EP0504091A1 - Composition pour le lavage machinal de la vaisselle sans phosphate - Google Patents

Composition pour le lavage machinal de la vaisselle sans phosphate Download PDF

Info

Publication number
EP0504091A1
EP0504091A1 EP92610015A EP92610015A EP0504091A1 EP 0504091 A1 EP0504091 A1 EP 0504091A1 EP 92610015 A EP92610015 A EP 92610015A EP 92610015 A EP92610015 A EP 92610015A EP 0504091 A1 EP0504091 A1 EP 0504091A1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
acid
automatic dishwashing
bleach
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
EP92610015A
Other languages
German (de)
English (en)
Other versions
EP0504091B1 (fr
Inventor
Anders Bjerre Kristensen
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.)
Cleantabs AS
Original Assignee
Cleantabs AS
Viking Industries
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=8093912&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0504091(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Cleantabs AS, Viking Industries filed Critical Cleantabs AS
Publication of EP0504091A1 publication Critical patent/EP0504091A1/fr
Application granted granted Critical
Publication of EP0504091B1 publication Critical patent/EP0504091B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2082Polycarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds

Definitions

  • the present invention relates to a phosphate-free automatic dishwashing composition
  • a phosphate-free automatic dishwashing composition comprising nonionic tenside, carboxylic acid, water-soluble alkaline compound and bleach as well as optionally one or more adjuvants or additives.
  • Conventional automatic dishwashing compositions are usually particulate/granular or liquid products, which, when used, produce a washing liquor of highly alkaline pH, frequently between 11 and 12.
  • the commonly applied dosage of such dishwashing compositions is between 30 and 60 g per wash cycle.
  • Conventional dishwashing compositions usually comprise phosphates to soften the water, tensides to loosen food and other undesirable residues, as well as chlorine bleaches.
  • a typical automatic dishwashing composition with chlorine and phosphate may comprise 22% by weight of phosphate, 25% by weight of anhydrous metasilicate, 22.5% by weight of sodium carbonate, 1.5-4.5% by weight of chlorine bleach and 2% by weight of nonionic tensides, based on an amount of 40 g per wash cycle (A.S. Davidson and B. Milwidsky, Synthetic Detergents 1987).
  • a large number of conventional automatic dishwashing compositions contain chlorine bleaches, often causing cutlery to tarnish and stain. This effect becomes more marked with decreasing pH.
  • the use of chlorine bleaches in highly alkaline dishwashing compositions has considerable disadvantages with respect to manufacture and storage, due to deterioration of other substances upon direct contact with active chlorine.
  • the stability of a chlorine bleach is always critical, posing additional difficulties, especially in connection with domestic storage and use, as toxic chlorine gases are easily released.
  • phosphate-free automatic dishwashing compositions of today include SUN PROGRESSTM, a phosphate-free, chlorine-free, non-corrosive automatic dishwashing powder available from Lever, Germany, and "Milde Kraft", another phosphate-free, chlorine-free, non-corrosive powder, marketed in Germany by Benckiser.
  • SUN PROGRESSTM a phosphate-free, chlorine-free, non-corrosive automatic dishwashing powder available from Lever, Germany
  • Milde Kraft another phosphate-free, chlorine-free, non-corrosive powder, marketed in Germany by Benckiser.
  • These known automatic dishwashing compositions still have several disadvantages.
  • the requirement of non-corrosiveness i.e. a relatively low alkalinity, can only be met at the cost of the good cleaning performance.
  • said compositions do not meet the requirement of also satisfactorily removing difficult stains, such as coffee or tea stains, when used in small dosages.
  • the bleach concentration rises slower over a longer period and does not reach the same maximum value as in pulverulent form.
  • the slow release of the bleach into the washing liquor also increases the tendency of active bleach radicals to be inactivated.
  • the bleach stabilizers display a slow release pattern, so that bleach stabilization becomes uncertain.
  • EP Publication No. 0.256.148 (Ussat et al.; Joh. A. Benckiser GmbH) discloses a cleaning and lime-removing agent for automatic dishwashing machines.
  • Such a product may, based on the anhydrous form, for instance comprise 60% by weight of citric acid, 38% by weight of amidosulphonic acid, 0.2% by weight of perfume and 1.8% by weight of nonionic tenside, cf. Example 1.
  • the product itself is, however, not a dishwashing composition, but rather intended to remove the kind of depositions formed after conventional use of the automatic dishwashing machine.
  • the basic composition comprises 1-40% by weight of citric acid or citrate for each part by weight of nonionic tenside.
  • the composition is further combined with 1-30 parts by weight of sodium metasilicate, 0-12 parts by weight of sodium carbonate and 0-4 parts by weight of further substances, such as neutral salt and chlorine bleaches.
  • Said automatic dishwashing composition includes, as mentioned, sodium metasilicate,which means that the dishwashing composition is corrosive.
  • US-PS No. 3.692.684 (Hentschel) (corresponding to SE accepted printed publication no. 352.652) pertains to detergent compositions, including those for automatic dishwashing machines.
  • the compositions are based on water softeners and detergency-increasing agents comprising alkali metal salts of organic, aliphatic and/or aromatic carboxylic acids and/or anhydrides thereof having a maximum of 8 carbon atoms in the hydrophobic part.
  • Examples of such automatic dishwashing compositions include the one of Example 7 comprising 3 parts nonionic tenside, 3 parts sodium alkylpolyglycolether phosphate, 25 parts sodium acetate, 25 parts sodium sulphate, 30 parts sodium citrate and 14 parts adjuvants, including perfume, colouring, bactericides and water.
