number of different procedures. However, preference is given to those processes in which the adhesive compound is formed by the action of adhesives and / or solvents and / or compressive or squeezing forces. Also in the case of heat sealing, a circumferential sealing seam, that is, a self-contained sealing seam is particularly preferred. For heat sealing of molded articles and film material, a number of different tools and processes are available to the person skilled in the art.
  • the heat seal is effected by the action of heated sealing tools.
  • the heat seal is effected by the action of a laser beam.
  • the heat seal is effected by the action of hot air.
  • the shaped body and the sealing element (s) are connected to one another by a heat-sealing seam.
  • the cavity of the detergent tablets according to the invention is preferably filled with one or more washing- or cleaning-active substances or substance mixtures.
  • the cavity is preferably of flowable washing and cleaning active preparations, preferably liquid (s), in particular melts, and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Compacted (e) filled.
  • liquid in the present application denotes substances or substance mixtures as well as solutions or suspensions which are in the liquid state of matter.
  • Powder is a general term for a form of division of solids and / or mixtures obtained by comminution, that is, grinding or crushing in the mortar (pulverizing), grinding in mills or as a result of atomization or freeze-drying.
  • a particularly fine division is often called atomization or micronization; the corresponding powders are called micro-powders.
  • powders have lower particle sizes below 5000 .mu.m, preferably less than 3000 .mu.m, preferably less than 1000 .mu.m, very particularly preferably between 50 and 1000 .mu.m and in particular between 100 and 800 .mu.m.
  • Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes.
  • Each of the methods known in the prior art for the agglomeration of particulate mixtures is in principle suitable for producing the solids contained in the agents according to the invention.
  • agglomerates used as solid (s) are, in addition to the granules, the compacts and extrudates.
  • Granules are aggregates of granules.
  • a granule (granule) is an asymmetric aggregate of powder particles.
  • Granulation methods are widely described in the art.
  • Granules can be prepared by wet granulation, by dry granulation or compaction and by melt solidification granulation.
  • the most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and leads most safely to granules with favorable properties.
  • the wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or Solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, said mixer can be equipped, for example, with stirring and kneading tools.
  • combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation.
  • the granulation is dependent on the starting material and the desired product properties under the action of low to high shear forces.
  • melt solidification melting
  • aqueous, slurries spray drying
  • solid substances which are sprayed at the top of a tower in a defined droplet size, solidify in free fall or dry and on Floor of the tower incurred as granules.
  • Melt solidification is generally particularly suitable for shaping low-melting substances which are stable in the melting temperature range (eg urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills.
  • Spray drying is used especially for the production of detergents or detergent ingredients.
  • extruder or perforated roll granulations in which powder mixtures optionally mixed with granulating liquid are plastically deformed during perforation by perforated disks (extrusion) or on perforated rolls.
  • the products of extruder granulation are also referred to as extrudates.
  • Detergent or detergent tablets characterized in that the cavity is filled with a flowable substance, preferably a particulate substance or a liquid, are particularly preferred.
  • the cavity is filled with a two- or more-phase agent.
  • the cavity has two openings on opposite sides of the shaped body (ring tablet), wherein the openings of the cavity are closed by two separate sealing elements and the cavity, that is the space enclosed by the shaped body and the separate sealing elements, is filled with a two- or multi-phase agent.
  • the two-phase or multi-phase agent may be one or more liquids, one or more solids, or a mixture of one or more liquids and 11066
  • Preferred agents are two-, three-, four- or five-phase.
  • Particularly preferred di- or multiphase agents comprise at least one liquid and at least one solid.
  • the individual phases are separated from one another by a separate separation layer.
  • separating layers can be sprayed or poured, for example.
  • separating layers of film materials in particular water-soluble polymeric film materials, are preferred.
  • Suitable water-soluble film materials are, in particular, the water-soluble polymers disclosed above as materials for the sealing elements.
  • molded body with a cavity, which two openings on opposite sides of the molding on (ring tablet), wherein the openings of the cavity are closed by two separate sealing elements and the cavity, that is, of the molded body and the sealed sealing elements enclosed Room, filled with a two- or multi-phase agent and at least two phases of the di- or multiphase agent are separated by a water-soluble film.
  • This particular embodiment is particularly suitable for the preparation of liquid and solid detergents or cleaning agents in a single metering unit.
  • molded body with a cavity which two openings on opposite sides of the molding on (ring tablet), wherein the openings of the cavity are closed by two separate sealing elements and the cavity, that is enclosed by the molding and the separate sealing elements
  • Room is filled with a two- or multi-phase agent, which comprises at least one liquid and at least one solid, and at least one liquid of the di- or multiphase agent of at least one solid of the di- or multiphase agent separated by a water-soluble film.
