EP1781768A1 - Corps moule detergent ou nettoyant pourvu d'un revetement - Google Patents

Corps moule detergent ou nettoyant pourvu d'un revetement

Info

Publication number
EP1781768A1
EP1781768A1 EP05769966A EP05769966A EP1781768A1 EP 1781768 A1 EP1781768 A1 EP 1781768A1 EP 05769966 A EP05769966 A EP 05769966A EP 05769966 A EP05769966 A EP 05769966A EP 1781768 A1 EP1781768 A1 EP 1781768A1
Authority
EP
European Patent Office
Prior art keywords
acid
coated
preferred
coating
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.)
Granted
Application number
EP05769966A
Other languages
German (de)
English (en)
Other versions
EP1781768B2 (fr
EP1781768B1 (fr
Inventor
Thomas Holderbaum
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34979903&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1781768(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL05769966T priority Critical patent/PL1781768T5/pl
Publication of EP1781768A1 publication Critical patent/EP1781768A1/fr
Application granted granted Critical
Publication of EP1781768B1 publication Critical patent/EP1781768B1/fr
Publication of EP1781768B2 publication Critical patent/EP1781768B2/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D17/0082—Coated tablets
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate

Definitions

  • the present invention relates to coated detergent tablets and to processes for their production.
  • the present application relates to shaped bodies which have a cavity in the form of a depression or a through hole and whose surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 .
  • 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.
  • tableted detergents or cleaners are less soluble than conventional powdered or liquid detergents or cleaners due to the high degree of densification of their constituents.
  • EP 846 754 A1, EP 846 755 A1 and EP 846 756 A1 (Procter & Gamble) describe coated detergent tablets which comprise a "core" of compacted, particulate detergent and cleaning agent and a "coating" dicarboxylic acids, in particular adipic acid, which optionally contain further ingredients, for example disintegration aids, are used as coating materials.
  • Coated detergent tablets are also the subject of European patent application EP 716 144 A2 (Unilever). According to the information in this document, the hardness of the tablets can be increased by a "coating", without affecting the disintegration and dissolution times.
  • coating agents film-forming substances, in particular copolymers of acrylic acid and maleic acid or sugar and polyethylene glycols are mentioned.
  • the object of the present application was therefore to provide laundry detergent or cleaning product tablets which are distinguished by a significantly improved solubility with respect to the known shaped articles of the prior art with the same or comparable breakage hardness.
  • the shaped bodies should have improved cold water solubility.
  • the resulting coated moldings should be free of further packaging. In particular, without further outer packaging of water-insoluble polymer films to be stored and transported.
  • This object has been achieved by a coating process for washing or make sure ⁇ moldings, in which the molding surface is coated with a surface coverage between 0.2 and 50 mg / cm 2 .
  • a process for producing a washing or cleaning agent shaped body comprising the steps of a) providing a shaped body which has a cavity in the form of a depression or a through hole; b) applying a coating agent to the surface of the shaped article, such that the surface coverage of the coated shaped article surface with the coating agent is between 0.2 and 50 mg / cm 2 .
  • Preferred processes according to the invention are characterized in that the surface area of the shaped body 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 coating compositions can be used as pure substances, for example in the form of their melts, but also as dispersions or solutions.
  • organic solvents are also suitable as dispersants, with aqueous dispersions or aqueous solutions being particularly preferred.
  • These dispersions or solutions, in particular the aqueous dispersions or solutions preferably have a weight fraction of the coating agent below 80% by weight, preferably below 65% by weight, more preferably below 50% by weight and in particular below 40% by weight .-%, in each case based on the total weight of the dispersion or the solution on.
  • the loading of the shaped body with the coating agent is preferably carried out by spraying.
  • spraying for spraying the moldings, all known to those skilled in the art for this purpose are suitable.
  • the spraying is preferably carried out by means of single-component or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
  • single-substance spray nozzles the use of a high melt pressure (5-15 MPa) is required, while spraying in two-component spray nozzles takes place with the aid of a stream of compressed air (at 0.15-0.3 MPa).
  • the spraying with dual-fluid spray nozzles is particularly with regard to possible blockages of the Nozzle cheaper, but more expensive due to the high compressed air consumption.
  • 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 nozzles in the process room can spray from top to bottom or from bottom to top.
  • Particularly preferred are methods in which the spraying device is integrated into the side walls bounding the process chamber and fixed there.
  • Particularly preferred are those methods in which two or more spraying devices are used in the process chamber, wherein at least two of the spraying devices differ with regard to their orientation, that is, with regard to their spraying direction.
  • the shaped body and the spraying device are moved relative to one another during the spraying process.
  • This movement can be realized both by a movement of the shaped body and by a movement of the spraying device or by the movement of the shaped body and spraying device.
  • Particularly preferred are those methods in which the spraying device is moved in at least one spatial direction, preferably in two or three spatial directions. If, at the same time, the shaped bodies are also moved, the direction of movement of the spraying device can, for example, run counter to or coincide with the direction of movement of the shaped bodies. Also, a movement of the spray device orthogonal to the direction of movement of the Form ⁇ body can be performed.
  • the moldings can be moved continuously and discontinuously into and through the process space of the spray device.
  • the drop diameter of the sprayed-on coating material or the sprayed coating dispersion or solution is preferably between 1 and 100 .mu.m, particularly preferably between 2 and 80 .mu.m, very particularly preferably between 4 and 70 .mu.m and in particular between 8 and 60 .mu.m.
  • the temperature of the sprayed coating material be ⁇ contributes preferably between 20 and 90 0 C 1 preferably between 25 and 6O 0 C, particularly preferably between 30 and 55 ° C and in particular between 40 and 5O 0 C.
  • a surface load of the shaped body surface by the sprayed liquid is between 0.1 and 200 mg / (cm 2 s), preferably between 0, 2 and 100 mg / (cm 2 s), more preferably between 0.4 and 50 mg / (m 2 s) and in particular between 0.8 and 20 mg / (cm 2 s).
  • the mandate of Stratification agent on the molding is preferably completed in less than 10 minutes, preferably less than 5 minutes, more preferably less than 2 minutes, most preferably less than 1 minute, and most preferably less than 0.5 minutes.
  • the detergent tablets are preferably present in isolated form, that is to say without direct contact with one another.
  • the process according to the invention thus differs from those coating processes in which ordered or disordered stacks or piles of shaped articles, for example in drum coats or coating pans, are coated.
  • Method characterized in that the coating agent is sprayed onto the molding, are particularly preferred.
  • the sprayed washing or cleaning agent shaped body is preferably dried after spraying.
  • the drying can be carried out, for example, thermally and / or by the action of a vacuum. In the case of thermal drying, methods using hot air or heat radiation are preferred. Drying temperatures are preferably between 35 and 90 0 C, preferably between 40 and 80 0 C and in particular between 50 and 70 ° C.
  • the drying of the moldings is generally not complete, that is, not the entire amount of solvent applied by the spraying is removed by the drying.
  • This evaporated fraction can be determined by weighing the uncoated molded body, the wet molded article before drying and the dried molded article, i. be determined from the measured before and after drying weight increase of the molding.
  • 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 their derivatives and their mixtures.
  • PVAL polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • polyethylene oxide polyethylene oxide
  • gelatin gelatin
  • cellulose and their derivatives and their mixtures.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerisation 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 87-99. 89 mol%, so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by specifying 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 highly 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 abbau ⁇ bar.
