DK166548B1 - PHOSPHATE-FREE MACHINE DISHWASH - Google Patents

Description

in DK 166548 B1

Technical area

The present invention relates to a phosphate-free machine dishwashing agent comprising non-ionic surfactant, carboxylic acid, water-soluble alkaline compound and bleach, and optionally one or more adjuvants or additives.

Technical Background 10 Conventional dishwashing detergents are usually in the form of particulate / granular or liquid products which, when used, provide a dishwashing water with a high alkaline pH, often between 11 and 12. The usual dose of such detergents is between 30 and 60 g for each wash cycle. Conventional dishwashing agents usually include phosphates to soften the water, surfactants to loosen food and other unwanted residues, and chlorine bleaches. A typical chlorine-containing and phosphate-containing dishwashing detergent intended for use in an amount of 40 20 g / ml. washing cycle may contain 22 wt% phosphate, 25 wt% anhydrous metasilicate, 22.5 wt% sodium carbonate, 1.5-4.5 wt% chlorine bleach and 2 wt% nonionic surfactant (A.S. Davidson and B. Milwidsky, Syntetic Detergents 1987).

25 High alkalinity has so far been considered necessary to obtain suitable cleaning properties, but it does cause several disadvantages. Soft metal objects such as aluminum are often attacked by such alkaline agents as the surfaces are etched. Likewise, in case of any scratches in 30 porcelain or glass, an attack that goes into depth in these materials can occur. Furthermore, high alkalinity can cause damage to plastic objects and to porcelain glaze. The high alkalinity also makes it difficult to incorporate enzymes. In addition, the highly alkaline environment can be devastating on the dishwasher, and it is dangerous to come in contact with the heavy base, which may cause problems with the use and storage of the agent especially in homes with children or animals.

2 DK 166548 B1

Many conventional dishwashing detergents contain chlorine compounds as bleach, which often causes cutlery to tarnish and stain. This effect is more pronounced the lower the pH value. Conversely, the use of chlorine bleaching agents in highly alkaline dishwashing agents presents great disadvantages in the preparation and storage, many materials being degraded by direct contact with active chlorine. The stability of chlorine bleach dl is also critical, and this causes further problems, i. for storage and use at home, with 10 easily released toxic chlorine vapors.

The use of chlorine bleach has the advantage that there is a markedly lower sensitivity to low washing temperatures, increased water hardness and the presence of heavy metal ions. This provides clear advantages in terms of the bleaching effect, since it is easier to formulate inexpensive detergents which have good bleaching properties even under difficult conditions such as low temperatures and hard water. A major disadvantage, however, is that the extremely high reactivity (which produces high diapers) completely excludes the use of enzymes that are now considered necessary if it is to be satisfactorily removed especially starchy but also protein-containing. food residues, which is especially a problem when using low-temperature program 25 or ecology program for reasons of resources and economy.

More recently, the environmental disadvantages of phosphates have become more aware, and therefore efforts are being made to replace phosphorus compounds and other environmentally harmful compounds.

S

30 substances with substances that have a similar effect, but which are more gentle to the environment.

A similar development is underway, as society and the individual citizen have in recent years become increasingly aware of the environmental and resource consequences of the large consumption of e.g. laundry detergents, detergents and detergents. Thus, there is an increasing need for detergents, with lower amounts of environmentally harmful and resource-consuming components than those normally used in the known detergents, an equally good or better cleaning effect can be achieved. With the present invention, substantial progress is made in this development.

Examples of the best phosphate-free dishwashing detergents known today are SUN PROGRESS®, a powdery phosphate-free, chlorine-free and non-corrosive dishwashing detergent from Lever, Germany, and Milde Kraft, which is also a phosphate-free. and chlorine-free, non-corrosive, powdery product marketed by Benckiser in Germany. However, these prior art washing machines in parts are still associated with certain disadvantages, the requirement that they must not be corrosive, that is, they do not have too high alkalinity, could only be met at the expense of a good cleaning effect. Thus, they do not meet the requirement that even the particularly difficult removable stains, such as coffee stains and tea stains, be satisfactorily removed when the detergent is used in a low dose.