  • sealing elements in this particularly preferred embodiment water-soluble films are preferably used.
  • the following table gives an overview of a series of preferred inventive washing or cleaning agent tablets with two-phase filling. The quantities are in each case based on the total weight of the molding or of the phase 1 or phase 2.
  • Surfactant preferably 10 to 50 bleaches
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Surfactant preferably 10 to 50 bleaches and 0.1 to 10
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Surfactant preferably 10 to 50
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Surfactant preferably 10 to 50 glass corrosion inhibitors
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Surfactant preferably 10 to 50 silver corrosion inhibitor
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Surfactant preferably 10 to 50 cationic or amphoteric
  • Surfactant preferably 10 to 50 bleaches
  • Surfactant preferably 10 to 50 bleaches and 0.1 to 10
  • Surfactant preferably 10 to 50
  • Surfactant preferably 10 to 50 glass corrosion inhibitors
  • Surfactant preferably 10 to 50 silver corrosion inhibitor
  • Surfactant preferably 10 to 50 cationic or amphoteric
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Enzyme preferably 10 to 50 bleaches
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Enzyme preferably 10 to 50 bleach and 0.1 to 10
  • Enzyme preferably 10 to 50 glass corrosion inhibitor
  • Enzyme preferably 10 to 50 silver corrosion inhibitor
  • Enzyme preferably 10 to 50 cationic or amphoteric
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • Solvent monophase with water-soluble liquid with 10 to 90 powder, granules or extrudate
  • solvent two-phase with water-soluble liquid with 10 to 90 powder, granules or extrudate 0.1-15 wt .-% foil wt .-% of nonionic surfactant and 0.1 to 100 wt .-% disintegration - preferably 10 to 50 cationic or amphoteric auxiliaries .-% organic polymers
  • detergent tablets according to the invention with a liquid surfactant-containing filling are particularly preferred.
  • These compositions in particular compositions containing a disintegration aid in the preferably tableted molded article, are distinguished from molded articles having a correspondingly increased surfactant content in the molded article by a very high cleaning performance, improved storage stability and improved processability, in particular tabletting of the molded articles.
  • washing or cleaning agent shaped bodies are particularly preferred, characterized in that the cavity is subdivided by a water-soluble film into two separate chambers, wherein such washing or cleaning agent shaped bodies are particularly preferred in which one of the two chambers with a liquid detergent composition which is other of the two chambers with a solid detergent composition.
  • the separation of the individual phases by means of a water-soluble film can be carried out in different ways.
  • the water-soluble films are adhesively bonded to the molded article.
  • the water-soluble films, preferably together with one of the sealing elements forms a receptacle, for example in the form of a bag or a pouch.
  • the water-soluble film used to separate the different detergent and cleaner compositions in the cavity preferably has a common sealing seam, preferably a common heat-sealing seam with one of the sealing elements closing the cavity.
  • these shaped articles preferably have a coating.
  • Detergent or detergent tablets according to the invention characterized in that the tablet is a coating are particularly preferred.
  • the shaped body surface is preferably coated with a surface coverage of between 0.2 and 50 mg / cm 2 .
  • Moldings which are preferred according to the invention are characterized in that the surface coverage of the molding is between 0.4 and 40 mg / cm 2 , preferably between 0.8 and 30 mg / cm 2 and in particular between 1 and 20 mg / cm 2 .
  • the proportion by weight of the coating in the total weight of the coated shaped body is preferably less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.7% by weight and in particular less than 0.4% by weight. ,
  • the shaped bodies preferably have a spray coating or a dip coating.
  • the spraying is preferably carried out by means of single-fluid or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
  • single-fluid spray nozzles the application of a high melt pressure (5-15 MPa) is required, while spraying in dual-fluid spray nozzles takes place by means of a stream of compressed air (at 0.15-0.3 MPa).
  • the spraying with two-component spray nozzles is more favorable, especially with regard to possible blockages of the nozzle, but more expensive due to the high consumption of compressed air.
  • three-component spray nozzles which, in addition to the stream of compressed air for atomization, are intended to prevent a further air-guiding system which prevents blockages and droplet formation at the nozzle.
  • the use of two-component spray nozzles preferably two-component spray nozzles with a fluid bore of between 1 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
  • the coating agents used are preferably water-soluble organic polymers.
  • the coating material comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof. Further details on these substances can be found earlier in the description.
  • Coating materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof, are preferred within the scope of the process according to the invention.