  • 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 consists of at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating material, it being preferred according to the invention that the film material comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmof, preferably 11,000 to 90,000 gmol -1 , particularly preferably 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 from about 200 to about 2100, preferably from about 220 to about 1890, more preferably from about 240 to about 1680, and most preferably from about 260 to about 1500.
  • Polyvinyialkohole 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 Polyvinyialkohole for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • Polyvinyialkohole are ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), Erkol 05-140 , 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).
  • aldehydes acetalization
  • ketones ketalization
  • Polyvinyl alcohols which have been found to be particularly acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous owing to their excellent 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.
  • Suitable water PVAL coating materials are those available under the name "SOLUBLON® ®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. PVAL Subtanzen. Their solubility in water can be adjusted precisely to the degree, and coating materials of this product series are obtainable 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 offered 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.
  • Gelatine 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 gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • 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.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically. Starch is composed of two components of different molecular weights: about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included.
  • amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position
  • the chain branches in the case of amylopectin to an average of 25 glucose building blocks by 1,6-binding branch-like structures with approximately 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the production of coatings in the context of the present invention. Examples of such chemically modified starches include products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • starches in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also 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 H 10 O 5 ) n and formally represents a ⁇ -1,4-polyacetal of cellobiose, which in turn is built up from 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.
  • Cellulosic 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 from esterifications or etherifications in which hydroxyhydrogen atoms have been substituted.
  • celluloses in where the hydroxy groups have been replaced by functional groups which are not bound by an oxygen atom, can be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Further preferred coating materials are characterized in that they comprise hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1, 9, and a molar substitution (average number of Hydroxypropo- xyl phenomenon per Anhy-droglucose unit of the cellulose) of 0.1 to 0.3, preferably from 0.15 to 0.25, having.
  • HPMC hydroxypropylmethylcellulose
  • a water-soluble organic polymer preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ether
  • a water-soluble organic polymer preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ether
  • coating agent preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ether
  • the inventive method is suitable for simple as well as repeated coating of the shaped body.
  • a method characterized in that the coating agent is applied to the molding by the moldings is repeatedly sprayed with a solution or a Dis ⁇ persion of the coating composition, are preferred according to the invention.
  • a "rangfa ⁇ che” or “repeated” coating of the molding takes place in such a way that the molding 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 after this repeated 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
  • a further subject of the present application is therefore a process for the preparation of a washing or cleaning agent shaped article comprising the steps a) providing a shaped body which has a cavity in the form of a trough or a through hole; b) Repeated application of a coating agent to the surface of the shaped article so that the surface coverage of the coated shaped article surface with the coating agent is between 0.2 and 50 mg / cm 2 for each coating operation.
  • Further 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 second or third coating material in the case of repeated coating of the shaped bodies are a) the LCST substances b) the waxes c) 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 conditions of use, the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment, for example between 2O 0 C, preferably 3O 0 C and 100 0 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), hydrodoxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC) , Methyl hydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose (PC) and mixtures thereof, preference being given to carboxymethylcellulose (
  • LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • Other polymers which show a lower critical Entmischungs ⁇ 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 intertwined 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 (VATGVV), a repeating unit in the natural Protein elastin and certain alginates.
  • LCST low 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 viscous and non-stringy, and have a strongly 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, sugarcane 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.
  • vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or
  • 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 usable as coating materials are compounds from others Classes of substances meeting the said softening point requirements. 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.
  • liquid and solid paraffins are preferably used as a solution or dispersion in an organic solvent or solvent mixture.
  • the use of paraffins without the addition of solvent in the form of melts or liquids is possible.
  • 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 hydrolysis 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 ° 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 articles 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 table below gives an overview of a number of particularly preferred sequences of these coating materials.
  • the coating marked as the first layer corresponds to the layer first applied to the shaped body.
  • the coating materials can be mixed with active ingredients and active ingredients. Dyes, fragrances or bitter substances are preferably added to the coating materials.
  • the spatial form of the detergent tablets is not subject to any restriction.
  • Examples are spatial bodies with a polygonal base, wherein the body represents a continuation of the polygonal base in the room.
  • Preferred examples of the polygonal body are prismatic bodies.
  • Examples of the prismatic body are trigonal prisms, rhombic prisms, orthorhombic prisms, tetragonal prisms, pentagonal prisms, hexagonal prisms, or octagonal prisms. Particularly preferred is a cuboid shape.
  • Examples of other suitable polygonal bodies are trigonal, tetragonal, rhombic, orthorhombic, hexagonal or octagonal pyramids and dipyramids.
  • the body may also be a hybrid of different geometric bodies. Preference is furthermore given to moldings with an oval or round base surface, wherein the body preferably again represents a continuation of the base surface in the room.
  • the volume of the washing or cleaning agent tablets is preferably between 12 and 30 ml, preferably between 15 and 25 ml and in particular between 17 and 22 ml.
  • the weight of the tablets is preferably between 10 and 25 g.
  • Such washing or cleaning product tablets are particularly suitable as dosing units for single use.
  • the dosage of these moldings is usually done via the metering chambers of washing machines or dishwashers.
  • the spatial form of the shaped body can therefore of course also be adapted to any irregular shapes of metering compartments / induction chambers of different washing machines and dishwashers.
  • a cuboid shape of the washing or cleaning agent shaped body is preferred insofar as this makes it possible to fill in the usual cuboid insufflation chambers or dishwashers best in terms of volume.
  • cuboid-shaped washing or cleaning agents can be stored very well in a space-saving manner.
  • moldings with convex or concave side surfaces can also be used.
  • a preferred embodiment of a shaped body with a concave side surface is the molded body.
  • the well volume of these shaped bodies preferably corresponds to at least 10% by volume, preferably at least 20% by volume and in particular at least 40% by volume of the molding volume (without the depression).
  • the detergent tablets may have a cavity in the form of a through hole.
  • the openings of this hole can be found in adjoining side surfaces and / or in opposite side surfaces of the molding. If the openings of the hole are located on mutually opposite sides of the shaped body, the corresponding shaped bodies are also referred to as ring shaped bodies or ring tablets.
