DETERGENTt COMPOSITION
10 claims: 7 independent, 3 dependent
- 1Phosphatfreies maschinelles Geschirrspülmittel, enthaltend Gerüststoff, Bleichmittel, nichtionisches Tensid, sowie weiterhin a) Copolymer, enthaltend i) Sulfonsäuregruppen-haltige Monomere ii) Monomere der allgemeinen Formel R 1 (R 2 )C=C(R 3 )-X-R 4 , in der R 1 bis R 3 unabhängig voneinander für -H, -CH 3 oder -C 2 H 5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH 2 -, -C(O)O- und -C(O)-NH-, und R 4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht, b) Methylglycindiessigsäure.
- 2Maschinelles Geschirrspülmittel nach Anspruch 1, dadurch gekennzeichnet, dass der Gewichtsanteil des Copolymers a) 4 bis 18 Gew.-%, vorzugsweise 6 bis 15 und insbesondere 6 bis 12 Gew.-% beträgt.
- 3Maschinelles Geschirrspülmittel nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass der Gewichtsanteil der Methylglycindiessigsäure b) 0,5 bis 20 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-% und insbesondere 0,5 bis 8 Gew.-% beträgt.
- 4Maschinelles Geschirrspülmittel nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass es 5 bis 60 Gew.-%, vorzugsweise 10 bis 50 Gew.-% und insbesondere 15 bis 40 Gew.-% Citrat enthält.
- 5Maschinelles Geschirrspülmittel nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass es 1 bis 20 Gew.-%, vorzugsweise 2 bis 15 Gew.-% und insbesondere 4 bis 12 Gew.-% Natriumpercarbonat enthält.
- 6Maschinelles Geschirrspülmittel nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass es das nichtionische Tensid in Mengen von 1 bis 10 Gew.-%, vorzugsweise 2 bis 8 Gew.-% und insbesondere 3 bis 6 Gew.-% enthält.
- 7Maschinelles Geschirrspülmittel nach einem der vorherigen Ansprüche, enthaltend a) 6 bis 15 Gew.-% Copolymer, umfassend i) Sulfonsäuregruppen-haltige Monomere ii) Monomere der allgemeinen Formel R 1 (R 2 )C=C(R 3 )-X-R 4 , in der R 1 bis R 3 unabhängig voneinander für -H, -CH 3 oder -C 2 H 5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH 2 -, -C(O)O- und -C(O)-NH-, und R 4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht b) 0,5 bis 10 Gew.-% Methylglycindiessigsäure c) 10 bis 50 Gew.-% Citrat d) 2 bis 15 Gew.-% Natriumpercarbonat e) 2 bis 8 Gew.-% nichtionisches Tensid
- 8Maschinelles Geschirrspülmittel nach einem der vorherigen Ansprüche, enthaltend a) 6 bis 15 Gew.-% Copolymer, umfassend i) Sulfonsäuregruppen-haltige Monomere ii) Monomere der allgemeinen Formel R 1 (R 2 )C=C(R 3 )-X-R 4 , in der R 1 bis R 3 unabhängig voneinander für -H, -CH 3 oder -C 2 H 5 steht, X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -CH 2 -, -C(O)O- und -C(O)-NH-, und R 4 für einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 22 Kohlenstoffatomen oder für einen ungesättigten, vorzugsweise aromatischen Rest mit 6 bis 22 Kohlenstoffatomen steht b) 0,5 bis 10 Gew.-% Methylglycindiessigsäure c) 10 bis 50 Gew.-% Citrat d) 2 bis 15 Gew.-% Natriumpercarbonat e) 2 bis 8 Gew.-% nichtionisches Tensid f) 1,0 bis 6 Gew.-% Enzym.
- 9Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine, unter Einsatz maschineller Geschirrspülmittel nach einem der Ansprüche 1 bis 8.
- 10Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass im Verlauf des Reinigungsverfahrens kein zusätzlicher Wasserenthärter und kein zusätzlicher Klarspüler in den Innenraum der Geschirrspülmaschine dosiert wird.
Independent claims10
173 paragraphs, as filed
0001The present patent application describes cleaning agents, in particular cleaning agents for the automatic cleaning of dishes. The subject of this application is, in particular, phosphate-free automatic dishwashing detergents.
0002Today, machine-washed dishes are often subject to higher demands than manually washed dishes. After machine cleaning, the dishes should not only be completely free of food residue, but should also not have any whitish stains caused by water hardness or other mineral salts that come from dried water droplets due to the lack of wetting agents.