  • Preferred shaped bodies have a multiple coating.
  • a “multiple” or “repeated” coating of the shaped body can take place in such a way that the shaped body is dried at least superficially between the individual coating steps.
  • the Coating steps are consequently interrupted by a drying step but at least by a waiting time, which preferably exceeds at least one minute, preferably at least two minutes and in particular at least three minutes. Drying steps which are carried out under more severe conditions, that is to say at elevated temperature and / or higher vacuum, can preferably be reduced to at least 10 seconds, particularly preferably at least 30 seconds, preferably at least 40 seconds and in particular to at least 50 seconds.
  • the surface coverage of the moldings with a multiple coating is preferably between 0.2 and 100 mg / cm 2 , preferably between 1 and 80 mg / cm 2 , more preferably between 10 and 70 mg / cm 2 and in particular between 20 and 60 mg / cm 2 ,
  • agents according to the invention in which the shaped body is coated twice, three times or four times. If the coating is repeated a number of times, it is also possible, depending on the field of application of the detergent tablets or cleaning agent tablets, to use different coating agents in the individual coating operations. Such agents, in which different coating materials are used, are particularly preferred according to the invention.
  • coating materials which are suitable in combination with the particularly preferred water-soluble polymers, for example in the form of a molten, dissolved or dispersed mixture, or as a second or third coating material in a repeated coating of the shaped bodies are a) the LCST substances a) the waxes a) the paraffins
  • LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as substances with lower critical demixing temperature. These substances are usually polymers. Depending on the application conditions, the lower critical solution temperature between room temperature and the temperature of the heat treatment should, for example, between 20 0 C, preferably 3O 0 C and 100 ° C, in particular between 30 0 C and 50 ° C.
  • the LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
  • alkylated and / or hydroxyalkylated polysaccharides are methylhydroxypropylmethylcellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), Methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydrdoxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose (PC) and mixtures thereof, wherein carboxymethylcellulose, methylcellulose,
  • LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of interconnected networks of the above (co) polymers.
  • polyethylene oxide or copolymers thereof such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGW), a repeating unit in the natural protein elastin, and certain alginates.
  • VATGW polyvinyl methyl ether
  • Mixtures of these polymers with salts or surfactants can also be used as the LCST substance.
  • the LCST lower critical demixing temperature
  • waxing is meant a number of natural or artificially derived substances which generally melt above 35 ° C without decomposition and are already slightly above the melting point, relatively low viscosity and non-stringy. They show a strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
  • the natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or raffia fat Mineral waxes such as ceresin or ozokerite (groundwax), or • petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
  • the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable as coating materials are compounds from other classes of substances which fulfill the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll ® 66 (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea). Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used as further substance.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms.
  • the wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the coating in the context of the present invention.
  • Paraffin is the term for a solid or liquid mixture of purified, saturated aliphatic hydrocarbons (paraffins). This is readily soluble in ether and chloroform but not soluble in water. Both liquid paraffins and paraffin melts can be used in the context of the present invention.
  • paraffin waxes have the advantage over the other natural waxes mentioned that the use of preferred washing or cleaning agent shaped articles coated with paraffin waxes in an alkaline cleaning agent environment does not result in hypersensitivity of the waxes (as for example in the case of wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes and low levels of iso and
  • the paraffin to be used according to the invention preferably has essentially no
  • Preferred coating materials contain at least one paraffin wax with a
  • the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 0 C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
  • Paraffin waxes applied in the form of their melts preferably solidify within 10 minutes, preferably within 5 minutes and especially within 2 minutes.
  • hydrophobic substances as a coating material is preferred in the present invention, since these substances improve the storage behavior of the laundry detergent or cleaner moldings according to the invention at high humidities.
  • the increased moisture resistance of the coated body makes it possible to dispense after application of a hydrophobic substance to a seal with a water-soluble or water-dispersible film.
  • this is only a preferred embodiment of the method according to the invention.
  • it may be preferable to apply a film to the hydrophobic-coated molded body.
  • the film can be fused at least proportionately with the coating, loosely, that enclose the body, or contain an air cushion, so that the molded body is additionally protected from mechanical effects.
  • the shaped bodies are coated twice, three times or four times, it being possible in each case for the coating processes to use the same or different coating materials.
  • coating materials from the group of water-soluble polymers (for example PVA, PVP, gelatin or LCST polymers) and the water-insoluble waxes and the paraffins.
  • the following table gives an overview of one Series of particularly preferred sequences of these coating materials.
  • the coating marked as the first layer corresponds to the first applied to the molding
  • the coating materials can be mixed with active ingredients and active ingredients. Dyes, fragrances or bitter substances are preferably added to the coating materials.