  • the moldings used in the process according to the invention may be, for example, cast bodies, (extruded) extrudates or compactates. With particular preference tablets are used as tablets. To prepare tablets, particulate premixes are compacted in a so-called matrix between two punches to form a solid compact. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction, plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved by a volumetric metering of the premix. This is due to a good flowability of the premix and a not too coarse grain structure, which is preferably achieved by screening with a sieve having a mesh size of 1, 6 mm, preferably of 1, 5 mm and in particular of 1, 4 mm.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, wherein the void volume decreases continuously within the Fül ⁇ ment between the punches.
  • the plastic deformation begins, in which the particles flow together and the formation of the shaped body occurs.
  • some of the premix particles are also crushed, and at even higher pressures sintering of the premix occurs.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and transported away by following transport devices. At this time, only the weight of the molded article is finally determined, since the compacts due to physical processes (Rückdeh ⁇ voltage, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used for pressure build-up, also the lower punch moves during the pressing operation on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used, in which the die or punches are fastened to an eccentric disk, which in turn is mounted on an axis with a certain rotational speed. The movement of these press-punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary according to the type of a few hundred to a maximum of 3000 tablets per hour.
  • the lower punch is as a rule not moved during the pressing process.
  • the resulting tablet has a hardness gradient, i. harder in the areas closer to the upper punch than in the areas closer to the lower punch.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being pushed out before the further filling.
  • sheath and point tablets which have an onion-shell-like construction, wherein in the case of the point tabs the top side of the core or core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 holes and an inner circle with 35 holes are simultaneously used for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • the tablets in the context of the present invention also multi-phase, in particular multi-layered, ausgestalten.
  • the moldings can be manufactured in saucepan ⁇ specific spatial form and predetermined size.
  • the training as a blackboard the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or ova ⁇ lem cross section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • ⁇ stands for the diametrical fracture stress (DFS) in Pa
  • P is the force in N, which leads to the pressure exerted on the molding, which causes the breakage of the molding
  • D is the molding diameter in meters
  • t is the height of the moldings.
  • the stability and hardness of the processed shaped bodies can be improved by the process according to the invention without impairing their decomposition and dissolution properties.
  • the shaped article is characterized by an increased breaking strength while the dissolution behavior remains the same.
  • this "contamination” should preferably be less than 10% by weight, preferably less than 5% by weight and in particular less than 3 wt .-% of the total amount of the applied coating agent amount.
  • preferred processes according to the invention are characterized in that the coating in step b) takes place on the outer surfaces of the molding with the cavity, but not within the cavity.
  • a preferred subject of the present application is therefore a process for the preparation of a laundry detergent or cleaning product tablet, comprising the steps of a) providing a tablet, preferably a tablet, having a cavity in the form of a trough or a through hole; b) applying a coating agent to the surface of the molding so that the surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 , wherein the coating on the strig ⁇ surfaces of the molding, but not within the Cavity is applied.
  • the coating of the shaped body is also repeated in this process variant, preferably twice, three times or four times.
  • the cavity of the above-described troughed or ring-shaped bodies is filled with a washing- or cleaning-active substance or a washing or cleaning-active substance mixture.
  • filler materials preference is given to a) particulate compositions from the group of powders, granules or extrudates or b) liquid or gel-form preparations.
  • liquid preparations for example, solutions or melts can be filled.
  • the filling of the cavity can be carried out before or after the application of the coating material, but also between two coating courses. Preference is given to processes in which the filling takes place after the coating of the shaped body.
  • the substances or mixtures of substances filled in the cavity can be fixed in the cavity in different ways.
  • the substances or substance mixtures are fixed in the cavity by adhesion.
  • the substances or mixtures of substances are present in a water-soluble or water-dispersible packaging, for example a deep-drawn bag or an injection-molded container, which at least partially fills the cavity and, for its part, with the molded article by adhesion or a mechanical connection, for example a latch, snap, plug or clamp connection is connected.
  • the cavity is preferably filled to at least 70% by volume, preferably at least 80% by volume, more preferably at least 90% by volume and in particular at least 95% by volume of its volume.
  • a water-soluble or water-dispersible film is sealed onto the coated surface of the shaped article, wherein the sealing is preferably carried out by heat sealing.
  • the sealed foil can perform a number of different functions.
  • a film is suitable for fixing the substances or substance mixtures filled in the cavity of the shaped body in this cavity.
  • the Bruchfes ⁇ activity and / or storage stability of the molding can be further increased.
  • the preferred film materials used are in particular the water-soluble polymers mentioned above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
  • a further subject matter of the present application is a coated detergent or cleaning product tablet, characterized in that the surface coverage of the coated tablet surface with the coating agent is between 0.2 and 50 mg / cm 2 .
  • preferred coated washing or cleaning agent tablets have a surface coverage of the coated tablet surface with the coating agent of 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 on.
  • the coating agent is preferably a water-soluble organic polymer, preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ethers.
  • the fracture hardness of the coated detergent tablets is preferably above 60 N, preferably above 80 N, particularly preferably above 100 N and in particular above 110 N.
  • the shaped bodies preferably have a cavity in the form of a depression or a through-going hole, wherein those shaped bodies which are coated on the outer surfaces but not within the cavity are particularly preferred.
  • the cavity of the shaped bodies according to the invention is preferably filled.
  • Preferred coated washing or cleaning agent shaped articles are characterized in that the shaped article comprises a coated surface and a water-soluble or water-dispersible film, wherein the coating and the water-soluble or water-dispersible film are at least partially fused together.
  • compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning-active substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors , Corrosion inhibitors, disintegrants, fragrances and perfume carriers.
  • the funds are therefore in usually water-soluble or water-dispersible.
  • the preferred ingredients of these agents will be described in more detail below.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight).
  • zeolite X) which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and as 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
  • Zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, 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 • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • these silicates are Na-SKS-1 (Na 2 Si 22 O 45 • x H 2 O, Ken yait), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 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 (X-Na 2 Si 2 O 5 )
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O • 5 H 2 O
  • Na-SKS-10 NaH Si 2 O 5 ⁇ 3 H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 0 5)
  • 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 2% by weight 3 wt .-% and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt. % and in particular at least 90 wt .-% of silicate of the general formula NaMSi- x O 2x + i • y H 2 O is.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates can be produced 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 in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles give washed-out 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 likewise 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.
