Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
• • 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
• • 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
• • 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
• • 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 in the form of a tablet or powder 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.
• JP-A-63 23216 discloses a dishwashing formulation containing 1-30 wt% hydroxy polyvalent carboxylic acid or salt thereof, 1-10 wt% macromolecular chelating agent, 35-85 wt% inorganic alkali agent, 0.2-5 wt% amylase and 5-25 wt% oxygen-based bleach.
• the hydroxy polyvalent carboxylic acid is used as salts thereof, that is sodium malate, sodium tartrate or sodium citrate.
• the amount of inorganic alkali agent is relatively high, e.g. 45.5 wt% with a ratio of 300 parts by weight inorganic alkali agent per 100 parts by weight of the bleach.
• 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.
• a phosphate-free automatic dishwashing composition in the form of a tablet or powder comprising a chlorine-free oxygen donating bleach,optionally one or more adjuvants or additives, and 20-150 parts by weight of alkalicarbonate or a mixture of alkalicarbonate and alkalibicarbonate, 8-150 parts by weight of polycarboxylate, 20-150 parts by weight of polyfunctional carboxylic acid having 2-10 carbon atoms and at least 2 functional groups selected from the group consisting of carboxyl and hydroxyl, with the proviso that at least one of said functional groups is carboxyl, 20-70 parts by weight of sodium silicate in the form of layer silicate or Na 2 O:SiO 2 in the ratio from 1:0.5 to 1:3.5, and 5-25 parts by weight of nonionic tenside, per 100 parts by weight of the bleach, the parts by weight being based on the anhydrous product without hydration water.
• 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, more preferably 57 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.
• 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 monoperoxy phthalic 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 Na 2 O:SiO 2 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 Na 2 SiO 5 , each layer consisting of SiO 4 -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 Na 2 SiO 5 , each layer consisting of SiO 4 -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
• 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 glycol-ether 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 BASF AG, UKANILTM 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-l-hydroxy-l,l-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 nitrilotri
• 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-l-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 (CH 2 COOH) 2 N-CH 2 CHOHCOOH 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, alkalibicarbonate, 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.
• % by weight Sodium percarbonate 22.0 Sodium carbonate 22.0 SOKALANTM
• PA 40 16.0
• Citric acid 15.0
• Sodium disilicate 10.0
• PLURAFACTM LF 403 4.0
• TERMAMYLTM 60 T 3.0 ESPERASETM 6.0 T 1.0
• This example illustrates a phosphonate-containing automatic dishwashing composition according to the invention to be used in an amount of 18 g per wash cycle.
• % by weight Sodium percarbonate 21.0 Sodium carbonate 19.0 SOKALANTM
• PA 40 16.0 Citric acid 15.0 Sodium disilicate 10.0 TAED 3711 7.0 DEQUESTTM 2016 D 5.0 PLURAFACTM LF 403 4.0 TERMAMYLTM 60 T 2.0 ESPERASETM 6.0 T 1.0 DEQUESTTM 2016 D: tetrasodium salt of 1-hydroxy-ethane-1,1-diphosphonic acid (HEDP), available from MONSANTO, Great Britain.
• HEDP 1-hydroxy-ethane-1,1-diphosphonic acid
• 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.
• Dishwashing composition Tea % Non-tea % Total %
• Example 1 56 59 56
• Example 2 59 58 57
• Example 3 20 69 38 Milde Kraft 42 68 61 DE 2.230.453 89 48 73
• 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.

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