  • Coated moldings are surprisingly characterized by a special adhesive strength of the connection between detergent tablets and the sealing element or the water-soluble film used as a separator in the cavity.
  • the preferred subject matter of the present application is therefore furthermore a coated molded body with a cavity which has two openings on opposite sides of the molded body (ring tablet), wherein the openings of the cavity are closed by two separate sealing elements and the cavity, that is, of the shaped body and the space enclosed by the separate sealing elements, with a two- or multiphase agent is filled and at least two phases of the di- or multiphase agent are separated by a water-soluble film.
  • this particular embodiment is particularly advantageous for the assembly of liquid and solid detergents or cleaners in a single metering unit.
  • Coated molded bodies with a cavity, which have two openings on opposite sides of the molded body (ring tablet), are therefore particularly preferred, the openings of the cavity being closed by two sealing elements which are separate from each other, and the cavity, that is, of the molded body and the sealing elements which are separate from one another enclosed space is filled with a two- or multi-phase agent, which comprises at least one liquid and at least one solid, and at least one liquid of the di- or multiphase agent of at least one solid of the di- or multiphase agent separated by a water-soluble film ,
  • a two- or multi-phase agent which comprises at least one liquid and at least one solid, and at least one liquid of the di- or multiphase agent of at least one solid of the di- or multiphase agent separated by a water-soluble film
  • sealing elements in this particularly preferred embodiment water-soluble films are preferably used.
  • the weight of washing or cleaning agent tablets 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 detergent tablets according to the invention are preferably made up in such a way that they can be dispensed via the Ein Hamptonkammem of textile washing machines or dishwashers.
  • the volume of preferred detergent tablets is therefore preferably between 4 and 50 ml, preferably between 6 and 30 ml and in particular between 8 and 25 ml.
  • Another object of the present application is a process for the preparation of a portioned detergent or cleaning agent, comprising the steps
  • a water-soluble or water-dispersible film is used as the sealing element in step b) and / or d).
  • the receiving chamber is filled with two different washing or cleaning-active substances or compositions, these different substances or compositions preferably being separated from one another by a water-soluble film material.
  • a further preferred subject matter of the present application is therefore a process for producing a portioned detergent or cleaner, comprising the steps of a) providing a washing or cleaning agent shaped body having a cavity which has two openings on opposite sides of the shaped body; a) sealing one of the openings with a first sealing element to form a receiving chamber formed by the sealing element and the molded body; a) partial filling of the receiving chamber; a) applying a water-soluble film material to the second opening of the
  • the molding of the film material in the partially filled cavity is preferably carried out by the action of pressure and / or vacuum.
  • the film material can be pretreated before or during the shaping by the action of heat and / or solvent and / or conditioning before by relative to ambient conditions changed relative humidity and / or temperatures.
  • the pressure can be applied by a tool which behaves like a "positive" to the acting as a "negative" cavity.
  • the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as a compressive force.
  • a receiving chamber is formed from the film material in the cavity.
  • This receiving trough is then filled in the subsequent step e) with a washing or cleaning-active substance.
  • the shape and the volume of the receiving trough will of course depend on the shape and the volume of the cavity of the molded article on which the process is based. Particularly preferred are those methods in which the volume the receiving trough formed by the film material is at least 5% by volume, preferably at least 10% by volume, very particularly preferably at least 20% by volume, of the volume of the washing or cleaning agent shaped body.
  • the negative pressure can be generated in the cavity by different procedures.
  • the sealing element applied in step b) has an opening through which a vacuum can be generated in the cavity.
  • the negative pressure in the cavity is created by applying a negative pressure to a hole or indentation which connects the cavity to the part of the surface of the shaped body (outside the cavity) which does not extend through the first sealing element Step b) is covered.
  • a hole may, for example, be a bore which connects the cavity to a side surface or the lower side of the molded body.
  • Such a bore preferably has a diameter below 5 mm, preferably below 3 mm and in particular below 2 mm.
  • the cavity can also be connected by more than one hole with one or more outer sides, the molded body also have more than one bore.
  • the shaped body can furthermore have notches.
  • These notches or grooves open into the opening of the cavity opening and lead from there preferably to a side surface of the molding.
  • the width of these notches is preferably less than 10 mm, preferably less than 7 mm, more preferably less than 4 mm and in particular less than 2 mm.
  • the depth of the notches is preferably in the range between 1 and 15 mm, preferably between 1 and 10 mm and in particular between 1 and 5 mm.