  • these silicate (s) preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, be present in detergents or cleaners in amounts of from 10 to 60% by weight, preferably 15 to 50 wt .-% and in particu lar from 20 to 40 wt .-%, each based on the weight of the washing or views ⁇ means contained.
  • compositions according to the invention or agents prepared by the process according to the invention as automatic dishwashing agents which is particularly preferred in the context of the present application.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to relatively high molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and, moreover, contribute to the cleaning performance.
  • Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of dihydrate (density 1, 91 like “3 , melting point 60 0 C) or in the form of monohydrate (density 2.04 like '3 ), the disodium hydrogen phosphate (secondary sodium phosphate ), Na 2 HPO 4 , which is anhydrous or with 2 moles (density 2.066 like '3 , loss of water at 95 ° C), 7 moles (density 1, 68 like "3 , melting point 48 ° C with loss of 5 H 2 O) and 12 moles of water (density 1, 52 "3 , melting point 35 0 C with loss of 5 H 2 O) can be used, but especially the Trinatri ⁇ umphosphat (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 0 C, also 88O 0 C given) and as decahydrate (density 1, 815-1 , 836 like "3 , melting point 94 ° C under loss of water), as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 .
  • the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade ,
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which can likewise 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 are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; It is also possible to use 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 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 metal 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 .-% , Particularly preferably below 4 wt .-% and in particular below 2 wt .-%, in each case based on the total weight of the washing or cleaning agent Lane ⁇ sets.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • 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, sugic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixtures of these , Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically 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.
  • Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or 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 Molisswer ⁇ te due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 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 proved 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 cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
  • biodegradable polymers from more than two different monomer units, for example those which contain, as monomers, salts of acrylic acid and maleic acid and also vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallyl sulfonic acid as monomers, and Contain sugar derivatives.
  • Further preferred copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • 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, terephthalic aldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molar masses in the range from 400 to 500 000 g / mol. .
  • Spanish is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 is preferred, where DE is a common measure of the reducing action of a polysaccharide in comparison to dextrose, which is a DE of 100 is.
  • DE dextrose equivalent
  • maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with relatively high 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.
  • Ethylenediamine-N, N'-disuccinate (EDDS) Queen ⁇ Trains t in the form of its sodium or magnesium salts.
  • EDDS Ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • Suitable men ⁇ conditions are in zeolite-containing 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 min. 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 which may be used are all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, detergents or cleaners, in particular detergents for automatic dishwashing, contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • alcohol ethoxylates with 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 mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alkoxy holethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow homolog distribution
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms.
  • R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms.
  • G is the symbol which represents a glycose unit with 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 stands.
  • 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 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 group or an oxyalkyl group having 1 to 8 carbon atoms, where C 1-4 alkyl or Phe nylreste are preferred
  • [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [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-aryl-oxy-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 which contain one or more Taigfett ⁇ alcohols having 20 to 30 EO in combination with a silicone defoamer.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • 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. Nioten ⁇ side, which have waxy consistency at room temperature, are also preferred.
  • surfactants which are solid at room temperature, are derived 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 / poly-oxypropylene ((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 which consists of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is selected from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 -AlkOhOl), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol ethylene oxide won.
  • the so-called "narrow rank ethoxylates" are particularly preferred.
  • ethoxylated nonionic surfactant selected from C 6-2O - monohydroxy alkanols or C 6 - 2 o-alkyl phenols or C 16-2 o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol were used.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of Vietnameseioni ⁇ 's surfactant from.
  • 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 makes up 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 surfactant.
  • nonionic surfactants with melting points above room temperature contain 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 Wt .-% 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 contains.
  • Nonionic surfactants which can be used with particular preference are beispielswei ⁇ se under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 OI y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x is 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 a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5.
  • 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, 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 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • 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 is -butyl, 2-butyl or 2-methyl-2-butyl radical
  • x is between 1 and 30
  • k and j are between 1 and 12, preferably between 1 and 5, preferably wherein 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, with one to ten EO or AO groups each being bonded to one another before a block follows from the respective other groups.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 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.
  • the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical containing 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 selected independently of one another from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are also suitable.
  • 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 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which are preferably have from 1 to 5 hydroxyl 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. From the group of the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, preferably from 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 is between 1 and 40.
  • end-capped poly (oxyalkylated) nonionic surfactants are preferably added, which are prepared according to the formula
  • radical R 1 which is linear or branched, saturated or unsaturated, aliphati ⁇ cal 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 Kohlen ⁇ atoms, which is a monohydroxylated intermediate group -CH 2 CH (OH) - be ⁇ neighbors.
  • x in this formula stands for values between 1 and 90.
  • radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably 4 to 22 carbon atoms, furthermore 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 a monohydroxylated intermediate group -CH 2 CH (OH) - adjacent and in which x for values between 40 and 80, preferably for Values between 40 and 60 are available.
  • 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 CH 2 OH obtained.
  • R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably -CH 3
  • x and y independently of one another are values between 1 and 32, wherein nonionic surfactants with values of x from 15 to 32 and y of 0.5 and 1.5 are 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 most preferred.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical average values which may be a whole or a fractional number for a specific product. Due to the production process, commercial products of the formulas mentioned are usually not made up of an individual representative but of mixtures, which may result in both the C chain lengths and the degrees of ethoxylation or alkoxylation-averaged mean values and, consequently, fractional numbers.