0003Modern automatic dishwashing detergents meet these requirements by integrating cleaning, caring, water-softening and rinse-active ingredients and are known to consumers, for example, as “2-in-1” or “3-in-1” dishwashing detergents. The automatic dishwashing detergents intended for private end users contain builders as an essential component for cleaning and rinsing success. On the one hand, these builders increase the alkalinity of the cleaning liquor, with fats and oils being emulsified and saponified as alkalinity increases, and on the other hand, they reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor. Alkaline metal phosphates have proven to be particularly effective builders, and for this reason they form the main component of the majority of commercially available automatic dishwashing detergents.
0004While phosphates are highly valued for their beneficial effects as a component of automatic dishwashing detergents, their use is not unproblematic from the perspective of environmental protection, since a significant portion of the phosphate ends up in waterways via household wastewater and especially in stagnant waters (lakes , barrages) play a worrying role in their over-fertilization. As a result of this phenomenon, also known as eutrophication, the use of pentasodium triphosphate in textile detergents has been significantly reduced by legal regulations in many countries, e.g. USA, Canada, Italy, Sweden, Norway, and completely banned in Switzerland. In Germany, detergents have been allowed to contain a maximum of 20% of this builder since 1984.
0005In addition to nitrilotriacetic acid, sodium aluminum silicates (zeolites) are used as phosphate substitutes in textile detergents. However, these substances are not suitable for use in automatic dishwashing detergents for various reasons. As an alternative to the alkali metal phosphates in automatic dishwashing detergents, a number of substitutes are being discussed in the literature, of which citrates deserve particular mention.
0006Phosphate-free automatic dishwashing detergents, which, in addition to a citrate, also contain carbonates, bleaches and enzymes, are used, for example, in European patents<patcit id="pcit0001" dnum="EP662117B1"><text>EP 662 117 B1</text></patcit> (Henkel KGaA) and<patcit id="pcit0002" dnum="EP692020B1"><text>EP 692 020 B1</text></patcit> (Henkel KGaA).
0007Another alternative to alkali metal phosphates, which is used as the sole builder but preferably in combination with citrates, is methylglycine diacetic acid (MGDA). Machine dishwashing detergents containing MGDA are described, for example, in the European patent<patcit id="pcit0003" dnum="EP906407B1"><text>EP 906 407 B1 (Reckitt Benckiser</text></patcit>) or in the European patent application<patcit id="pcit0004" dnum="EP1113070A2"><text>EP 1 113 070 A2 (Reckitt Benckiser</text></patcit>).
0008<patcit id="pcit0005" dnum="EP1721962A"><text>EP-A-1721962</text></patcit> describes phosphate-free, automatic dishwashing agents that contain non-ionic surfactants, MGDA, percarbonate and citrate, but no copolymers containing sulfonic acid groups.<patcit id="pcit0006" dnum="WO2006106332A"><text>WO 2006/106332</text></patcit> describes phosphate-free, automatic dishwashing detergents that contain non-ionic surfactants, MGDA, citrate and copolymers containing sulfonic acid groups, but no bleaching agents.
0009<nplcit id="ncit0001" npl-type="b"><text>Potthoff-Karl et al. (SOFW Journal Soaps, Oils, Fats, Waxes, Verlag für Chemische Industrie, Augsburg, DE, Vol. 122, No. 6, May 1, 1996, pages 392-394 and 396</text></nplcit>) describe phosphate-free, automatic dishwashing detergents that contain non-ionic surfactants, MGDA, percarbonate and citrate, but no copolymers containing sulfonic acid groups.
0010<patcit id="pcit0007" dnum="WO2005090541A"><text>WO 2005/090541</text></patcit> discloses, among other things, a phosphate-free, automatic dishwashing detergent that contains surfactants, citrate, bleach and copolymers containing sulfonic acid groups, but no MGDA.
0011<patcit id="pcit0008" dnum="US5308532A"><text>US 5,308,532</text></patcit> describes aminoacryloyl-containing terpolymers and automatic dishwashing detergents containing them, although the disclosed dishwashing detergents do not contain MGDA.
0012The subsequently published international pafent publication<patcit id="pcit0009" dnum="WO2007052064A"><text>WO 2007/052064</text></patcit> describes phosphate-free, automatic dishwashing detergents that contain surfactants, citrate, bleach and copolymers containing sulfonic acid groups, as well as MGDA.