  • the first film material is applied by applying a negative pressure to a hole or indentation which connects the cavity to the part of the surface of the molded article (outside the cavity), not through the first film material from step b) is covered, formed in the cavity.
  • the negative pressure in the cavity can be generated by applying a negative pressure to the shaped body surface (outside the cavity).
  • a negative pressure to the shaped body surface (outside the cavity).
  • the abovementioned washing or cleaning agent tablets are suitable for such a process.
  • particulate starting mixtures can thus be produced moldings which have sufficient porosity, by applying a negative pressure on the surface of the shaped body, which is not covered by the film material within the Cavity sufficient vacuum to generate, to pull the opening of the cavity covering sheet material deep in this cavity.
  • the first sheet material is produced by applying a negative pressure to the part of the surface of the shaped body (outside the cavity), which is not covered by the sheet material from step b) deep drawn into the cavity.
  • the negative pressure in the cavity is produced by the air in the cavity below the film material applied in step d) being conveyed "through the tablet", that is to say by applying a negative pressure to bores specially set for this purpose,
  • the negative pressure in the cavity is created by the air in the cavity below the film applied in step d) passing through holes in this film material is removed from the cavity.
  • Processes according to the invention in which the negative pressure is generated both in the cavity, ie below the film material applied in step d), and also outside the cavity, above the film material applied in step d), are particularly preferred.
  • Such a particularly advantageous process procedure can be realized, for example, by placing the molded body covered with the film material in a vacuum chamber.
  • the film web applied in step d) is sealed with the filled container in such a way that the container is closed on all sides and in particular no air can pass through the openings of the film web applied in step d) into the container. If the sealed container is then removed from the vacuum chamber, the atmospheric pressure acting on the container from outside causes the outer walls of the container, in particular the film web applied in step d), to fit tightly against the molded body into the cavity.
  • a method for producing a dosing unit for detergents or cleaning compositions comprising the steps of a) providing a shaped body having at least one cavity, which has two openings on opposite sides of the shaped body; b) sealing one of the openings with a first sealing element to form a receiving chamber formed by the sealing element and the molded body; c) Partial filling of the receiving chamber; d) applying a water-soluble film web to the second opening of the shaped body and molding the film material in the cavity to form a further receiving chamber by the covered with the film web moldings is placed in a vacuum chamber and in this chamber, a negative pressure is generated, whereby in the cavity thereby creating a negative pressure such that the air in the cavity below the foil escapes at least partially through openings in the foaming material placed in step b); e) filling the further receiving chamber; f) sealing the second opening with a second sealing element, are preferred in the context of the present application.
  • a particularly preferred method comprises the step of a) providing a shaped body having at least one cavity, which has two openings on opposite sides of the shaped body; b) sealing one of the openings with a first water-soluble film to form a receiving chamber formed by the film and the molded body; 5 011066
  • washing or cleaning active composition preferably a solid washing or cleaning active composition which particularly preferably contains at least one substance from the group of builders, enzymes, bleaching agents, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors;
  • a washing or cleaning-active composition preferably a liquid washing or cleaning-active composition, which particularly preferably contains at least one nonionic surfactant;
  • compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , 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.
  • zeolite X and zeolite A are 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 n Na 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O
  • 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 layered silicates of general formula NaMSi x O 2x + 1 • y H 2 O are used, wherein M is 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.
  • • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • Examples of these silicates are 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 O 17 • x H 2 O) or Na SKS-4 (Na 2 Si 4 O 9 • x H 2 O, Makatite).
  • crystalline phyllosilicates of the formula NaMSi x O 2x + - I ⁇ y H 2 O, in which x is 2.
  • Na-SKS-5 CX-Na 2 Si 2 O 5
  • Na-SKS-7 B-Na 2 Si 2 O 5 , natrosilite
  • 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 (NaHSi 2 O 5 )
  • 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 particularly 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 at least 90 wt. % to silicate of the general formula NaMSi x O 2x + 1 • y H 2 O acts.
  • 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.
  • 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 with 2 mol (density 2.066 like '3 , water loss at 95 °), 7 mol (density 1, 68 like "3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol Water (density 1, 52 like "3 , melting point 35 ° with loss of 5 H 2 O) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4 , which as dodecahydrate, as decahydrate (corresponding to 19-20% P 2 O 5 ) and in anhydrous form (corresponding to 39-40% P 2 O 5 )
  • Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 .
  • the tetrasodium diphosphate sodium pyrophosphate
  • Na 4 P 2 O 7 which in anhydrous form (density 2.534 like “3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with loss of water)
  • potassium salt potassium diphosphate potassium 4 P 2 O 7 .