  • nonionic surfactants can be used not only as individual components 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 those mixtures which contain two, three, four or more nonionic surfactants which are described by means of different general formulas can be.
  • anionic surfactants used are those of the sulfonate and sulfates type.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates containing 12 -i 8 alkanes drolyse from C for example by sulfochlorination or sulfoxidation and subsequent Hy ⁇ or neutralization can be obtained.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taig ⁇ fatty acids are suitable.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • Fatty acid glycerines are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as 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 can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali metal and especially sodium salts of the sulfuric acid endeavourester the C 12 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 2 o-oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C S alkyl sulfates and C- ⁇ -C-is-alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -n-alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci 2- i 8 - Fatty alcohols with 1 to 4 EO are suitable.
  • EO ethylene oxide
  • Ci 2- i 8 - Fatty alcohols with 1 to 4 EO are suitable. You will be in Because of their high foaming behavior only in relatively small amounts, spielmik in amounts of 1 to 5 wt .-%, used.
  • 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 e 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.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable fatty acid soaps are fatty acids 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. %. 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 and can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain Groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of Acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, of vinylpyrrolidone-methoimidazolinium chloride copolymers, of quaternized polyvinyl alcohols or of the polyesters specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 mers.
  • 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, for example, be 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 independently of one another are H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 independently of one another are an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has from 1 to 6 carbon atoms, which is 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-toluenesulfonate (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 (CHs) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • X " chloride as DADMAC (diallyldimethylammonium chloride) bezeich ⁇ net.
  • cationic or amphoteric polymers comprise a monomer unit of the general formula
  • R 1 HC CR 2 -C (O) -NH- (CH 2 ) -N + R 3 R 4 R 5
  • X ' in the R 1 , R 2 , R 3 , R 4 and R 5 independently of one another represent a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched one 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 H and x is an integer between 1 and 6.
  • C 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 their derivatives Derivatives, the allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred amphoteric polymers which can be used are selected from the group of the alkylacrylamide / acrylic-isocyanic copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers which cationically derivatized alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / AI-kymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids unsaturated carboxylic acids and optionally further ionic
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltri alkylammonium 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, in addition to one or more anionic monomers, comprise methacrylamidoalkyl trialkyl ammonium chloride and dimethyl (di-allyl) ammonium chloride as cationic monomers.
  • amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltri-alkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylyldialkylammonium chloride / dimethylcyclodially ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl - (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / Alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • the polymers are present in prefabricated form.
  • encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions is suitable, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating agent, preferably by means of water-insoluble coating agent from the group of waxes or paraffins having a melting point above 30 0 C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.
  • Detergents or cleaning agents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the detergent or cleaning agent.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally wei ⁇ nic 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, with -NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or for -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1 propanesulfonic acid, 3-methacrylamido-2-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.
  • Suitable further ionic or nonionic monomers are, in particular, 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, methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:
  • the copolymers may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) being combined with all the representatives from group ii) and all representatives from group iii) can nen ⁇ .
  • 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 copolymerizing acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the sulfonic acid-containing acylic acid derivative is copolymerized with methacryic acid, the result is another polymer whose use is also preferred.
  • the corresponding copolymers contain the structural units of the formula
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • the sulfonic acid groups may be completely or partially in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced.
  • metal ions preferably alkali metal ions and in particular against Sodium ions.
  • the use of partially or fully neutralized sulfonic acid group-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 containing 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 intended use.
  • Preferred detergents or cleaners are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1, and in particular from 5000 to 15,000 gmol -1 .
  • the bleaching agents are a washing or cleaning-active substance used with particular preference.
  • the sodium percarbonate, the sodium perborate tetrahydrate and the sodium perborate monohydrate have special significance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrazates and peracid salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • 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-
  • a bleaching agent and 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 salts thereof with cations such as potassium and sodium.
  • heterocyclic N-bromo- and N-chloroamides for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof 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 dishwashing detergents, are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, more preferably from 3.5 to 20% by weight, and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate.
  • the active oxygen content of the washing or cleaning agents, in particular the machine dishwashing detergents is in each case, based on the total weight of the composition, preferably between 0.4 and 10% by weight, particularly preferably between 0.5 and 8% by weight .-% 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-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU ), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
  • R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, 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 Alkenylarylrest with a C - ⁇ - 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
  • bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylene diamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acyl-limide, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nano-nyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyvalent Alcohols, in particular triacetin, ethylene glycol di-acetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-
  • 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 phenol-sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8 % By weight, in particular from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the bleach activator-containing agents.
  • TAED tetraacetylethylenediamine
  • NOSI N-nonanoylsuccinimide
  • bleach catalysts can also be used.
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt 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.
  • 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 ( ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of the manganese sulfate are added in conventional amounts, preferably in an amount of up to 5% by weight.