0013Despite previous efforts, manufacturers of automatic dishwashing detergents have not yet succeeded in providing phosphate-free automatic dishwashing detergents that are comparable to or even exceed phosphate-containing detergents in terms of their cleaning and rinsing performance. However, such equality of performance is a prerequisite for the successful market launch of phosphate-free cleaning products, since the majority of end consumers, despite broad public discussion of environmental policy issues, will always decide against an ecologically advantageous product if it does not meet the market standard in terms of its price and/or performance.
0014In view of this initial situation, the task of the present application was to provide a phosphate-free automatic dishwashing detergent which is comparable to or even exceeds conventional phosphate-containing cleaning agents in terms of its cleaning performance as well as its final rinsing results and its performance in terms of deposit inhibition.
0015It was found that automatic dishwashing detergents which, in addition to copolymers containing sulfonic acid groups, also contain methylglycinediacetic acid, have excellent cleaning and rinsing performance even without the addition of alkali metal phosphates.
0016A first subject of the present invention is therefore a phosphate-free automatic dishwashing detergent containing builder, bleach, nonionic surfactant, and more<ol id="ol0001" compact="compact"><li>a) Copolymer containing<ol id="ol0002" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or - C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms, b) methylglycine diacetic acid.</li></ol></li></ol>
0017A first characteristic component of agents according to the invention are the copolymers a) containing sulfonic acid groups, which, in addition to a monomer containing sulfonic acid groups, contain at least one further monomer of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms. The copolymers a) can have two, three, four or more different monomer units.
0018The monomers containing sulfonic acid groups are those of the formula R<sup>5</sup>(R<sup>6</sup>)C=C(R<sup>7</sup>)-X-SO<sub>3</sub>H preferred, in the R<sup>5</sup> to R<sup>7</sup> independently for -H, -CH<sub>3</sub>, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with -NH<sub>2</sub>, -OH or -COOH substituted alkyl or alkenyl radicals or for -COOH or -COOR<sup>4</sup> stands, where R<sup>4</sup> is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X represents an optional spacer group selected from -(CH<sub>2</sub>)<sub>n</sub>- with n = 0 to 4, -COO-(Ch<sub>2</sub>)<sub>k</sub>- with k = 1 to 6, -C(O)-NH-C(CH<sub>3</sub>)<sub>2</sub>- and -C(O)-NH-CH(CH<sub>2</sub>Ch<sub>3</sub>)-.
0019Preferred among these monomers are those of the formulas H<sub>2</sub>C=CH-X-SO<sub>3</sub> H<sub>2</sub>C=C(CH<sub>3</sub>)-X-SO<sub>3</sub>H HO<sub>3</sub>SX-(R<sup>6</sup>)C=C(R<sup>7</sup>)-X-SO<sub>3</sub>H, in which R<sup>6</sup> and R<sup>7</sup> are independently selected from -H, -CH<sub>3</sub>, -CH<sub>2</sub>Ch<sub>3</sub>, -CH<sub>2</sub>Ch<sub>2</sub>Ch<sub>3</sub>, -CH(CH<sub>3</sub>)<sub>2</sub> and X represents an optional spacer group selected from -(CH<sub>2</sub>)<sub>n</sub>- with n = 0 to 4, -COO-(CH<sub>2</sub>)<sub>k</sub>- with k = 1 to 6, -C(O)-NH-C(CH<sub>3</sub>)<sub>2</sub>- and -C(O)-NH-CH(CH<sub>2</sub>Ch<sub>3</sub>)-.
0020Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propane-sulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
0021In the polymers, the sulfonic acid groups can be present entirely or partially in neutralized form, that is, the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
0022The monomer distribution of the copolymers preferably used according to the invention is for copolymers which only contain monomers from the groups. i) and ii) preferably each contain 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii ), each based on the polymer.
0023The molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol<sup>-1</sup>, preferably from 4000 to 25,000 gmol<sup>-1</sup> and in particular from 5000 to 15,000 gmol<sup>-1</sup> exhibit.
0024Unsaturated carboxylic acids are particularly preferably used as ionic monomers. Unsaturated carboxylic acids of the general formula R are particularly preferred<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)COOH, in the R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub>, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with-NH<sub>2</sub>, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR<sup>4</sup> stands, where R<sup>4</sup> is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms.