  • 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:
  • sodium tripolyphosphate potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • 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, more preferably more than 10: 1 and in particular more than 20: 1. 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 mentioned, 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 wt .-%, 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.
  • % preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9 wt.% Of carbonate (s) 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 of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • 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. 5 011066
  • 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 .-%.
  • 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.
  • Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • 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
  • Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.
  • 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.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • 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 group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • preferred surfactants low-foaming nonionic "surfactants.
  • detergents or cleaning agents in particular Detergent for automatic dishwashing nonionic surfactants, in particular nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per Mo! Alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, Ci 2-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C. 12-18 -Alkoho- Ie with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -i 4 -alcohol with 3 EO and Ci 2 -i 8 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical mean values which, for a specific product, may correspond to an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • 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 and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • 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.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula
  • 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.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [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.
  • surfactants are further used which contain one or more Taigfettalkohole with 20 to 30 EO in combination with a silicone defoamer.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference. Particular preference is given to nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • 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 polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred, solid at room temperature nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 -alcohol), preferably a C 18 -alcohol and at least 12 moles, preferably obtained at least 15 mol and in particular at least 20 moles of ethylene oxide.
  • C 16-20 -alcohol a straight chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol and at least 12 moles, preferably obtained at least 15 mol and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow rank ethoxylates" are particularly preferred.
  • the C 6 - 2 o monohydroxyalkanols or C 6 . 2 o-alkylphenols or C ⁇ o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained used.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25% by weight, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • 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 moles 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.
  • Non-ionic surfactants that can be used with particular preference are available, for example, under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 are further particularly preferred nonionic surfactants.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants 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 one Is methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • 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, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • 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 is for Values between 1 and 30
  • k and j are for 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.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 .
  • 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 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. Examples of alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, such as 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.
  • 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.
  • R 2 or R 3 is a radical -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.
  • nonionic surfactants having a C 9-15 alkyl group 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.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical and x stands for values between 1 and 40.
  • R 3 in the abovementioned general formula is H.
  • nonionic surfactants are preferred in which 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.
  • those end-capped poly (oxyalkylated) nonionic surfactants are preferred which are in accordance with the formula
  • 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 which is adjacent to a monohydroxylated intermediate group - CH 2 CH (OH) -.
  • x in this formula stands for values between 1 and 90.
  • radical R 1 which in addition to a 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 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH (OH) - and in which x is between 40 and 80, preferably between 40 and 60.
  • 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 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH (
  • the corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be prepared, for example, by reacting a terminal epoxide of the formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] x-1 CH 2 Obtained CH 2 OH.
  • 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 , and x and y independently of one another for values between 1 and 32, with nonionic surfactants having values of x of 15 to 32 and y of 0.5 and 1.5 being most 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.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the production process, commercial products of the formulas mentioned mostly do not consist of an individual representative but of mixtures, which means that average values and, consequently, fractional numbers can result for both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather 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.
  • Preferred surfactants of the sulfonate type are C 3-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • Alkanesulfonates which are obtained from Ci 2 -i 8 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 containing 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 the Schwefelhoffreraumester C 2 -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.
  • Ci 2 -Ci ⁇ -alkyl sulfates and Ci 2 -C 15 - alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • the 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 2 i-alcohols such as 2-methyl-branched Cg-n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • 1- fat alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small quantities, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -i 8 - fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be 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.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” in the context 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 dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 ,
  • 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.
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
  • 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 from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p Toluene sulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • 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 (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -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
  • R1HC CR2-C (O) -NH- (CH 2) -N + R 3 R4R5
  • 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 2 -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6.
  • X " chloride also referred to as MAPTAC (Methyacrylamidopropyl- 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 usable 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
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyl trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers come from the group of methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the
  • amphoteric polymers from the group of:
  • 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, fusible
  • Coating composition preferably by means of water-insoluble coating agent from the
  • 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.
  • the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent is.
  • 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 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-trimethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
  • 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.
  • copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid,
  • 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 Copolymerisatio ⁇ of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the 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 sulphonic acid groups, as a result of which the structural units in the molecule are changed.
  • the sulfonic acid groups may be wholly or partially in neutralized form, that is, the acidic acid of the sulfonic acid group in some or all of them Sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular against sodium ions.
  • metal ions preferably alkali metal ions and in particular against sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • 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.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • 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 washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmof 1 , preferably from 4000 to 25,000 gmol "1 and in particular from 5000 to 15,000 gmol " 1 .