  • Hentschel does not mention the dosage of such an automatic dishwashing agent. It has therefore to be assumed that Hentschel has used the conventional, high dosage of approx. 40 g per wash cycle. Neither does Hentschel mention a bleach, for which reason said composition is hardly successful in removing coffee and tea stains satisfactorily.
  • phosphate-free automatic dishwashing compositions None of the known phosphate-free automatic dishwashing compositions has proven effective enough to remove, for instance, coffee or tea stains, when it is simultaneously required that the composition may not comprise chlorine bleaches, may not act as a corrosive and may only be used at small dosages.
  • the object of the present invention is to provide a phosphate-free automatic dishwashing agent meeting these requirements.
  • the object of the invention is accomplished by a phosphate-free automatic dishwashing composition comprising nonionic tenside, carboxylic acid, water-soluble alkaline compound and bleach as well as optionally one or more adjuvants or additives, characterized by the bleach being a chlorine-free oxygen donating bleach, and by the automatic dishwashing composition comprising
  • the dishwashing composition Due to the low alkalinity the dishwashing composition is easy on the automatic dishwashing machine, plates and cutlery, as well as being environmentally friendly. Low alkalinity also means a considerably reduced risk of corrosive action. Thus, it is no longer necessary to use a child-proof package, as is expected to be introduced in Denmark by law in 1992 for potentially corrosive products.
  • a further advantage of the dishwashing composition is that it can be compressed to tablets without losing the bleaching effect. As mentioned above, tablets ensure a uniformly low dosage and prevent overdosage.
  • the tablet shape also allows for an automatic dosing of the dishwashing composition in automatic dishwashing machines of the future.
  • the dishwashing composition according to the invention comprises at least 20 parts by weight, such as at least 50 parts by weight, preferably 75 parts by weight, and particularly preferred at least 85 parts by weight of alkalicarbonate or a mixture thereof with alkalibicarbonate per 100 parts by weight of the bleach and not more than 150 parts by weight, such as not more than 140 parts by weight, preferably 115 parts by weight, and particularly preferred not more than 105 parts by weight per 100 parts by weight of the bleach.
  • the amount of polycarboxylate is at least 8 parts by weight, such as at least 20 parts by weight, preferably 35 parts by weight, and particularly preferred at least 64 parts by weight per 100 parts by weight of the bleach and not more than 150 parts by weight, such as not more than 100 parts by weight, preferably 85 parts by weight, and particularly preferred not more than 78 parts by weight per 100 parts by weight of the bleach.
  • the polycarboxylate is preferably a polyacrylate and/or a maleic acid/acrylic acid copolymer having a molecular weight of 3,000-150,000.
  • the amount of polyfunctional carboxylic acid is at least 20 parts by weight, such as at least 33 parts by weight, preferably at least 53 parts by weight, and particularly preferred at least 59 parts by weight per 100 parts by weight of the bleach and not mroe than 150 parts by weight, such as not more than 100 parts by weight, preferably 80 parts by weight, and particularly preferred not more than 73 parts by weight per 100 parts by weight of the bleach.
  • the polyfunctional carboxylic acid is preferably selected from the group consisting of citric acid, malic acid, tartaric acid, glutaric acid, tartronic acid, gluconic acid, salicylic acid, isoserine diacetic acid, NTA and EDTA.
  • the amount of sodium silicate is at least 20 parts by weight, such as at least 22 parts by weight, preferably 34 parts by weight, and particularly preferred at least 40 parts, and not more than 70 parts by weight, such as not more than 66 parts by weight, preferably 54 parts by weight, and particularly preferred not more than 48 parts by weight per 100 parts by weight of the bleach.
  • the sodium silicate is preferably sodium disilicate and/or a so-called clay or "layer silicate", i.e. a silicate, which in Germany is termed "Schichtsilikat".
  • the amount of nonionic tenside is at least 5 parts by weight, such as at least 7 parts by weight, preferably 11 parts by weight, and particularly preferred at least 13 parts by weight, and not more than 25 parts by weight, such as not more than 22 parts by weight, preferably 19 parts by weight, and particularly preferred not more than 17 parts by weight per 100 parts by weight of the bleach.
  • the chlorine-free, oxygen donating bleach is preferably a peroxy compound or a perhydrate.
  • the automatic dishwashing composition according to the invention advantageously comprises 10-33 parts by weight of a sequestrant and/or 15-45 parts by weight of a bleach activator per 100 parts by weight of chlorine-free oxygen donating bleach.
  • the automatic dishwashing composition according to the invention is advantageously manufactured in the form of a tablet.
  • the automatic dishwashing composition according to the invention is advantageously such that a solution of 1% by weight of said composition in water results in a pH-value of 7-10.5, preferably 8-10.0. This pH-value ensures the non-corrosiveness of the dishwashing composition.
  • a distinctive characteristic of the present invention is the polyfunctional carboxylic acid acting like a complex-forming agent during the wash by binding the polyvalent cations in the water and thus stabilizing the washing process, especially the bleaching process.
  • a polyvalent carboxylic acid has a positive influence on the dissolving time, in case the automatic dishwashing composition has the form of a tablet, as the polyfunctional carboxylic acid reacts with carbonate ions present by giving off bubbles.
  • the effervescent effect has a significant influence on the removal of tea and coffee stains.
  • polyfunctional carboxylic acids include aliphatic, cyclic and aromatic polyfunctional carboxylic acids having at least one carboxyl group and additionally at least one more carboxyl or hydroxyl group, preferably several such functional groups, selected from the group consisting of COOH and OH. Salts as well as lacton, ester, alkoxylate, amine, diamine and sulphonate derivatives, as well as sulphate compounds thereof, are also included. Preferred salts are alkali metal salts, especially sodium salts.