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The difficulty of finding substitutes for phosphate in dishwashing detergents is highlighted in an article by W. Wichelhaus and H. Andree, Endwicklungstendenzen bei MaschinengeschirrspUhlmit-teln, Tenside Surf. That. 27, (1990) 1, pages 52-56, which states on column 25 on page 55: "Despite the many efforts of detergents, manufacturers have so far failed to formulate phosphate-free detergents which, with regard to their total, Performance spectrum is as good as conventional products. The few 30 phosphate-free products available on the market show above all the lack of performance reserve due to heavy soiling or high water hardness. " In the above article by Wichelhaus and Andree, it is proposed 35 to work with liquid dishwashing detergents to make it easier to dispense the detergent at suitably low doses. Another way is to prepare the machine dishwashing liquid in the form of tablecloths, which provide a convenient way to ensure a low and yet sufficient dosage.

However, such tablet preparation causes problems, since it has been found that if a powder detergent formulation suitable for removing difficult stains, such as tea stains, is pressed into tablets, there is a deterioration in the effectiveness against tea stains. One possible explanation for this phenomenon may be that among the drug constituents e-10 necessary for the removal of coffee and tea stains, as well as bleach-stabilizing components when dispensed in the form of a powder, are rapidly dissolved in the washing water, which - at the concentration of bleaching agent rapidly reaches a maximum value, where an effective bleaching effect occurs on the said hard removable stains. When the detergent is used in the form of tablets, especially if difficult conditions such as hard water and low temperature are present, the bleach will dissolve more slowly in the washing water and therefore the bleach concentration will increase slowly over a longer period and not reach the same. maximum value as in powdered dosage. The slower release of the bleach to the dishwashing water will also increase the tendency for inactivation of the active bleaching radicals, and also the bleach stabilizing components will exhibit a slow release profile so that the stabilization of the bleach also becomes more uncertain.

EP Publication No. 0,256,148 (Ussat et al .; Joh. A. Benckiser GmbH) discloses a cleaning and descaling agent for dishwashers. Such a product can be counted on anhydrous basis e.g. Contain 60 wt% citric acid, 38 wt% amidosulfonic acid, 0.2 wt% perfume and 1.8 wt% nonionic surfactant, cf. Example 1. However, this product is not in itself a detergent, but is intended to remove the coatings. formed after conventional use of the dishwasher.

DE Publication No. 2,230,453 (Filcek et al .; Benckiser) discloses a basic composition for use in both washing machines and dishwashers. The basic composition comprises 1-40% by weight of citric acid or citrate to 1 part by weight of nonionic surfactant and, when the agent is a machine dishwashing detergent, combined with an additional 1-30 parts by weight of sodium metasol in cat, 0-12 parts by weight of sodium carbonate and 0-4 parts by weight of additional materials , such as neutral salt and chlorine bleach. The said dishwashing detergent has, as mentioned, a content of sodium methasicate, which makes such a detergent corrosive.

10 From US Patent No. 3,692,684 (Hentschel) (which corresponds to SE Patent Laid-Open No. 352,652), universal cleaners, including one designed for machine washing, are known. The agents are made up of water softeners and wash effect enhancers which are alkaline salts of organic, aliphatic and / or aromatic carboxylic acids and / or anhydrides thereof having a hydrophobic moiety of not more than 8 carbon atoms. As an example of a machine dishwashing agent, Example 7 is disclosed comprising 3 parts nonionic surfactant, 3 parts sodium alkyl polyglycol ether phosphate, 25 parts sodium acetate, 25 parts 20 sodium sulfate, 30 parts sodium citrate, and 14 parts excipients comprising perfume, dye, bactericide and water. Hentschel does not specify what dose such a dishwashing detergent should be used, and it must be assumed that Hentschel has used the conventional high dose of approx. 40 g per wash cycle. 25 Hentschel also does not disclose the use of bleach and the agent will thus hardly be able to remove coffee and tea stains satisfactorily.