  • Enzymes can be used to increase the washing or cleaning performance of detergents or cleaning agents. 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 accordingly preferably used. Washing or cleaning agent containing enzymes vor ⁇ preferably in total amounts of 1 x 10 "-6 to 5 wt .-% based on active protein. The Prote ⁇ can inkonzentration using known methods, determined, for example the BCA method and the biuret method become.
  • subtilisin type examples thereof are the subtilisin 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 which can no longer be assigned to the subtilisins in the narrower sense and the proteases TW3 and TW7.
  • subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvserd, 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 ®, re lase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, which from under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® Genencor, which serves under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, In ⁇ , under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® from Amano Pharmaceuti- cals Ltd., Nagoya, Japan, and the proteinase under the name K-16 from Kao Corp., Tokyo, Japan, available enzymes.
  • 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 enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
  • ⁇ -amylase Development products of this ⁇ -amylase are nencor from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from the company Ge under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ® available.
  • the ⁇ -amylase of ⁇ . amyloliquefaciens is sold by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B.. stearothermophilus under the names BSG ® and Novamyl ®, also from the Company Novozy ⁇ mes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. 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 ® span ⁇ Lich. From Genencor, for example, the lipases or cutinases can be used, whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • mannanases which are combined under the term hemicellulases.
  • Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA 1 USA. The from ß.
  • subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect , 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 electron flow at greatly varying redox potentials between the oxidizing enzymes and the soiling (mediators).
  • the enzymes originate, for example, either originally from microorganisms, such as the genus 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 methods which are in themselves established, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, the action of 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 compositions, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or with stabilizers.
  • the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray-drying or extrusion of the enzyme solution zu ⁇ together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes 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 chemicals impermeable protective layer.
  • additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes can be additionally applied.
  • Such capsules are applied according to methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • Vor ⁇ geous enough such granules, for example, by applying polymeric film-forming, low-dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
  • a protein and / or enzyme can be protected, especially during storage, against damage such as inactivation, denaturation or degradation, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, for example 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 agents constitutes a preferred embodiment of the present invention.
  • One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are aminoalcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to Ci 2, 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 can additionally stabilize 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 are used, for example 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. Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation.
  • 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 increased 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 originate 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 not more than 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of insoluble zinc salts which are particularly preferred 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 glass corrosion inhibitor-containing agent effect.
  • the exact content of the agents on the zinc salt or zinc salts is of course dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the compositions should be. Since the insoluble zinc salts remain largely unchanged during the Geschirmentsvorgangs, 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 preferably 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 poorly 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 change corrosively, in particular no clouding, streaks or scratches, but also no iridescence of the glass surfaces are caused.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic sheu ⁇ ren 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 which prefers 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.
  • the spectrum of the inventively preferred zinc salts of organic acids ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l have, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 2O 0 C water temperature).
  • the first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor used is 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 zinc nitrate. Zinc ricinoleate, zinc abate and zinc oxalate are also preferred.
  • the content of cleaning agents with zinc salt is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight, or the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 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 alkylaminotriazole.
  • 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention which may be mentioned are: propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl -, Undecyl-, -Dodecyl-, -Isononyl-, Versatic-10-Alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert-butylphenyl) -, - (4-Methoxyphenyl) -, - (2-, 3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, 3-amino-1, 2,4-triazole.
  • 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.
  • cleaning agent formulations frequently 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, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phosphoroglucin, pyrogallol or derivatives of these classes of compounds are used.
  • salt and Komite plexieri inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce often use.
  • 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 comprise all conventional one-, two- or three-fold 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 which are monodentate or polydentate;
  • the term "ligand" within the meaning of the invention is e.g. in "Rompp 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) are not zero, then, depending on whether there is a cationic or an anionic charge surplus, either one or more of the above-mentioned.
  • Anions or one or more cations e.g. Sodium, potassium, Ammoni ⁇ umionen, for the charge balance.
  • Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [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) - [I -hydroxyethane-1, 1 - diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 ,
  • metal salts or metal complexes are generally commercially available substances for the purpose of silver corrosion protection without prior. Cleaning in the detergents or cleaning agents can be used.
  • 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 resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, ie completely coated with a water-tight material, but 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 point Schmelz ⁇ should ideally be in the range between 45 C C and 65 0 C and preferably in the range 50 0 C to 60 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 are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinylpyrrolidone
  • 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.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents, so that preferred washing and cleaning agents contain such cellulose-based disintegrating 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% by weight .-% contain.
  • Pure cellulose has the formal gross composition (C 6 H 10 Os) n 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 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 from esterification or etherification 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. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • microcrystalline cellulose As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, but leave the crystalline regions (about 70%) intact ,
  • a subsequent desaggregation 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 auxiliaries preferably a disintegrants based on cellulose, preferably in granular, cogranulated or compacted form, are present in the 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, based in each case on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegrating additives.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon 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 that release, for example, nitrogen, oxygen or hydrogen, the bubbling system used in the washing and cleaning agent will be selectable on the basis of both economic and ecological 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 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.