  • polyfunctional carboxylic acids are lactic acid, malic acid, tartronic acid, gluconic acid, glutaric acid, citric acid, tartaric acid and salicylic acid, most preferred is citric acid, preferably in the anhydrous form.
  • a further suitable polyfunctional carboxylic acid may be a mixture of dicarboxylic acids available from BASFTM AG under the trade name SOKALANTM DCS in the form of a white powder.
  • Suitable chlorine-free oxygen donating bleaches are perhydrates and peroxy compounds, as well as mixtures thereof.
  • Perhydrates preferably include alkali metal compounds of perborates in the form of tetra- or monohydrates, perborax, percarbonates, persilicates, citrate perhydrates as well as perhydrates of urea and melamine compounds.
  • acidic persalts such as persulphates (e.g.
  • perbenzoates and peroxycarboxylic acids, such as peroxyphthalate, magnesium monoperoxyphthalic acid, diperoxyphthalic acid,2-octyl-diperoxysuccinic acid, diperoxydodecane dicarboxylic acid, diperoxyazelaic acid, imidoperoxycarboxylic acid, as well as salts and mixtures thereof.
  • Particularly preferred bleaches are sodium percarbonate and sodium perborate.
  • the inventive dishwashing composition may contain alkalicarbonate alone, for example sodium carbonate, or a combination of alkalicarbonate and alkalibicarbonate, for example in the weight ratio from 100:1 to 1:10, calculated as the sodium compounds.
  • polycarboxylates used include polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, metaconic acid, aconitic acid, methylene malonic acid, citraconic acid etc., as well as copolymers of said carboxylic acids either with each other or with other ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl alcohol, vinylmethyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid or crotonic acid.
  • the molecular weight of the polycarboxylates may be in the range of 1,000-1,000,000, preferably 2,000-100,000 and most preferred 7,000-30,000.
  • the sodium silicate used may advantageously be a sodium silicate having a Na2O:SiO2 ratio of 1:0.5 to 1:3.5, preferably 1:1.9 to 1:3.5, and more preferred of 1:2 to 1:3.5.
  • Suitable sodium silicates include so-called clays or "layer silicates", i.e. compounds having the stoicheiometric composition Na2SiO5, each layer consisting of SiO4-tetrahedrons. It has been shown that such compounds may complement or completely replace conventional silicates.
  • clays or "layer silicates" i.e. compounds having the stoicheiometric composition Na2SiO5, each layer consisting of SiO4-tetrahedrons. It has been shown that such compounds may complement or completely replace conventional silicates.
  • One of the advantages of clays is their excellent ability to bind magnesium ions, which play an important role in the deposition of lime on the heating elements of an automatic dishwashing machine.
  • a preferred clay is the one sold under the trade
  • Tensides suitable for incorporation in the dishwashing composition according to the invention may be any low-foaming nonionic tenside, especially alkylene oxide adducts (adducts of ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide (BO) and mixtures thereof) with alcohols, thioalcohols, diols, fatty acids, fatty acid amides, alkane sulphonamides, alkyl amines as well as alkyl phenols rendered low-foaming by, for instance, substituting the free hydroxyl groups of the polyalkylene glycolether moieties by an ether or acetal group.
  • Nonionic tensides particularly suitable for incorporation in the automatic dishwashing composition are, for instance, mentioned in GB-PS No. 2.206.601 and the publications cited therein.
  • fatty alcohol/EO adducts and/or fatty alcohol/EO/PO adducts such as PLURAFACTM LF 403 available from BASFTM AG, UKANIL FM 2136 and SYNPERONICTM RA 30 available from ICI or DEHYPONTM LT 104 or DEHYDOLTM LS 54 available from Henkel KGaA.
  • the tenside may be used in varying amounts, depending on whether adjuvants, such as glycerol, are incorporated at the same time.
  • the amount of nonionic tenside is preferably 13-21, more preferred 15-19, for instance approx. 17 parts by weight per 100 parts by weight of the bleach.
  • the preferred amount of nonionic tenside is 9-17, more preferred 11-15, for instance approx. 13 parts by weight per 100 parts by weight of the bleach.
  • the adjuvant may be glycerol in an amount of 2-7, preferably 3-5, parts by weight per 100 parts by weight of the bleach. In some cases the addition of an adjuvant, such as glycerol, may improve the product, for instance as regards storage stability.
  • the dishwashing composition according to the invention may further comprise a sequestrant having a dispersing and complex-binding (sequestering) effect, such as nitrilotriacetic acid (NTA), isoserine diacetic acid, ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), hyroxyethylethylene diamine triacetic acid (HEEDTA), ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP), diethylene triamine penta(methylene phosphonic acid) (DETPMP), aminotrimethylene phosphonic acid (ATMP) as well as phytic acid and its derivatives including salts thereof, especially alkali metal or alkaline earth metal salts.
  • a sequestrant having a dispersing and complex-binding (sequestering) effect such as nitrilotriacetic
  • Salts of phytic acid include the dodecane sodium salt of phytic acid (inositolhexaphosphoric acid) available from Sigma Chemical Company, USA.
  • Particularly preferred sequestrants are the disodium and tetrasodium salt, respectively, of ethane-1-hydroxy-1,1-diphosphonic acid, available in the form of a free-flowing powder under the trade names SEQUION 10 NAPDR and DEQUESTTM 2016 D, respectively, from G. Bozetto S.p.A., Filago, Italy, and Monsanto PLC,Great Britain, respectively.
  • Phosphonic acid compounds do not only possess complex-binding properties contributing to i.a. stabilizing the bleaches present, but also, due to their high dispersability, so-called threshold properties, i.e. precipitation-limiting properties.