DE-Publication No. 2,323,355 (Dankworth et al., Benckiser) discloses a phosphate-free machine dishwashing agent which comprises as a complex linker 5-35% by weight of a mixture consisting of citric acid and a cyclic pentacarboxylic acid. Whenever possible, bleach is exclusively chlorine-based bleach. Dankworth's dishwashing detergent further contains 35 from 1 to 95% by weight of water-soluble alkaline compounds, exemplified in the exemplary embodiments, for example, by sodium metasol in cat and sodium hydroxide, which means that such dishwashing agents are corrosive.

6 DK 166548 B1

None of the previously known phosphate-free machine dishwashers have been found to be sufficiently effective, e.g. for removing coffee and tea stains when at the same time requiring that the agent must not contain chlorine-based bleach, must not appear corrosive and must be usable in a low dose.

It is the object of the present invention to provide a phosphate-free dishwashing detergent that meets these desires.

Description of the Invention

This is achieved with a phosphate-free machine dishwashing agent comprising nonionic surfactant, carboxylic acid, water-soluble alkaline compound and bleach, together with optionally an additional 15 or more adjuvants or additives, characterized in that the bleaching agent is a peroxide or peroxyhydrate, and the machine dishwashing agent comprises: 50 -140 parts by weight of alkali carbonate, 20 35-100 parts by weight of polycarboxylate, 33-100 parts by weight of a polyfunctional carboxylic acid having 2-10 carbon atoms and at least 2 functional groups selected from C00H and OH, 22-66 parts by weight of sodium silicate selected from layer silicate and 25 compounds with the composition Na 2 O: SiO 2 in the ratio 1: 1.9 to 1: 3.5, and 7 to 22 parts by weight of nonionic surfactant, per 100 parts by weight of bleach, where the parts are based on 30 anhydrous products without hydrate water.

The machine dishwashing detergent according to the invention has the following advantages:

The low alkalinity makes the detergent gentle on the dishwasher, dishes and cutlery and makes the detergent more environmentally friendly. The low alkalinity also significantly reduces the risk of corrosion, and it will not be necessary to use a child-safe packaging, which is expected to be introduced by law in 1992 for products with corrosion hazard.

The use of peroxide or peroxyhydrate as a bleach means avoiding the risk of chlorine release during and after washing, and during storage. It is possible to incorporate enzymes into the dishwashing detergent so as to ensure a significantly better cleaning effect against proteinaceous and starchy food residues. It is also possible to incorporate 10 perfumes in the dishwasher.

The detergent further has the advantage that it can be formulated in tablet form without loss of the bleaching effect, which in itself gives the advantages that, when using tablets, a uniformly low dosage can be ensured and prevent overdose. The tablet form also provides an opportunity for automatic dishwashing detergent to be used in future dishwashers.

In the dishwashing detergent according to the invention, the content of alkali carbonate is at least 50 parts by weight, preferably at least 75 parts by weight and especially preferably at least 85 parts by weight per unit weight. 100 parts by weight of bleach and at most 140 parts by weight, preferably at most 115 parts by weight and especially preferably at most 105 parts by weight per unit weight. 100 parts by weight 25 bl egemi ddel.

The content of polycarboxylate is at least 35 parts by weight, preferably at least 57 parts by weight and particularly preferably at least 64 parts by weight per unit weight. 100 parts by weight of bleach and at most 100 parts by weight, preferably at most 85 parts by weight and especially preferably at most 78 parts by weight per unit weight. 100 parts by weight of bleach.

The polycarboxylate is preferably a polyacrylate and / or a malic acid / acrylic acid copolymer having a molecular weight of 3,000-150. 35 000.

The content of the polyfunctional carboxylic acid is at least 33 parts by weight, preferably at least 53 parts by weight, and particularly preferred. 100 parts by weight of bleach and at most 100 parts by weight, preferably at most 80 parts by weight and especially preferably at most 73 parts by weight per unit weight. 100 parts by weight of bleach.