  • 2 to 20% by weight preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15 are preferred as effervescent system, preferably 2 to 12% by weight and in particular 3 to 10% by weight of an acidifying agent, in each case based on the total weight of the agent used.
  • Suitable acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution are, for example, boric acid and also alkali metal hydrogensulfates, alkali metal dihydrogenphosphates and other inorganic salts.
  • organic acidifying agents are preferably used, the citric acid being a particularly preferred acidifying agent.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as amidosulfonic acid are also usable.
  • a commercially available Acidifizie ⁇ agent in 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 (max 33 wt%).
  • 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 as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarboxylate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl n-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 ionones, ⁇ > isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • perfume oils may also contain natural fragrance mixtures, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Natural fragrance mixtures such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galena oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil are also suitable.
  • the general description of the perfumes that can be used generally represents the different substance classes of fragrances.
  • 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 or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances.
  • the base note consists for the most part of less volatile, ie adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.
  • Adhesive-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, Bayöl, Bergottottöl, Champacablütenöl, Edeltannenöl, Edeltannenzapfen oil, Elemiöl, Eucalyptusöl, Fennelöl, Fichtennadelöl, Galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gum turmeric oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine needle oil, copa ⁇ va balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, Lavender oil, lemongrass oil, lime oil, tangerine oil, balm oil, musk comeal oil, myrrh oil,
  • fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate , Benzyl valerate, borneol, bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol,
  • 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 volatile fragrances are alkyl isothiocyanates (Aikylsenföle), butanedione, limonene, linalool, Linaylacetat 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.
  • Cyclodextrins for example, have proven useful as such carrier materials, with the cyclodextrin-perfume complexes additionally being able to be coated with further auxiliaries.
  • Preferred dyes the selection of which presents no difficulty to a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity towards the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic dishes not to stain them.
  • 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), which is provided as a commercial product, for example, as Basa ⁇ cid ® Green 970 from BASF, Ludwigshafen, and mixtures of these. 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 comprise one or more substances from the group of electrolytes, pH-adjusting agents, fluorescers, hydrotopes, antifogging agents, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-caking 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.
  • pH adjusters In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Usable here are all known acids or alkalis, unless their use is not from application or ecological for reasons of consumer protection. 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.
  • be ⁇ preferred means comprise 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, farblo ⁇ se, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 and 150,000, and viscosities between 10 and 1,000,000 mPa-s.
  • Suitable antiredeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on nonionic cellulose ethers and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their Deriva ⁇ th, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners may be added to detergents to remove graying and yellowing of the treated fabrics, which will be absorbed by the fiber and cause lightening and fake bleaching by exposing the invisible ultraviolet radiation to visible whitening
  • the ultraviolet light absorbed from sunlight is emitted as weakly bluish fluorescence and gives 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 (flavonic), 4,4'-biphenylene -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and the substituted heterocycles pyrene derivatives.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also something- Serosoluble, acidic group-containing polyamides are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products verwen ⁇ can, for example, degraded starch, aldehyde starches, etc.
  • polyvinylpyrrolidone is useful.
  • graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as 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 washability.
  • 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.
  • the impregnation of the impregnating agents in the form of solutions or emulsions of the active compounds in question can be facilitated by adding wetting agents which reduce the surface tension.
  • a further field of application of repellents and impregnating agents is the water-repellent finishing of textiles, tents, tarpaulins, leather, etc., in which, in contrast to water-sealing, the fabric pores are not closed, ie the fabric remains breathable (hydrophobing).
  • the hydrophobizing agents 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 hydrophobizing agents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, tin salts. organic compounds and glutaric dialdehyde and perfluorinated compounds.
  • the 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 bacteriostatic agents 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 antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines, and also organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus enable an improved discharge 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) di- methylbenzylammoniumchloride are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional Avivage bin is achieved.
  • Softeners can be used to care for the textiles and to improve the textile properties such as a softer "handle” (avivage) and reduced electrostatic charge (increased wearing comfort).
  • the active substances in fabric softening formulations are "esterquats", quaternary ammonium compounds having two hydrophobic radicals, such as, for example, disteryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups as predetermined breaking points in their hydrophobic residues contain the biodegradation.
  • esters having improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Further suitable as a finish is dimethylolethyleneurea.
  • Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out behavior of washing 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-CI bonds.
  • Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimetylpolysiloxanes.
  • UV absorbers which are applied to the treated textiles and improve the lightfastness of the fibers.
  • Compounds which have the desired properties are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position which are active by radiationless deactivation.
  • substituted benzotriazoles in the 3-position 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 endogenous urocanic acid.
  • protein hydrolysates are further active substances preferred in the context of the present invention from the field of detergents and cleaners.
  • Protein hydrolysates are product mixtures which are 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, e.g. Soy, almonds, rice, pea, potato and wheat protein hydrolysates.
  • protein hydrolysates is preferred as such, it is also possible to use other amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, in their place. It is likewise possible to use derivatives of the protein tetrolyzates, for example in the form of their fatty acid condensation products.
  • the nonaqueous solvents which can be used according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, Diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (sulfuric nitro compounds (nitrobenzene), halogenated hydrocarbons (dichloromethane, chloroform, tetrachlor
  • a solvent mixture which is particularly preferred in the context of the present application is, for example, benzene, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, particularly 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
EP05769966.2A 2004-08-20 2005-07-28 Corps moule detergent ou nettoyant pourvu d'un revetement Active EP1781768B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05769966T PL1781768T5 (pl) 2004-08-20 2005-07-28 Powlekana kształtka środka piorącego lub czyszczącego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004040330A DE102004040330A1 (de) 2004-08-20 2004-08-20 Beschichteter Wasch- oder Reinigungsmittelformkörper
PCT/EP2005/008180 WO2006021284A1 (fr) 2004-08-20 2005-07-28 Corps moule detergent ou nettoyant pourvu d'un revetement