  • Some of the above-mentioned sequestrants are polyfunctional carboxylic acids comprising the obligatory carboxyl group and at least one further functional group selected from the group consisting of carboxyl and hydroxyl. Moreover, nitrogen is also present in the molecule. Based on the presence of said functional groups (OH and COOH) it has to be assumed that said sequestrants may be incorporated as the polyfunctional carboxylic acid, a requisite component of the automatic dishwashing composition according to the invention, or as a part thereof.
  • Such compounds are, for instance, isoserine diacetic acid, NTA and EDTA.
  • Isoserine diacetic acid having the formula (CH2COOH)2N-CH2CHOHCOOH is expected to be marketed by BASFTM AG, Germany, within the next 1-2 years in the form of a liquid product comprising 40% isoserine diacetic acid.
  • the product is expected to be the future substitute for EDTA and can be used in the dishwashing composition according to the invention.
  • isoserine diacetic acid is considered for use in the inventive dishwashing composition in tablet form, it will be necessary for isoserine diacetic acid to be available in the form of a stable powder with sufficient acidity to react with the alkaline salts, such as alkalicarbonates, thereby releasing carbon dioxide.
  • NTA and EDTA fulfill this condition and can thus advantageously be used in the inventive dishwashing composition both in tablet form and in any other form.
  • Non-limiting examples thereof include N-acyl compounds and O-acyl compounds, such as acylated amines, diamines, amides, acylated glycolurils, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulphuryl amides, cyanurates and imidazolines, carboxylic acid anhydrides, acylated sugar compounds, acylated ester compounds etc.
  • N-acyl compounds and O-acyl compounds such as acylated amines, diamines, amides, acylated glycolurils, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulphuryl amides, cyanurates and imidazolines, carboxylic acid anhydrides, acylated sugar compounds, acylated ester compounds etc.
  • TAED tetraacetyl methylene diamine
  • TAED tetraacetyl ethylene diamine
  • TAGU tetraacetyl glycoluril
  • PAGE pentaacetyl glucose
  • NOBS nonanoyloxybenzene sulphonate
  • TAED in the form of a granulate having an active content of 85-98% by weight.
  • the bleach activators are described in greater detail in GB-PS No. 2.040.983 and GB-PS No. 1.473.201.
  • the automatic dishwashing composition according to the invention is advantageously manufactured in the form of a tablet to be used in a dosage of, for instance, one or two tablets per wash cycle.
  • tablet adjuvants have usually to be added, for instance in the form of sodium acetate, sodium sulfate, starch, glycerol, polyethylene glycol, preferably of a molecular weight of 100-10,000, polyvinyl pyrrolidone (PVP), polyvinyl polypyrrolidone (PVPP) or a stearate compound, such as sodium stearate.
  • Such tablet adjuvants ensure suitable consistency and granulation.
  • the tablets are manufactured in a manner known per se.
  • a basic powder fraction comprising bleach, polyfunctional carboxylic acid, alkalicarbonate, alkalibicarbonte, polycarboxylate, sodium silicate and enzymes.
  • the nonionic tenside is sprayed on, whereupon one or more adjuvants are sprayed on or added.
  • the mixture is subjected to a final stirring lasting 2-10 minutes.
  • the resulting powder mix is compressed to tablets of a diameter of, for instance, 32 mm in a tablet press (eg. Fette Perfecta 4B).
  • the thickness of the manufactured tablet depends on its desired weight and formulation, and is usually in the range of 13-20 mm. Further examples of manufacturing tablets are disclosed in DE-PS No. 355.626, US-PS No. 328.880 and DE-PS No. 3.827.895.
  • This example describes an automatic dishwashing composition in pulverulent form to be used in an amount of 18 g dishwashing composition per wash cycle.
  • SOKALANTM PA 40 sodium salt of a polyacrylate in pulverulent form having a molecular weight of approx. 15,000, available from BASFTM, Germany.
  • TAED 3711 tetraacetyl ethylene diamine, available from HOECHST AG, Germany.
  • PLURAFACTM LF 403 low-foaming nonionic tenside in the from of an ethoxylated fatty alcohol, available from BASFTM, Germany.
  • TERMAMYLTM 60 T amylolytic enzyme, available from Novo Nordisk A/S, Denmark.
  • ESPERASETM 6.0 T proteolytic enzyme, available from Novo Nordisk A/S, Denmark.
  • DEQUESTTM 2016 D tetrasodium salt of 1-hydroxy--ethane-1,1-diphosphonic acid (HEDP), available from MONSANTO, Great Britain.
  • This example relates to a dishwashing composition in the form of a tablet having a weight of 18 g and formulated as the dishwashing composition according to Example 2, apart from citric acid being replaced by an equivalent amount of trisodium citrate dihydrate.
  • This modification increases the alkalinity of the dishwashing composition.
  • the tablet does, however, not possess the advantageous effervescent effect obtained by means of citric acid.
  • the following dishwashing trials have shown that said dishwashing composition displayed a strong tendency to over-foam although the nonionic tenside used was low-foaming.
  • the alkalinity was determined by measuring the pH using 1% aqueous solutions of different dishwashing compositions. The results are shown in the table below:
  • the dishwashing compositions according to Examples 1, 2 and 3 were used in amounts of 18 g per wash cycle.
  • Melde Kraft a phosphate-free, chlorine-free, non-corrosive product available from Benckiser, was used in an amount of 24 g per wash cycle.
  • the dishwashing composition according to DE 2. 230. 453 has fewer points for "non-tea", although its dosage is 40 g per wash cycle. On the other hand, it is better at removing tea stains than the dishwashing composition according to the invention (Examples 1 and 2). However, the product has a high alkalinity of 12.1.
  • Table 2 also shows the proportions of the essential components as parts by weight per 100 parts by weight of the bleach and the performance scores for tea, non-tea and total.
EP92610015A 1991-03-15 1992-03-12 Composition pour le lavage machinal de la vaisselle sans phosphate Expired - Lifetime EP0504091B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK47091A DK166548B1 (da) 1991-03-15 1991-03-15 Phosphatfrit maskinopvaskemiddel
DK470/91 1991-03-15
DK47091 1991-03-15