The polyfunctional carboxylic acid is preferably selected from citric acid, malic acid, tartaric acid, glutaric acid, tartaronic acid, gi uconic acid, salicylic acid, isoserindiacetic acid, NTA and EDTA.

The sodium silicate content is at least 22 parts by weight, preferably 10 at least 34 parts by weight, and most preferably at least 40 parts by weight, and at most 66 parts by weight, preferably at most 54 parts by weight, and most preferably at most 48 parts by weight. 100 parts by weight of bleach.

The sodium silicate is preferably sodium silicate and / or 1 is a so-called layer silicate.

The content of nonionic surfactant is at least 7 parts by weight, preferably at least 11 parts by weight and especially preferably at least 13 parts by weight and at most 22 parts by weight, preferably at most 19 parts by weight and especially 20 preferably at most 17 parts by weight. 100 parts by weight of bleach.

The bleach is preferably a per-compound or a perhydrate.

The machine dishwashing detergent according to the invention advantageously contains an additional 10-33 parts by weight of sequestering agent and / or 15-45 parts by weight of bleach activator per minute. 100 parts by weight of bleach.

The dishwasher detergent can advantageously be prepared in tablet form.

30

The dishwashing detergent according to the invention may advantageously have such a composition that at a solution of 1% by weight in water it gives a pH value of 7-10.5, preferably 8-10.0. Such a pH value ensures that the detergent does not appear corrosive.

35

The scope of the applicability of the invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and specific examples, indicating preferred embodiments of the invention, are provided by way of illustration only, as various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art. on the basis of the detailed description.

DETAILED DESCRIPTION OF THE INVENTION An essential feature of the present invention is the polyfunctional carboxylic acid which, during the washing process, acts as an actual complexing agent which binds the multivalent cations of the water thereby stabilizing the washing process, especially the bleaching process. The polyhydric carboxylic acid also has a favorable effect on the dissolution time when the machine dishwashing agent is formulated as a tablet, the polyfunctional carboxylic acid giving some effervescent effect upon reaction with the carbonate ions present. This shower effect has surprisingly been found to have a significant influence on the cleaning of tea and coffee stains 20.

As useful polyfunctional carboxylic acids may be mentioned aliphatic, cyclic or aromatic polyfunctional carboxylic acids containing at least one carboxyl group and an additional 25 at least one additional carboxyl group or hydroxy group and preferably several such functional groups selected from C00H and OH. Also included are salts and lactone derivatives, ester derivatives, alkoxylate derivatives, amine derivatives, diamine derivatives, sulfonate derivatives or sulfate compounds thereof.

30

Particularly preferred polyfunctional carboxylic acids include lactic, malic, tartaric, gluconic, glutaric, citric, tartaric and salicylic acids. The most preferred is citric acid, which is preferably used in anhydrous form.

35

In addition, as a polyfunctional carboxylic acid, a mixture of dicarboxylic acids supplied by BASF® AG under the trade name SOKALAN® DCS in the form of a white powder can be used. The product is a compound of the formula C00H (CH2) nC00H where n = 2 - 4.

5 Examples of useful bleaches include perhydrates and per-compounds as well as mixtures thereof. Preferably, the perhydrates include alkali metal compounds of perborates which may be present as tetra and monohydrates, perborax, percarbonates, persilicates, citrate perhydrates and perhydrates 10 of urea and melamine compounds. In addition, acidic salts such as persulfates (e.g. caroates), perbenzoates and peroxycarboxylic acids such as peroxyphthalate, magnesium monoperoxyphthalic acid, diperoxyphthalic acid, 2-octyldiperoxyacetic acid, di-peroxydodecandicarboxylic acid, diperoxyazelic acid, As particularly preferred bleaches may be mentioned sodium percarbonate and sodium perborate.

For bleaching systems, reference is made to P. Kuzel 20 and Th. Reader, Tenside Surf. That. 27 (1990) 1, pages 23-28.

Examples of the polycarboxylate used are polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, metaconic acid, acutinic acid, methylene malonic acid, citraconic acid 25 and the like, and copolymers of said carboxylic acids among themselves or with other ethylenically unsaturated compounds, , isobutylene, vinylalcohol, vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid or crotonic acid.