0025Particularly preferred monomers containing carboxyl groups are acrylic acid, methacrylic acid, ethacrylic acid, -chloroacrylic acid, -cyanoacrylic acid, crotonic acid, -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid. Citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
0026In addition to at least one monomer containing sulfonic acid groups, copolymers according to the invention also contain at least one monomer of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms.
0027According to the invention, phosphate-free automatic dishwashing detergents containing builders, bleaches, non-ionic surfactants, and others<ol id="ol0003" compact="compact"><li>a) Copolymer containing<ol id="ol0004" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>
0028According to the invention, monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup> used, in the R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms.
0029The subject of this application is therefore phosphate-free automatic dishwashing detergents containing builders, bleaches, non-ionic surfactants, and more<ol id="ol0005" compact="compact"><li>a) Copolymer containing<ol id="ol0006" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid</li></ol>
0030Particularly preferred monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup> are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene -1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane -1, ethylcyclohexyne, 1-octene, -olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octaclecene and C22- -olefin, 2-styrene, - methylstyrene, 3-methylstyrene, 4-propylslyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, acrylic acid -2-Ethylhexyl ester, 2-ethylhexyl methacrylate,<i>N</i>-(2-Ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate,<i>N</i>-(Octyl)acrylamide, lauryl acrylate, lauryl methacrylate,<i>N</i>-(Lauryl)acrylamide, stearyl acrylate, stearyl methacrylate,<i>N</i>-(Stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and<i>N</i>-(Behenyl)acrylamide or mixtures thereof.
0031The automatic dishwashing detergents according to the invention contain methylglycinediacetic acid (MGDA) as a second essential component. The methylglycindiacetic acid can be present in the agents according to the invention in the form of the free acid, as a partially neutralized or completely neutralized. In a particularly preferred embodiment, the methylglycine diacetic acid is in the form of an alkali metal salt.
0032According to the invention, machine dishwashing detergents preferably contain one or more builders as a further essential component. The builders include in particular silicates, carbonates and organic cobuilders.
0033Examples of organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These substance classes are described below.
0034Useful organic builders are, for example, the polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to mean those carboxylic acids that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and are therefore also used to adjust a lower and milder pH value of detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.
0035Particularly preferred automatic dishwashing detergents according to the invention contain citrate as one of their essential builders. Automatic dishwashing detergents, characterized in that they contain 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate, are preferred according to the invention. Citrate or Citric acid has proven to be the most effective builder in combination with MGDA and the copolymers containing sulfonic acid groups in terms of cleaning performance and rinse performance.
0036Phosphate-free automatic dishwashing detergents containing 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate, bleach, nonionic surfactant, and more<ol id="ol0007" compact="compact"><li>a) Copolymer containing<ol id="ol0008" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycine diacetic acid are preferred according to the invention.</li></ol>
0037Further preferred embodiments are: Phosphate-free automatic dishwashing detergents containing 10 to 50% by weight of citrate, bleach, non-ionic surfactant, and more<ol id="ol0009" compact="compact"><li>a) Copolymer containing<ol id="ol0010" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>
0038Machine dishwashing detergents according to the invention preferably contain crystalline layered silicates of the general formula NaMSi as a builder<sub>x</sub>O<sub>2x+1</sub> · y H<sub>2</sub>O, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20.
0039Amorphous sodium silicates with a modulus Na can also be used<sub>2</sub>O: SiO<sub>2</sub> from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably delayed in dissolution and have secondary washing properties.
0040Machine dishwashing detergents preferred in the context of the present invention contain 2 to 15% by weight, preferably 3 to 12% by weight and in particular 4 to 8% by weight of silicate(s).
0041Particular preference is given to using carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 10 to 40% by weight and in particular from 15 to 30% by weight, based on the weight of the automatic dishwashing detergent.
0042Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol.
0043Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, can be preferred from this group.
0044Copolymeric polycarboxylates are also suitable, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular mass, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.
0045The (co-)polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co-)polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
0046Other suitable builders are the phosphonates. The complex-forming phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as a sodium salt, with the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). The preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. HEDP from the phosphonate class is preferably used as the builder. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, particularly if the agents also contain bleach, it may be preferred to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
0047A preferred automatic dishwashing detergent within the scope of this application contains one or more phosphonates from the group<ol id="ol0011" compact="compact"><li>a) aminotrimethylenephosphonic acid (ATMP) and/or its salts;</li><li>b) ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and/or their salts;</li><li>c) Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and/or their salts;</li><li>d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and/or its salts;</li><li>e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and/or its salts;</li><li>f) Hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and/or their salts;</li><li>g) Nitrilotri(methylenephosphonic acid) (NTMP) and/or their salts.</li></ol>
0048Machine dishwashing detergents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.