Publications (2)

Publication Number Publication Date
EP0504091A1 true EP0504091A1 (fr) 1992-09-16
EP0504091B1 EP0504091B1 (fr) 1999-06-09

Family

ID=8093912

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92610015A Expired - Lifetime EP0504091B1 (fr) 1991-03-15 1992-03-12 Composition pour le lavage machinal de la vaisselle sans phosphate

Country Status (4)

Country Link
EP (1) EP0504091B1 (fr)
DE (1) DE69229366T2 (fr)
DK (1) DK166548B1 (fr)
ES (1) ES2132113T3 (fr)

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0512371A2 (fr) * 1991-05-02 1992-11-11 DISPO-Kommerz AG Agents granulaires sans phosphate pour lavage de vaisselle en machine
WO1994016045A1 (fr) * 1993-01-18 1994-07-21 Unilever N.V. Composition pour lave-vaisselle contenant un inhibiteur de corrosion
WO1994023011A1 (fr) * 1993-04-01 1994-10-13 Henkel Kommanditgesellschaft Auf Aktien Comprimes stables bifonctionnels de produits de lavage a faible alcalinite, sans phosphates, sans metasilicates et sans polymeres, pour lave-vaisselle, et leur procede de production
WO1994026859A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produit i de protection de l'argent contre la corrosion
WO1994026860A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produits de protection de l'argent contre la corrosion ii
EP0628627A1 (fr) * 1993-06-07 1994-12-14 JOH. A. BENCKISER GmbH Agent builder hydrosoluble, adoucisseur d'eau
WO1995000623A1 (fr) * 1993-06-28 1995-01-05 Henkel Kommanditgesellschaft Auf Aktien Detergent pour lave-vaisselle contenant des adjuvants
EP0634483A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions de blanchiment stabilisées
WO1995012654A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle
WO1995012653A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation du carbonate de calcium dans les lave-vaisselle
EP0659874A1 (fr) * 1993-12-23 1995-06-28 The Procter & Gamble Company Compositions détergents
WO1995020030A1 (fr) * 1994-01-25 1995-07-27 Unilever N.V. Co-granules et pastilles detergentes produites a l'aide desdits co-granules
WO1995021908A1 (fr) * 1994-02-10 1995-08-17 Henkel Kommanditgesellschaft Auf Aktien Comprime contenant des adjuvants
WO1996012783A1 (fr) * 1994-10-20 1996-05-02 Henkel Kommanditgesellschaft Auf Aktien Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine
EP0736085A1 (fr) * 1993-12-21 1996-10-09 The Procter & Gamble Company Composition detergente contenant du percarbonate et de l'amylase
US5591703A (en) * 1993-04-27 1997-01-07 The Procter & Gamble Company Liquid or granular automatic diswashing detergent compositions containing builder, enzyme and low molecular weight, modified polyacrylate copolymers
US5597789A (en) * 1993-04-27 1997-01-28 The Procter & Gamble Company Liquid or granular automatic dishwashing detergent compositions containing silicate and low molecular weight modified polyacrylate coploymers
WO1997003177A1 (fr) * 1995-07-13 1997-01-30 Joh. A. Benckiser Gmbh Produit vaisselle sous forme de pastilles pour lave-vaisselle
WO1997009411A1 (fr) * 1995-09-01 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation de produits granules precurseurs de detergents de faible alcalinite
WO1997031096A1 (fr) * 1996-02-23 1997-08-28 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de pastilles d'agent detergent pour lave-vaisselle
US5663133A (en) * 1995-11-06 1997-09-02 The Procter & Gamble Company Process for making automatic dishwashing composition containing diacyl peroxide
EP0799886A2 (fr) * 1996-04-03 1997-10-08 Cleantabs A/S Tablettes de détergent pour du linge
US5695903A (en) * 1994-12-21 1997-12-09 Agfa-Gevaert Ag Process for developing irradiated radiation-sensitive recording materials
EP0812241A1 (fr) * 1995-03-01 1997-12-17 Charvid Limited Liability Company Composition de nettoyage non caustique comprenant un compose peroxygene et un silicate particulier, et procede pour preparer cette composition
EP0812808A1 (fr) * 1996-06-12 1997-12-17 Cleantabs A/S Comprimés pour adoucir l'eau
EP0812905A2 (fr) * 1996-06-14 1997-12-17 Rohm And Haas Company Comprimés détergents
EP0815192A1 (fr) * 1995-03-11 1998-01-07 The Procter & Gamble Company Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
US5710115A (en) * 1994-12-09 1998-01-20 The Procter & Gamble Company Automatic dishwashing composition containing particles of diacyl peroxides
US5719111A (en) * 1995-02-17 1998-02-17 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing a solid detergent block
WO1998014548A2 (fr) * 1996-10-02 1998-04-09 Herbert Schmitz Procede de production d'un produit de nettoyage, notamment sous forme de poudre pour lave-vaisselle
US5763378A (en) * 1995-04-17 1998-06-09 The Procter & Gamble Company Preparation of composite particulates containing diacyl peroxide for use in dishwashing detergent compositions
EP0847438A1 (fr) * 1995-07-25 1998-06-17 The Procter & Gamble Company Compositions detergentes sous forme solide compacte
WO1998045400A1 (fr) * 1997-04-09 1998-10-15 Benckiser N.V. Adjuvant adoucissant de l'eau soluble dans l'eau
EP0881282A1 (fr) * 1997-05-27 1998-12-02 The Procter & Gamble Company Pains de détergents, et leur procédé de fabrication
WO1999006521A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Pastille detergente
US5888954A (en) * 1993-05-08 1999-03-30 Henkel Kommanditgesellschaft Auf Aktien Corrosion inhibitors for silver
WO1999028431A1 (fr) * 1997-11-28 1999-06-10 Henkel Kommanditgesellschaft Auf Aktien Procede pour produire des comprimes detergents pour lave-vaisselle
WO1999031215A1 (fr) * 1997-12-17 1999-06-24 The Procter & Gamble Company Comprime detergent
US5972040A (en) * 1993-12-21 1999-10-26 The Procter & Gamble Company Detergent compositions containing percarbonate and amylase
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
WO2000058435A1 (fr) * 1999-03-25 2000-10-05 Henkel Kommanditgesellschaft Auf Aktien Pastilles comportant un adjuvant
GB2353800A (en) * 1999-09-02 2001-03-07 Procter & Gamble Antibacterial detergent compositions
US6462006B1 (en) 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
FR2831181A1 (fr) * 2001-10-23 2003-04-25 Rhodia Polyamide Intermediates Tablette antitartre acide et son utilisation en lavage automatique de la vaisselle
FR2831180A1 (fr) * 2001-10-23 2003-04-25 Rhodia Polyamide Intermediates Formulation solide bicomposant pour le lavage automatique de la vaisselle et procede de lavage automatique de la vaisselle
WO2003048291A1 (fr) * 2001-11-30 2003-06-12 Ecolab, Inc. Compositions actives stabilisees d'oxygene
US6599871B2 (en) 1997-08-02 2003-07-29 The Procter & Gamble Company Detergent tablet
US6602837B1 (en) 1994-12-09 2003-08-05 The Procter & Gamble Company Liquid automatic dishwashing detergent composition containing diacyl peroxides
WO2008135450A1 (fr) * 2007-05-03 2008-11-13 Unilever Plc Système adjuvant de détergence ('builder') destiné à une composition détergente
WO2009040728A1 (fr) * 2007-09-24 2009-04-02 The Procter & Gamble Company Procédé de lavage de vaisselle
WO2010094924A1 (fr) * 2009-02-23 2010-08-26 Reckitt Benckiser N.V. Produit détergent contenant du percarbonate
EP2228426A1 (fr) * 2009-03-13 2010-09-15 Rohm and Haas Company Additif de réduction de tartre pour systèmes de lavage automatique de la vaisselle
WO2012081130A1 (fr) * 2010-12-17 2012-06-21 花王株式会社 Composition de nettoyage en poudre pour machines de nettoyage automatisées
JP2014028870A (ja) * 2009-03-13 2014-02-13 Rohm & Haas Co 自動食器洗浄システムのためのスケール低減添加剤
EP3181671A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181672A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3266860A1 (fr) * 2016-07-08 2018-01-10 The Procter and Gamble Company Procédé de fabrication d'une particule
US10421927B2 (en) 2015-12-17 2019-09-24 The Procter & Gamble Company Automatic dishwashing detergent composition comprising benzotriazole and nonionic surfactant mixture
US10683471B2 (en) 2015-12-17 2020-06-16 The Procter & Gamble Company Automatic dishwashing detergent composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0240315A2 (fr) * 1986-04-02 1987-10-07 Kao Corporation Composition de blanchiment
EP0313144A2 (fr) * 1987-10-23 1989-04-26 Unilever N.V. Compositions détergentes et de blanchiment sans phosphates
EP0414197A2 (fr) * 1989-08-22 1991-02-27 Joh. A. Benckiser GmbH Composition pour le lavage en machine à laver la vaisselle
EP0429124A1 (fr) * 1989-11-21 1991-05-29 The Procter & Gamble Company Compositions sans chlore pour le lavage automatique de la vaisselle