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The molecular weight of the polycarboxylate may range from 1000-1,000,000, preferably 2000-100,000 and most preferably 7000-30,000.

35 For polycarboxy1 ater, reference can be made to an article by J. Perner and H.-W. Neumann, entitled "Polycarboxy1 Eating in Cleaning Textiles and Non-Textile Substrates", Tenside Surfactants Detergents 24 (1987) 6, pages 334-340.

DK 166548 ΒΊ 11

The sodium silicate used may advantageously have the composition Na 2 O: SiO 2 in the ratio of 1: 1.9 to 1: 3.5, preferably from 1: 2 to 1: 3.5. Also used as sodium silicate, so-called layer silicates, i.e. compounds with the stoichiometric composition Na 2 SiO 5, in which the individual layers comprise SiO 2 tetrahedrons, having been found to be capable of complementing or completely replacing conventional sodium silicates. An advantage of layer silicates is that they also have an excellent ability to bind magnesium ions, which play a not insignificant role 10 in depositing lime on the heaters of the dishwashers. A preferred layer silicate is one supplied as a granular with the trade name SKS-6, by HOECHST® AG, Frankfurt am Main, Germany.

The surfactants which can be used in the detergent of the invention can be any non-foaming nonionic surfactant, in particular alkylene oxide adducts (ethylene oxide adducts (EO), propylene oxide (PO) and / or butylene oxide (BO) and mixtures thereof) of alcohols, thioalcohols , diols, fatty acids, 20 fatty acid amides, alpha-cansulfonamides, alkylamines as well as alkylphenols which have been rendered weakly foaming e.g. by substituting the free hydroxyl groups of the polyalkylene glycol ether residues with ether or acetal groups. A mention of nonionic surfactants particularly suitable for use in machine dishwashing detergents is found e.g. in GB Patent No. 2,206,601 and the writings cited therein.

It is preferred to use fatty alcohol EO adducts and / or fatty alcohol EO PO adducts such as e.g. PLURAFAC® LF 403 from 30 BASF® AG, UKANIL FM 2136 and SYNPERONIC® RA 30 from ICI or DEHYPON® LT 104 or DEHYD0L® LS 54 from Henkel KGaG.

When choosing nonionic surfactant, it should be noted that products that do not contain chlorine bleach are not nearly as demanding with regard to the choice of stable 1 scouring surfactants. Thus, as is the case with chlorine bleach-containing products, it is not necessary to use particularly expensive surfactants that can withstand the reaction between chlorine and surfactant. Such reactions between chlorine and surfactant may cause the foaming properties to disappear or odor nuisance to occur.

The amount of surfactant used may vary depending on whether adjuvants such as glycerol. If the surfactant is used without adjuvants, the amount of nonionic surfactant is preferably 13-21, particularly preferably 15-19 such as e.g. ca. 17 parts by weight of nonionic surfactant per 100 parts by weight of bleach, 10 while the amount of nonionic surfactant when used together with adjuvants is preferably 9-17, particularly preferably 11-15 such as e.g. ca. 13 parts by weight of nonionic surfactant per unit weight. 100 parts by weight of bleach. The excipient used may e.g. constitute glycerol in an amount of 2-7, preferably 3-5 parts by weight per day. 100 parts by weight of bleach. Use of excipients such as glycerol may in some cases improve the product, e.g. in terms of storage stability.

Further, in the detergent of the invention there may be a sequestering agent having a sequestering and complex binding action such as nine trilotriacetic acid (NTA), iso-serine diacetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DETPA), hydroxyethylacetic acid ( ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), ethylenediamine tetra (methylene phosphonic acid) (EDTMP), diethylenetriamine penta (methylene phosphonic acid) (DETPMP), amino-trimethylene phosphonic acid (ATMP), and phytic acid and phytic acid derivatives, including such salts , in particular with alkali metal or alkaline earth metal. As the phytic acid salt may be mentioned the dodecane sodium salt of phytic acid (inositol hexaphosphoric acid) provided by Sigma Chemical Company, USA. Particularly preferred sequestering agents are the disodium and tetrasodium salt of ethane-1-hydroxy-1,1-diphosphonic acid, respectively, supplied in the form of a light-flowing powder under the respective 35 trade names SEQUION 10 NAPDR and DEQUEST® 2016 D by G. Bozetto SpA, respectively. Filago, Italy and Monsanto PLC, England. Such phosphonic acid compounds have, in addition to the complex binding properties which, among other things, help to stabilize the bleaches present, in addition, so-called threshold properties (ie, precipitation-limiting properties) due to their large sequestering capacity.