  • the bleaching agents are a particularly preferred washing or cleaning substance.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the 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 [phthaliminoperoxyhexanoic acid (PAP)] , o-
  • Nonenylamidopersuccinates and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, Diperoxybrassylic acid, diperoxyphthalic acids, the 2-Decyidiperoxybutan-1, 4-dioic acid, N 1 N terephthaloyl di (6-aminopercaproic acid) may be used.
  • 1,12-diperoxycarboxylic acid 1,9-diperoxyazelaic acid, diperocysebacic acid, Diperoxybrassylic acid, diperoxyphthalic acids
  • 2-Decyidiperoxybutan-1, 4-dioic acid N 1 N terephthaloyl di (6-aminopercaproic acid
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • 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 agents 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.
  • Bleach activators are used in laundry detergents or cleaners, for example, to achieve an improved bleaching effect when cleaned at temperatures of 60 ° C and below.
  • As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylene-diamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxonexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) , N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2.5 diacetoxy-2,5-dihydrofuran.
  • Further bleach activators preferably used in
  • R 1 is -H, -CH 3, a C 2 - 24 alkyl or alkenyl group, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a Ci -24 alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -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 -CN X " or (HO-CH 2 -CH 2 ) 3 N (+) CH 2 -CN X " are particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH 3 ) 3 N (+) CH 2 -CN X ' , in which X "is an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.
  • 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 the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylene diamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acet
  • 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) preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.
  • bleach catalysts In addition to the conventional bleach activators or at their location also so-called bleach catalysts can be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes.
  • 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 bleach activator-containing agent used. But in special cases, more bleach activator can be used.
  • detergents or cleaners enzymes can be used. 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 cleaners contain enzymes preferably in total amounts of I x 10 -6 W s 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • 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 ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens or from B. stearothermophilus and their improved for use in detergents and cleaners further developments.
  • the B. licheniformis enzyme from Novozymes under the name Termamyl ® and from the company Genencor available 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 B. amyloliquefaciens is sold by Novozymes under the name BAN ®, and variants derived from the ⁇ - amylase ß. stearothermophilus under the names BSG ® and Novamyl ®, likewise 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, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange 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.
  • 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. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Suitable mannanases are, for example, under the names Available Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® E31L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • the .beta.-glucanase obtained from B. subtilis 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.
  • additional active ingredients for example stabilizers, emulsifiers, pigments, Bleaching or dyes are 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 polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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, such as 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 amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said 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.
  • combinatons of stabilizers are used, for example of 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.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.
  • a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
  • Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 J 2 ) and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
  • 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 Wt .-%, each based on the total glaskorrosioninhibitorumble agents effect.
  • the exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.
  • the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts.
  • the insoluble zinc salts have a particle size below 1, 7 millimeters.
  • 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 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 especially above 5 g / l (all solubilities at 20 0 C water temperature).
  • the first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, 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.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or Aikylaminotriazol.
  • Examples of the 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention can be: propyl, butyl, pentyl, heptyl, octyl, nonyl, decylyl -, undecyl, - dodecyl, -sononyl, -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.
  • the alkylamino-1,2,4-triazoles or their physiologically tolerated salts are present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 wt .-% used.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, for example 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, 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 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) - [I -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 ,
  • 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 production (contact method) is suitable, as well as by diluting a Ti (SO 4 ) 2 solution of resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, ie completely coated with a waterproof 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 processes, such as Sandwik melt coating processes 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 dissolves easily during the silver treatment or melts quickly.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 5O 0 C to 6O 0 C.
  • 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.
  • disintegration aids so-called tablet disintegrants
  • these compositions in order to shorten the disintegration times.
  • tablet disintegrants or disintegrants according to Römpp (9th edition, Bd. 6, p 4440) and Voigt "textbook of pharmaceutical technology” (6th edition, 1987, pp. 182-184) understood excipients which ensure the rapid disintegration of tablets into water or gastric juice and for the release of the drugs in resorbable form.
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents used are cellulose-based disintegrating agents, so that preferred washing and cleaning agents contain such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
  • 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, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • CMC carboxymethylcellulose
  • 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.
  • 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 admixing with 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 Celiulose As a further disintegrating agent based on cellulose or as a component of this component microcrystalline Celiulose 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 disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • 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. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, 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 acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • the alkali metal carbonates or bicarbonates 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 that release carbon dioxide from the alkali salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates,
  • Alkali metal dihydrogen phosphates and other inorganic salts preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent.
  • organic acidifying agents Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic suifonic acids such as amidosulfonic 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.