0049Of course, the automatic dishwashing detergents according to the invention can contain two or more different phosphonates. Particular preference is given to automatic dishwashing detergents which contain both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates, the weight ratio of HEDP to DTPMP being between 20:1 and 1:20, preferably between 15:1 and 1:15 and in particular between 10:1 and 1:10.
0050In a preferred embodiment of the present invention, the proportion by weight of the phosphonate(s) in the total weight of the automatic dishwashing detergent is less than the proportion by weight of the polymer(s) a). In other words, those agents are particularly preferred in which the ratio of the weight fraction of polymer a) to the weight fraction of the phosphonate is 200:1 to 2:1, preferably 150:1 to 2:1, particularly preferably 100:1 to 2:1, very particularly preferably 80:1 to 3:1 and in particular 50:1 to 5:1.
0051Preferred automatic dishwashing detergents according to the invention further contain one or more bleaching agents. Among the bleaching agents used in water are H<sub>2</sub>O<sub>2</sub> Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance as providing compounds. Other useful bleaching agents include peroxypyrophosphates, citrate perhydrates and H<sub>2</sub>O<sub>2</sub> providing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminooperic acid or diperdodecanedioic acid.
0052Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with alkylperoxyacids and arylperoxyacids being particularly mentioned as examples.
0053Automatic dishwashing detergents, characterized in that they contain 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate, are preferred according to the invention.
0054Phosphate-free automatic dishwashing detergents containing builder, 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate, nonionic surfactant, and further<ol id="ol0012" compact="compact"><li>a) Copolymer containing<ol id="ol0013" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>are preferred according to the invention.
0055Further preferred embodiments are: Phosphate-free automatic dishwashing detergent, containing builder, 2 to 15% by weight of sodium percarbonate, non-ionic surfactant, and more<ol id="ol0014" compact="compact"><li>a) Copolymer containing<ol id="ol0015" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>
0056Substances that release chlorine or bromine can also be used as bleaching agents. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
0057In order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below, the automatic dishwashing detergents according to the invention can additionally contain bleach activators. Compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid can be used as bleach activators. Substances which carry O- and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving to be particularly suitable.
0058These bleach activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and particularly preferably 2 to 6% by weight. , each based on the total weight of the bleach activator-containing agents, used.
0059In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be used. These substances are bleach-intensifying transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru ammine complexes can also be used as bleaching catalysts.
0060Manganese complexes in the oxidation state II, III, IV or IV are particularly preferably used, which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst(s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me/TACN). Suitable manganese complexes are, for example, [Mn<sup>III</sup><sub>2</sub>(µ-O)<sub>1</sub>(µ-OAc)<sub>2</sub> (TACN)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>, [Mn<sup>III</sup>Mn<sup>IV</sup>(µ-O)<sub>2</sub>(µ-OAc)<sub>1</sub>(TACN)<sub>2</sub>](BPh<sub>4</sub>)<sub>2</sub>, [Mn<sup>IV</sup><sub>4</sub>(µ-O)<sub>6</sub>(TACN)<sub>4</sub>](ClO<sub>4</sub>)<sub>4</sub>, [Mn<sup>III</sup><sub>2</sub>(µ-O)<sub>1</sub>(µ-OAc)<sub>2</sub> (Me-TACN)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>, [Mn<sup>III</sup>Mn<sup>IV</sup>(µ-O)<sub>1</sub>(µ-OAc)<sub>2</sub>(Me-TACN)<sub>2</sub>](ClO<sub>4</sub>)<sub>3</sub>, [Mn<sup>IV</sup><sub>2</sub>(µ-O)<sub>3</sub>(Me-TACN)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> and [Mn<sup>IV</sup>2(µ-O)<sub>3</sub>(Me/Me-TACN)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub>(OAc = OC(O)CH<sub>3</sub>).
0061Automatic dishwashing detergents, characterized in that they further contain a bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me<sub>3</sub>-TACN) or 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane (Me<sub>4</sub>-TACN) are preferred according to the invention, since the aforementioned bleaching catalysts in particular can significantly improve the cleaning result.
0062The aforementioned bleach-intensifying transition metal complexes, in particular with the central atoms Mn and Co, are used in usual amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0. 01% by weight to 0.30% by weight, in each case based on the total weight of the bleach activator-containing agents, used. However, in special cases, more bleach activator can be used.