5

Some of the aforementioned sequestering agents are polyfunctional carboxylic acids which, in addition to the one mandatory carboxylic acid, also contain at least one additional functional group selected from carboxyl and hydroxy while also containing nitrogen in the molecule. As a result of said functional groups (OH and C00H), it is believed that such sequestrants may be included as the polyfunctional carboxylic acid which is a mandatory part of the machine dishwashing detergent according to the invention or as part thereof. Such compounds are e.g. isoses in ndi acetic acid, NTA and EDTA. Iso-acetic acid having the formula (CH2COOH) 2N-CH2CHOHCOOH, which is expected to be marketed by BASF AG, Germany over a 1-2 year period in the form of a liquid product containing 40%, is expected to be the future replacement for EDTA, and will could be used in the detergent of the invention, however, in the case of tablets on the condition that the compound can be supplied as a stable powder with sufficient acid action to react with basic salts such as alkali carbonates to form carbon dioxide. NTA and EDTA already meet such conditions, and therefore may also be advantageously used in the case of tablets in the detergent according to the invention.

In order to obtain a sufficient bleaching effect, if the washing is carried out at lower temperatures in the range 40-60 ° C, there may be added bleach activators. As non-limiting examples there may be mentioned N-acyl compounds and O-acyl compounds such as acylated amines, diamines, amides, acylated glycoluriles, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulforyl amides, cyanurates and 35 imidazolines, carboxylic anhydrides, acylated sugar compounds, acylated ester compounds and the like. Particularly preferred are the tetraacetylmethylenediamine, tetraacetyl-ethylene diamine (TAED), and higher homologs, tetraacetylglycoluril (TAGU), pentaacetylglycose (PAGE), p . Most preferred is TAED, which may be present as a granulate having an active content of 85-95% by weight.

A more detailed description of bleach activators can be found in GB patent specification 2040983 and GB patent specification 1473201.

As previously mentioned, machine detergent according to the invention can advantageously be prepared in the form of tablets, intended for use e.g. one or two tablets for each washing cycle. In the manufacture of tablets, tablet adjuvants are usually added e.g. in the form of starch, glycerol, polyethylene glycol, preferably having a molecular weight of 100-10,000, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone (PVPP) or a stearate compound, such as sodium stearate.

Such tablet adjuvants ensure adequate consistency and granulation.

Tablet preparation 11 per day takes place in a manner known per se, first forming a base powder fraction comprising bleach, polyfunctional carboxylic acid, alkali carbonate, polycarboxylate, sodium silicate and enzymes. After briefly stirring for 1-5 minutes, the nonionic surfactant is sprayed, after which one or more tablet adjuvants can be sprayed or added followed by a sieve blend for 2-10 minutes. The resulting powder mixture is pressed into tablets having a diameter of e.g. 32 30 mm in a tablet press (e.g., Grease Perfects 4B). The thickness of the tablets produced depends on the desired tablet weight and formulation and is usually between 13 and 20 mm. Further examples of tablet preparation are disclosed in U.S. Patent No. 355,626, U.S. Patent No. 328,880, and U.S. Patent No. 3,827,895.

The invention is illustrated in the following by means of some examples.