  • 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, ⁇ c-lsomethylionon and methyl cedrylketone , among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes like limes and pinas.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • 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, kanga 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, Moisturizer Oil, Myrrh Oil, Clo
  • 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 , Bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol,
  • Methyl anthranilate p-methylacetophenone, methylchavikol, p-methylquinoline, methyl-naphthyl ketone, methyln-nonylacetaldehyde, methyl n-nonyl ketone, muscone, beta-naphtholethyl ether, beta-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, ⁇ -phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrol, salicylic acid isoamyiester, salicylic acid methyl ester, salicylic acid hexyl ester, cyclohexyl salicylate, s
  • 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.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • 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 selected dye concentrations in the range of some 10 "2 to 10 ⁇ 3 wt .-%.
  • the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 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 substances from the group of electrolytes, pH regulators, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners,
  • Grayness inhibitors anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents 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 can be added to laundry detergents or cleaners to eliminate graying and yellowing of the treated fabrics, which are absorbed by the fiber and cause lightening and faking Bleaching action by converting invisible ultraviolet radiation into visible longer wavelength light, wherein the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and gives a pure white with the yellow color of the grayed or yellowed laundry.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene,
  • Methylumbelliferones coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems, and heterocyclic substituted 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.
  • polyvinylpyrrolidone is useful.
  • Cellulosic ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, can furthermore be used as graying inhibitors
  • Methylhydroxyethylcellulose methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
  • 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 polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical.
  • 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 However, due to its insufficient biodegradability, this compound is increasingly being replaced by quaternary ammonium compounds which contain ester groups as biodegradation breakpoints in their hydrophobic residues Such esterquats having improved biodegradability are obtainable, for example, by mixing mixtures of methyldiethanolamine and / or or triethanolamine is esterified with fatty acids and the reaction products are then quaternized with alkylating agents in a manner known per se.
  • 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 include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own 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 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.
  • protein hydrolysates are preferred as such, 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. Also possible is the use of derivatives of protein hydrolysates, 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, dimethylsulfoxide, sulfolane), nitro compounds (nitrobenzene), halogenated hydrocarbons (dich
  • 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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  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des corps moulés d'agent de lavage ou de nettoyage, comprenant une cavité qui présente au moins deux ouvertures à la surface du corps moulé. L'invention se caractérise en ce que les ouvertures de la cavité sont refermées par deux éléments de scellement séparés. Les corps moulés conviennent à la confection commune de compositions d'agent de lavage ou de nettoyage solides et liquides ou aptes à l'écoulement, dans une unité de dosage.
EP05803738A 2004-10-22 2005-10-14 Agents de lavage ou de nettoyage Withdrawn EP1802736A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004051553A DE102004051553B4 (de) 2004-10-22 2004-10-22 Wasch- oder Reinigungsmittel
PCT/EP2005/011066 WO2006045452A1 (fr) 2004-10-22 2005-10-14 Agents de lavage ou de nettoyage

Publications (1)

Publication Number Publication Date
EP1802736A1 true EP1802736A1 (fr) 2007-07-04

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP05803738A Withdrawn EP1802736A1 (fr) 2004-10-22 2005-10-14 Agents de lavage ou de nettoyage

Country Status (4)

Country Link
US (1) US20070244025A1 (fr)
EP (1) EP1802736A1 (fr)
DE (1) DE102004051553B4 (fr)
WO (1) WO2006045452A1 (fr)

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DE102005022786B4 (de) * 2005-05-12 2016-09-15 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmitteldosiereinheit
US9611451B2 (en) * 2012-09-06 2017-04-04 John Moore Metal-safe solid form aqueous-based compositions and methods to remove polymeric materials in electronics manufacturing
EP2970831B1 (fr) 2013-03-14 2019-03-27 Ecolab USA Inc. Détergent contenant des enzymes et composition de prétrempage et procédés d'utilisation
US10851331B2 (en) 2017-04-27 2020-12-01 Ecolab Usa Inc. Solid controlled release carbonate detergent compositions
CN111225970A (zh) 2017-11-14 2020-06-02 埃科莱布美国股份有限公司 固体控释苛性碱洗涤剂组合物
US11518961B2 (en) 2019-09-27 2022-12-06 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
CN114854504B (zh) * 2022-05-16 2024-02-23 佛山市顺德区美的洗涤电器制造有限公司 高效洗碗机专用洗涤剂组合物

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Also Published As

Publication number Publication date
DE102004051553A1 (de) 2006-04-27
DE102004051553B4 (de) 2007-09-13
WO2006045452A1 (fr) 2006-05-04
US20070244025A1 (en) 2007-10-18

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