Publications (3)

Publication Number Publication Date
EP1781768A1 true EP1781768A1 (fr) 2007-05-09
EP1781768B1 EP1781768B1 (fr) 2010-02-10
EP1781768B2 EP1781768B2 (fr) 2014-10-08

Family

ID=34979903

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05769966.2A Active EP1781768B2 (fr) 2004-08-20 2005-07-28 Corps moule detergent ou nettoyant pourvu d'un revetement

Country Status (6)

Country Link
US (2) US20080255020A1 (fr)
EP (1) EP1781768B2 (fr)
AT (1) ATE457344T1 (fr)
DE (2) DE102004040330A1 (fr)
PL (1) PL1781768T5 (fr)
WO (1) WO2006021284A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005022786B4 (de) * 2005-05-12 2016-09-15 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmitteldosiereinheit
DE102008060470A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102008060471A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
ES2601906T3 (es) * 2010-05-17 2017-02-16 Dalli-Werke Gmbh & Co. Kg Pastillas de detergente que tienen más de cuatro superficies laterales
EP2970831B1 (fr) 2013-03-14 2019-03-27 Ecolab USA Inc. Détergent contenant des enzymes et composition de prétrempage et procédés d'utilisation
JP6810060B2 (ja) * 2015-06-09 2021-01-06 ダウ グローバル テクノロジーズ エルエルシー ３ｄ印刷用支持材料
DE102018106720A1 (de) * 2018-03-21 2019-09-26 Miele & Cie. Kg Reinigungsmittelkörper zur Verwendung in einem als Waschmaschine oder Geschirrspülmaschine ausgebildeten Reinigungsgerät und Reinigungsgerät

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324038A (en) * 1964-04-17 1967-06-06 Procter & Gamble Detergent composition
US4460490A (en) * 1980-12-18 1984-07-17 Jeyes Group Limited Lavatory cleansing blocks
CA2171616C (fr) † 1993-12-30 2005-07-26 Bernard Joseph Heile Article detergent hygroscopique stable
GB9422924D0 (en) 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
US6232284B1 (en) * 1996-12-06 2001-05-15 The Procter & Gamble Company Coated detergent tablet with disintegration means
ES2294784T3 (es) 1996-12-06 2008-04-01 THE PROCTER & GAMBLE COMPANY Pastilla de detergente recubierta.
JP2001509837A (ja) † 1997-11-26 2001-07-24 ザ、プロクター、エンド、ギャンブル、カンパニー 圧縮部分および非圧縮部分の双方を有する多層洗剤タブレット
ATE387486T1 (de) * 1999-03-12 2008-03-15 Procter & Gamble Parfümierte waschmitteltablette
DE19920118B4 (de) * 1999-05-03 2016-08-11 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung und Verfahren zu seiner Herstellung
DE19932765A1 (de) † 1999-07-14 2001-01-18 Henkel Kgaa Befüllte Wasch- und Reinigungsmittelformkörper
DE19940547A1 (de) * 1999-08-26 2001-03-01 Henkel Kgaa Wasch- oder Reinigungsmittelformkörper mit Partialcoating
DE19959875A1 (de) * 1999-12-10 2001-07-05 Henkel Kgaa Preßverfahren für mehrphasige Formkörper
DE10010760A1 (de) † 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
DE10026334A1 (de) 2000-05-26 2001-12-06 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Pfropfcopolymer-Beschichtung
DE10064635A1 (de) * 2000-12-22 2002-07-04 Henkel Kgaa Wasch-und Reinigungsmittelformkörper mit Partialcoating
DE10064985A1 (de) * 2000-12-23 2002-07-11 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung
DE10233564A1 (de) * 2002-07-24 2003-10-16 Henkel Kgaa Wasch- und Reinigungsmittelportionen mit Umhüllung
DE10254313A1 (de) † 2002-11-21 2004-06-09 Henkel Kgaa Verfahren zur Herstellung befüllter Wasch- und Reinigungsmittelformkörper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006021284A1 *

Also Published As

Publication number Publication date
PL1781768T5 (pl) 2015-05-29
DE102004040330A1 (de) 2006-03-02
ATE457344T1 (de) 2010-02-15
DE502005008999D1 (de) 2010-03-25
US20090029055A1 (en) 2009-01-29
US20080255020A1 (en) 2008-10-16
WO2006021284A1 (fr) 2006-03-02
EP1781768B2 (fr) 2014-10-08
EP1781768B1 (fr) 2010-02-10
PL1781768T3 (pl) 2010-07-30

Similar Documents

Publication Publication Date Title
DE102004030318B4 (de) Mehrkammer-Pouch
DE102004020720A1 (de) Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln
EP1776448B2 (fr) Procede de fabrication d'agents de lavage ou de nettoyage en portions
EP1802734A1 (fr) Agent de lavage ou de nettoyage
EP1781768A1 (fr) Corps moule detergent ou nettoyant pourvu d'un revetement
WO2006045452A1 (fr) Agents de lavage ou de nettoyage
WO2006018107A1 (fr) Agents de lavage et de nettoyage contenant des produits de rinçage et des acides amines soufres
EP1888736B1 (fr) Unite de dosage de produit de lavage ou de nettoyage
EP1572858B1 (fr) Detergents et nettoyants sous forme de corps fa onnes de grand volume
EP1802735A1 (fr) Agents de lavage ou de nettoyage
EP1340808B1 (fr) Corps moulés nettoyants parfumés
EP1340807B1 (fr) Corps moulés contenant des tensio-actifs ajoutés postérieurement
DE102004062704A1 (de) Verfahren zur Herstellung eines portionierten Wasch- oder Reinigungsmittels
WO2006063724A1 (fr) Outil de coupe destine a des bandes de films
WO2006066721A1 (fr) Unite de dosage pour detergent ou nettoyant
DE10237198A1 (de) Portionierte Wasch- oder Reinigungsmittel mit Phosphat II
EP1859018A1 (fr) Corps moule de lavage ou de nettoyage multiphase
WO2006045453A1 (fr) Unite dosee de lessive ou detergent
DE102004030148A1 (de) Verfahren zur Herstellung von Portionspackungen für wasch- oder reinigungsaktive Substanzen
WO2006066722A1 (fr) Detergent ou nettoyant emballe

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070105

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20070710

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HOLDERBAUM, THOMAS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 502005008999

Country of ref document: DE

Date of ref document: 20100325

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100210

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20100210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100521

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100611

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100610

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100511

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100510

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

26 Opposition filed

Opponent name: RECKITT BENCKISER N.V.

Effective date: 20101110

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20100731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100210

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100731

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100811

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20141008

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 502005008999

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 502005008999

Country of ref document: DE

Effective date: 20141008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141008

REG Reference to a national code

Ref country code: PL

Ref legal event code: T5

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20160623

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20160721

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 457344

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170728

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20190722

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170728

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230724

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20230720

Year of fee payment: 19

Ref country code: FR

Payment date: 20230725

Year of fee payment: 19

Ref country code: DE

Payment date: 20230719

Year of fee payment: 19