Example 1 15 DK 166548 B1 This example discloses a powder dishwasher detergent intended for use in an amount of 18 g of detergent 5 per liter. wash cycle: weight%

Sodium percarbonate 22.0

Sodium carbonate 22.0 SOKALAN® PA 40 16.0

Citric Acid 15.0

Sodium Dissilicate 10.0 TAED 3711 7.0 PLURAFAC® LF 403 4.0 15 TERMAMYL® 60T 3.0 ESPERASE® 6.0 T 1.0 SOKALAN PA 40 is a powdered polyacrylate in the form of the sodium salt having a molecular weight of approx. 15,000, supplied by BASF, 20 Germany.

TAED 3711, tetraacetylethylenediamine, is supplied by H0ECHST AG, Germany.

25 PLURAFAC LF 403 is a non-foaming nonionic surfactant in the form of ethoxylated fatty alcohol, supplied by BASF, Germany.

TERMAMYL 60T is an amylolytic enzyme, supplied by NOV0-NODDISK, Denmark.

30 ESPERASE 6.0 T is a proteolytic enzyme supplied by N0V0-NORDISK, Denmark.

Example 2 35 This example illustrates a phosphonate-containing machine dishwashing detergent according to the invention intended for use at a dose of 18 g / ml. wash cycle.

16 DK 166548 B1 wt%

Sodium percarbonate 21.0

Sodium carbonate 19.0 SOKALAN PA 40 16.0 Citric acid 15.0

Sodium disisi 1 in cat 10.0 TAED 3711 7.0 DEQUEST® 2016 D 5.0 PLURAFAC LF 403 4.0 10 TERMAMYL 60T 2.0 ESPERASE 6.OT 1.0 DEQUEST 2016 D is the tetrasodium salt of 1-hydroxy-ethanol. 1,1-diphosphonic acid (HEDP) supplied by MONSANTO, England.

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Example 3 The present example relates to a detergent tablet weighing 18 g, formulated in the same manner as the detergent 20 of Example 2, except that the citric acid has been replaced by an equivalent amount of trisodium citrate dihydrate. With this change, the detergent has a higher alkalinity, and the tablet does not have the beneficial shower effect obtained by using citric acid. In the washing experiments mentioned below, this detergent showed a strong tendency for foaming, although the nonionic surfactant used was low-foaming.

Combination experiments Measuring pH 30

To assess the alkali level, pH measurements have been made on 1% aqueous solutions of various detergents. The results are shown in the following table: 35 DK 166548 B1 17

Detergent pH

Mild Power 10.8 SUN PROGRESS (Liver) 10.6 DE 2,230,453 * 12.1 5 Example 2 9.6

Example 1 9.5

Washing tests 10 Comparative tests have been performed under the following test conditions:

Dishwasher: Cylinda E 1500 temperature: 55 ° C - no pre-wash, 15 water hardness: 20 ° dH, soiling: in accordance with the guidelines of the International Electrotechnical Commission (IEC), number of dishes: 12.

20 In the wash experiments, point values are given as follows:

After each dish, each cup, plate, knife, fork, etc. is evaluated on a scale of 1 to 5 points. The point values are calculated for teacups and, moreover, porcelain and cutlery, and 25 a total point value is also calculated. The point values obtained in these experiments are given in the following table, where 100% is the maximum achievable point value.

30 35 DK 166548 B1 18

Average point values after 12 dishwashing attempts

Detergent Tea% Non-Tea% Total%

Example 1 56 59 56 5 Example 2 59 58 57

Example 3 20 69 38

Mild Power 42 68 61 DE 2,230,453 * 89 48 73 10 * Detergent according to Example 3 of DE Publication No. 2,230,453, dosage.pr. wash 40 g.

The detergents of Examples 1, 2 and 3 were used in an amount of 18 g / ml. wash cycle.

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Mild Kraft is a phosphate-free and chlorine-free, non-corrosive product supplied by Benckiser and is used at a dose of 24 g / ml. wash cycle.

20 It appears from the experiments that the detergent from DE 2,230,453 gives a lower point value for "non-tea", although dosing at 40 g / d. dishwashing. In contrast, the removal of tea stains is better than that of the dishwashing detergent according to the invention (Examples 1 and 2), but on the other hand it is also strongly alkaline with a pH of 12.1.