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06323216A (ja) * 1993-05-18 1994-11-22 Aisan Ind Co Ltd 燃料ポンプ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0240315A2 (fr) * 1986-04-02 1987-10-07 Kao Corporation Composition de blanchiment
EP0313144A2 (fr) * 1987-10-23 1989-04-26 Unilever N.V. Compositions détergentes et de blanchiment sans phosphates
EP0414197A2 (fr) * 1989-08-22 1991-02-27 Joh. A. Benckiser GmbH Composition pour le lavage en machine à laver la vaisselle
EP0429124A1 (fr) * 1989-11-21 1991-05-29 The Procter & Gamble Company Compositions sans chlore pour le lavage automatique de la vaisselle

Cited By (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0512371A2 (fr) * 1991-05-02 1992-11-11 DISPO-Kommerz AG Agents granulaires sans phosphate pour lavage de vaisselle en machine
EP0512371A3 (en) * 1991-05-02 1995-06-14 Dispo Kommerz Ag Granular phosphate-free agents for automatic dishwashing
WO1994016045A1 (fr) * 1993-01-18 1994-07-21 Unilever N.V. Composition pour lave-vaisselle contenant un inhibiteur de corrosion
WO1994023011A1 (fr) * 1993-04-01 1994-10-13 Henkel Kommanditgesellschaft Auf Aktien Comprimes stables bifonctionnels de produits de lavage a faible alcalinite, sans phosphates, sans metasilicates et sans polymeres, pour lave-vaisselle, et leur procede de production
US5691293A (en) * 1993-04-01 1997-11-25 Henkel Kommanditgesellschaft Auf Aktien Stable, dual-function, phosphate-, metasilicate- and polymer-free low-alkali detergent tablets for dishwashing machines and a process for their production
US5597789A (en) * 1993-04-27 1997-01-28 The Procter & Gamble Company Liquid or granular automatic dishwashing detergent compositions containing silicate and low molecular weight modified polyacrylate coploymers
US5591703A (en) * 1993-04-27 1997-01-07 The Procter & Gamble Company Liquid or granular automatic diswashing detergent compositions containing builder, enzyme and low molecular weight, modified polyacrylate copolymers
WO1994026859A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produit i de protection de l'argent contre la corrosion
US5888954A (en) * 1993-05-08 1999-03-30 Henkel Kommanditgesellschaft Auf Aktien Corrosion inhibitors for silver
WO1994026860A1 (fr) * 1993-05-08 1994-11-24 Henkel Kommanditgesellschaft Auf Aktien Produits de protection de l'argent contre la corrosion ii
EP0628627A1 (fr) * 1993-06-07 1994-12-14 JOH. A. BENCKISER GmbH Agent builder hydrosoluble, adoucisseur d'eau
WO1995000623A1 (fr) * 1993-06-28 1995-01-05 Henkel Kommanditgesellschaft Auf Aktien Detergent pour lave-vaisselle contenant des adjuvants
EP0634483A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions de blanchiment stabilisées
WO1995012654A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle
US5786315A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
US5786314A (en) * 1993-11-03 1998-07-28 The Procter & Gamble Company Control of calcium precipitation in automatic dishwashing
WO1995012653A1 (fr) * 1993-11-03 1995-05-11 The Procter & Gamble Company Limitation de la precipitation du carbonate de calcium dans les lave-vaisselle
EP0736085A4 (fr) * 1993-12-21 1997-03-19 Procter & Gamble Composition detergente contenant du percarbonate et de l'amylase
EP0736085A1 (fr) * 1993-12-21 1996-10-09 The Procter & Gamble Company Composition detergente contenant du percarbonate et de l'amylase
US5972040A (en) * 1993-12-21 1999-10-26 The Procter & Gamble Company Detergent compositions containing percarbonate and amylase
EP0659874A1 (fr) * 1993-12-23 1995-06-28 The Procter & Gamble Company Compositions détergents
WO1995020030A1 (fr) * 1994-01-25 1995-07-27 Unilever N.V. Co-granules et pastilles detergentes produites a l'aide desdits co-granules
AU702040B2 (en) * 1994-01-25 1999-02-11 Unilever Plc Co-granules and detergent tablets formed therefrom
WO1995021908A1 (fr) * 1994-02-10 1995-08-17 Henkel Kommanditgesellschaft Auf Aktien Comprime contenant des adjuvants
US5900399A (en) * 1994-02-10 1999-05-04 Henkel Kommanditgesellschaft Auf Aktien Tablet containing builders
WO1996012783A1 (fr) * 1994-10-20 1996-05-02 Henkel Kommanditgesellschaft Auf Aktien Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine
US6602837B1 (en) 1994-12-09 2003-08-05 The Procter & Gamble Company Liquid automatic dishwashing detergent composition containing diacyl peroxides
US5710115A (en) * 1994-12-09 1998-01-20 The Procter & Gamble Company Automatic dishwashing composition containing particles of diacyl peroxides
US5695903A (en) * 1994-12-21 1997-12-09 Agfa-Gevaert Ag Process for developing irradiated radiation-sensitive recording materials
US5900352A (en) * 1994-12-21 1999-05-04 Agfa-Gevaert Ag Developer for irradiated radiation-sensitive recording materials
US5719111A (en) * 1995-02-17 1998-02-17 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing a solid detergent block
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
EP0812241A4 (fr) * 1995-03-01 1999-08-18 Charvid Limited Liability Comp Composition de nettoyage non caustique comprenant un compose peroxygene et un silicate particulier, et procede pour preparer cette composition
US6043207A (en) * 1995-03-01 2000-03-28 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound, meta/sesqui-silicate, chelate and method of making same in free-flowing, particulate form
EP0812241A1 (fr) * 1995-03-01 1997-12-17 Charvid Limited Liability Company Composition de nettoyage non caustique comprenant un compose peroxygene et un silicate particulier, et procede pour preparer cette composition
EP0815192A1 (fr) * 1995-03-11 1998-01-07 The Procter & Gamble Company Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
EP0815192A4 (fr) * 1995-03-11 1999-09-22 Procter & Gamble Composition detergente comportant un compose polycarboxylique polymere, un chelateur et une enzyme amylase
