EP0504091A1 - Composition pour le lavage machinal de la vaisselle sans phosphate - Google Patents
Composition pour le lavage machinal de la vaisselle sans phosphate Download PDFInfo
- 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
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- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- 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
- C11D17/0091—Dishwashing tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic 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.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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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)
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)
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)
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 |
-
1991
- 1991-03-15 DK DK47091A patent/DK166548B1/da not_active IP Right Cessation
-
1992
- 1992-03-12 ES ES92610015T patent/ES2132113T3/es not_active Expired - Lifetime
- 1992-03-12 DE DE1992629366 patent/DE69229366T2/de not_active Expired - Lifetime
- 1992-03-12 EP EP92610015A patent/EP0504091B1/fr not_active Expired - Lifetime
Patent Citations (4)
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)
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 |
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