The use of trisodium citrate dihydrate in place of citric acid (Example 3) results in a significant deterioration in the removal of tea stains.

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Mild Kraft, which represents the best phosphate-free and chlorine-free, non-corrosive products on the market, provides, at use at a dose of 24 g, significantly less removal of tea stains compared to the detergents of Examples 1 35 and 2 used in an amount of 18 g per wash cycle.

Claims (9)

Sodium Perborate Monohydrate 21.0 Sodium Carbonate 22.0 19.0 19.0 19.0 SOKALAN PA 40 16.0 16.0 12.0 16.0 Polyfunct. carboxylic acid 15.0 10.0 15.0 15.0 Sodium di sieve in cat 5.0 SKS-6 (layer silicate) 10.0 10.0 5.0 10.0 TAED 3711 7.0 7.0 7 , 0 7.0 DEQUEST 2016 D 3.0 Isoserinediacetic acid 5.0 8.0 3.0 PLURAFAC LF 403 4.0 4.0 4.0 4.0 4.0 20 TERMAMYL 60 T 3.0 2.0 3.0 3 , 0 ESPERASE 6.0 T 1.0 1.0 ESPERASE / SAVINASE® 2.0 / 2.0 T 2.0 2.0 Patent claims. 25 ------------------ 1. Phosphate-free machine dishwashing detergent comprising nonionic surfactant, carboxylic acid, water-soluble alkaline compound and bleach, and optionally one or more adjuvants or additives, characterized in that, for example, the diet is a peroxide or peroxyhydrate and that the dishwashing detergent comprises 50 to 140 parts by weight of alkali carbonate. 35-100 parts by weight of polycarboxylate, 33-100 parts by weight of polyfunctional carboxylic acid with 2-10 carbon atoms and at least 2 functional groups selected from carboxyl and hydroxy, DK-166548 B1 22-66 parts by weight of sodium silicate selected from the layer silicate and compounds of the composition Na 2 O: SiO2 in a ratio of 1: 1.9 to 1: 3.5, and 7-22 parts by weight of non-ionic surfactant, 5 per cent. 100 parts by weight of bleach, where the parts are based on anhydrous products without hydrate water. Machine detergent according to claim 1, characterized in that it comprises: 75-115 parts by weight of alkali carbonate, 57-85 parts by weight of polycarboxylate, 53-80 parts by weight of polyfunctional carboxylic acid, 34-54 parts by weight of sodium silicate, and 11-19 parts by weight of non-ionic surfactant per liter. 100 parts by weight of bleach, where the parts are based on anhydrous products without hydrate water. Machine dishwashing detergent according to claim 1, characterized in that it comprises: 85-105 parts by weight alkali carbonate, 64-78 parts by weight polycarboxylate, 59-73 parts by weight polyfunctional carboxylic acid, 40-48 parts by weight sodium silicate and 13-17 parts by weight nonionic surfactant 30 100 parts by weight of bleach, where the parts are based on anhydrous products without hydrate water. Machine detergent according to claim 1, characterized in that the polycarboxylate is a polyacrylate and / or a maleic acid / acrylic acid copolymer having a molecular weight of 3000-150,000. Machine dishwashing detergent according to claim 1, characterized in that the polyfunctional carboxylic acid is selected from ci- DK 166548 B1 tronic acid, malic acid, tartaric acid, glutaric acid, tartronic acid, gluconic acid, salicylic acid, isoserindiacetic acid, NTA or EDTA. Machine dishwashing detergent according to claim 1, characterized in that the sodium silicate used is sodium disilicate. Machine dishwashing detergent according to claim 1, characterized in that it further comprises 10-33 parts by weight of sequestering agent and / or 15-45 parts by weight of bleach activator per unit weight. 100 10 parts by weight of bleach, where the parts are based on anhydrous products without hydrate water. Machine detergent according to claim 1, characterized in that it is manufactured in tablet form. 15 Machine dishwashing detergent according to claim 1, characterized in that at a solution of 1% by weight in water it gives a pH value of 7-10.5. 20 25 30 35