US5763378A (en) * 1995-04-17 1998-06-09 The Procter & Gamble Company Preparation of composite particulates containing diacyl peroxide for use in dishwashing detergent compositions
US6194368B1 (en) 1995-07-13 2001-02-27 Joh A. Benckiser, Gmbh Dishwasher product in tablet form
WO1997003177A1 (fr) * 1995-07-13 1997-01-30 Joh. A. Benckiser Gmbh Produit vaisselle sous forme de pastilles pour lave-vaisselle
EP0847438A4 (fr) * 1995-07-25 1999-11-10 Procter & Gamble Compositions detergentes sous forme solide compacte
EP0847438A1 (fr) * 1995-07-25 1998-06-17 The Procter & Gamble Company Compositions detergentes sous forme solide compacte
WO1997009411A1 (fr) * 1995-09-01 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation de produits granules precurseurs de detergents de faible alcalinite
US5663133A (en) * 1995-11-06 1997-09-02 The Procter & Gamble Company Process for making automatic dishwashing composition containing diacyl peroxide
WO1997031096A1 (fr) * 1996-02-23 1997-08-28 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de pastilles d'agent detergent pour lave-vaisselle
EP0799886A3 (fr) * 1996-04-03 1998-11-18 Cleantabs A/S Tablettes de détergent pour du linge
EP0799886A2 (fr) * 1996-04-03 1997-10-08 Cleantabs A/S Tablettes de détergent pour du linge
EP0812808A1 (fr) * 1996-06-12 1997-12-17 Cleantabs A/S Comprimés pour adoucir l'eau
EP0812905A3 (fr) * 1996-06-14 1999-09-15 Rohm And Haas Company Comprimés détergents
EP0812905A2 (fr) * 1996-06-14 1997-12-17 Rohm And Haas Company Comprimés détergents
WO1998014548A3 (fr) * 1996-10-02 2000-08-24 Herbert Schmitz Procede de production d'un produit de nettoyage, notamment sous forme de poudre pour lave-vaisselle
WO1998014548A2 (fr) * 1996-10-02 1998-04-09 Herbert Schmitz Procede de production d'un produit de nettoyage, notamment sous forme de poudre pour lave-vaisselle
US6334904B1 (en) * 1997-04-09 2002-01-01 Reckitt Benckiser N.V. Water-soluble, water-softening builder
WO1998045400A1 (fr) * 1997-04-09 1998-10-15 Benckiser N.V. Adjuvant adoucissant de l'eau soluble dans l'eau
EP0881282A1 (fr) * 1997-05-27 1998-12-02 The Procter & Gamble Company Pains de détergents, et leur procédé de fabrication
WO1998054284A1 (fr) * 1997-05-27 1998-12-03 The Procter & Gamble Company Pastilles et leur procede de production
US6355607B1 (en) 1997-05-27 2002-03-12 The Procter & Gamble Company Tablets, and process for making tablets
US6599871B2 (en) 1997-08-02 2003-07-29 The Procter & Gamble Company Detergent tablet
WO1999006521A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Pastille detergente
WO1999028431A1 (fr) * 1997-11-28 1999-06-10 Henkel Kommanditgesellschaft Auf Aktien Procede pour produire des comprimes detergents pour lave-vaisselle
WO1999031215A1 (fr) * 1997-12-17 1999-06-24 The Procter & Gamble Company Comprime detergent
US6462006B1 (en) 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
WO2000058435A1 (fr) * 1999-03-25 2000-10-05 Henkel Kommanditgesellschaft Auf Aktien Pastilles comportant un adjuvant
GB2353800A (en) * 1999-09-02 2001-03-07 Procter & Gamble Antibacterial detergent compositions
WO2003035819A1 (fr) * 2001-10-23 2003-05-01 Rhodia Polyamide Intermediates Tablette antitartre acide et son utilisation en lavage automatique de la vaisselle
FR2831180A1 (fr) * 2001-10-23 2003-04-25 Rhodia Polyamide Intermediates Formulation solide bicomposant pour le lavage automatique de la vaisselle et procede de lavage automatique de la vaisselle
FR2831181A1 (fr) * 2001-10-23 2003-04-25 Rhodia Polyamide Intermediates Tablette antitartre acide et son utilisation en lavage automatique de la vaisselle
WO2003048291A1 (fr) * 2001-11-30 2003-06-12 Ecolab, Inc. Compositions actives stabilisees d'oxygene
WO2008135450A1 (fr) * 2007-05-03 2008-11-13 Unilever Plc Système adjuvant de détergence ('builder') destiné à une composition détergente
WO2009040728A1 (fr) * 2007-09-24 2009-04-02 The Procter & Gamble Company Procédé de lavage de vaisselle
EP2045315A1 (fr) * 2007-09-24 2009-04-08 The Procter and Gamble Company Procédé pour laver la vaisselle
WO2010094924A1 (fr) * 2009-02-23 2010-08-26 Reckitt Benckiser N.V. Produit détergent contenant du percarbonate
JP2014028870A (ja) * 2009-03-13 2014-02-13 Rohm & Haas Co 自動食器洗浄システムのためのスケール低減添加剤
JP2011038071A (ja) * 2009-03-13 2011-02-24 Rohm & Haas Co 自動食器洗浄システムのためのスケール低減添加剤
EP2228426A1 (fr) * 2009-03-13 2010-09-15 Rohm and Haas Company Additif de réduction de tartre pour systèmes de lavage automatique de la vaisselle
US8680033B2 (en) 2009-03-13 2014-03-25 Rohm And Haas Company Scale-reducing additive for automatic dishwashing systems
WO2012081130A1 (fr) * 2010-12-17 2012-06-21 花王株式会社 Composition de nettoyage en poudre pour machines de nettoyage automatisées
WO2017105827A1 (fr) * 2015-12-17 2017-06-22 The Procter & Gamble Company Composition de détergent pour lave-vaisselle automatique
EP3181672A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
EP3181671A1 (fr) * 2015-12-17 2017-06-21 The Procter and Gamble Company Composition de detergent de lave-vaisselle automatique
WO2017105857A1 (fr) * 2015-12-17 2017-06-22 The Procter & Gamble Company Composition de détergent pour lave-vaisselle
US10421927B2 (en) 2015-12-17 2019-09-24 The Procter & Gamble Company Automatic dishwashing detergent composition comprising benzotriazole and nonionic surfactant mixture
US10683471B2 (en) 2015-12-17 2020-06-16 The Procter & Gamble Company Automatic dishwashing detergent composition
US10808207B2 (en) 2015-12-17 2020-10-20 The Procter & Gamble Company Automatic dishwashing detergent composition
EP3266860A1 (fr) * 2016-07-08 2018-01-10 The Procter and Gamble Company Procédé de fabrication d'une particule
US10377969B2 (en) 2016-07-08 2019-08-13 The Procter & Gamble Company Process for making a particle

Also Published As

Publication number Publication date
DK47091A (da) 1992-09-16
DE69229366T2 (de) 1999-10-07
DK47091D0 (da) 1991-03-15
EP0504091B1 (fr) 1999-06-09
DK166548B1 (da) 1993-06-07
DE69229366D1 (de) 1999-07-15
ES2132113T3 (es) 1999-08-16

Similar Documents

Publication Publication Date Title
EP0504091B1 (fr) Composition pour le lavage machinal de la vaisselle sans phosphate
US5898025A (en) Mildly alkaline dishwashing detergents
EP0692019B1 (fr) Briquettes de detergent solide
AU2006310249B2 (en) Detergent composition
US6194368B1 (en) Dishwasher product in tablet form
EP0893491B1 (fr) Compositions détergentes pour lave-vaisselle automatiques
EP0737738B1 (fr) Comprimés d'agent de blanchiment
US5650017A (en) Washing process and composition
CA2145663A1 (fr) Detergents legerement alcalins pour machines a laver la vaisselle
CA2223609A1 (fr) Pastilles pour lave-vaisselle contenant un systeme de blanchiment a l'oxygene
EP2392639B1 (fr) Mélange d'un agent tensioactif avec un composé solide pour améliorer la performance de rinçage de détergents pour le lavage automatique de la vaisselle
CA2040307A1 (fr) Comprimes de detergent efferverscent
EP0508934A1 (fr) Composition détergente pour le linge
US10316277B2 (en) High performance laundry powder unit dose and methods of making the same
CA2166277A1 (fr) Detergents pour lave-vaiselle renfermant un adjuvant biodegradable
EP0541475B1 (fr) Composition pour le lavage automatique de la vaisselle
JPH05132696A (ja) 織物付着防止のための組成物及び方法
CA2166186A1 (fr) Detergents pour lave-vaisselle, renfermant un adjuvant biodegradable
JP3827824B2 (ja) 衣料用洗剤組成物
EP2000460A1 (fr) Nouveaux agents tensioactifs pour compositions détergentes
EP0463802B1 (fr) Procédé pour prévention de l'incrustation sur le tissu
JPS61108697A (ja) 重合体含有洗剤組成物

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL

17P Request for examination filed

Effective date: 19930304

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

Owner name: CLEANTABS A/S

17Q First examination report despatched

Effective date: 19980114

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL

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

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: 19990609

Ref country code: FR

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: 19990609

Ref country code: BE

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: 19990609

REF Corresponds to:

Ref document number: 69229366

Country of ref document: DE

Date of ref document: 19990715

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2132113

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: BIANCHETTI - BRACCO - MINOJA S.R.L.

EN Fr: translation not filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: CLARIANT GMBH

Effective date: 20000308

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20020209

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

Ref country code: DE

Payment date: 20110325

Year of fee payment: 20

Ref country code: GB

Payment date: 20110325

Year of fee payment: 20

Ref country code: ES

Payment date: 20110323

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20110329

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69229366

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69229366

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20120311

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20120313

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20120604

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 EXPIRATION OF PROTECTION

Effective date: 20120311

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 EXPIRATION OF PROTECTION

Effective date: 20120313