0063The agents according to the invention also contain surfactants. The group of surfactants includes non-ionic, anionic, cationic and amphoteric surfactants.
0064Surprisingly, it was found that the bleaching effect of lead catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes can be increased by the addition of hydrophobically modified acid-containing copolymers.
0065A preferred subject of this application is therefore a phosphate-free, bleach-containing automatic dishwashing detergent<ol id="ol0016" compact="compact"><li>a) Copolymer containing<ol id="ol0017" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid.</li><li>c) Citrate</li><li>d) Bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes</li></ol>
0066Some exemplary recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the table below:<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="43mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="31mm" /><colspec colnum="4" colname="col4" colwidth="31mm" /><colspec colnum="5" colname="col5" colwidth="31mm" /><thead valign="middle"><row><entry>ingredient</entry><entry>Recipe 1 [% by weight]</entry><entry>Recipe 2 [% by weight]</entry><entry>Recipe 3 [% by weight]</entry><entry>Recipe 4 [% by weight]</entry></row></thead><tbody valign="middle"><row><entry>Citrate</entry><entry>5 up to 60</entry><entry>10 up to 55</entry><entry>15 until 50</entry><entry>15 until 50</entry></row><row><entry>Sodium percarbonate</entry><entry>1 until 20</entry><entry>2 to 15</entry><entry>4 until 10</entry><entry>4 until 10</entry></row><row><entry>bleach catalyst</entry><entry>0.01 to 3</entry><entry>0.02 to 2</entry><entry>0.02 to 2</entry><entry>0.02 to 1</entry></row><row><entry>Copolymer<sup>1</sup></entry><entry>0.1 to 30</entry><entry>0.5 to 25</entry><entry>1.0 to 20</entry><entry>1.0 to 20</entry></row><row><entry>MGDA</entry><entry>0.5 to 20</entry><entry>0.5 to 20</entry><entry>0.5 to 10</entry><entry>0.5 to 8</entry></row><row><entry>Misc</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry></row><row rowsep="0"><entry namest="col1" nameend="col5" align="left"><sup>1</sup> Copolymer containing</entry></row><row rowsep="0"><entry namest="col1" nameend="col5" align="left">i) Monomers containing sulfonic acid groups</entry></row><row><entry namest="col1" nameend="col5" align="left">ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</entry></row></tbody></tgroup></table></tables>
0067Automatic dishwashing detergents, characterized in that they contain nonionic surfactant(s) in amounts of 1 to 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight, are preferred according to the invention.
0068All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Suitable nonionic surfactants include, for example, alkyl glycosides of the general formula RO(G)<sub>x</sub>, in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms, preferably stands for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
0069Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
0070Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
0071Low-foaming nonionic surfactants are used as preferred surfactants. Detergents or cleaning agents, in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C<sub>12-14</sub>-Alcohols with 3 EO or 4 EO, C<sub>9-11</sub>-Alcohol with 7 EO, C<sub>13-15</sub>-Alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C<sub>12-18</sub>-Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C<sub>12-14</sub>-Alcohol with 3 EO and C<sub>12-18</sub>-Alcohol with 5 EO. The ethoxylation levels reported represent statistical averages, which may correspond to a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
0072Particular preference is therefore given to ethoxylated nonionic surfactants, which are made from C<sub>6-20</sub>-Monohydroxyalkanols or C<sub>6-20</sub>-alkylphenols or C<sub>16-20</sub>-Fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is made from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C<sub>16-20</sub>-Alcohol), preferably a C<sub>18</sub>-Alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Of these, the so-called “narrow range ethoxylates” are particularly preferred.
0073Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are particularly preferably used.
0074Nonionic surfactants that have a melting point above room temperature are particularly preferred. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, particularly preferably between 25 and 60°C and in particular between 26.6 and 43.3°C, is/are particularly preferred .
0075Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used that are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s and in particular above 40 Pa s. Nonionic surfactants, which have a wax-like consistency at room temperature, are also preferred depending on their intended use.
0076Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are also used with particular preference.
0077The nonionic surfactant, which is solid at room temperature, preferably has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or The alkylphenol content of such nonionic surfactant molecules preferably accounts for more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule account for up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic identify surfactants.
0078Surfactants to be used preferably come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.
0079Other particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend, which contains 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 wt. -% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
0080Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants in the context of the present invention. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups bonded to each other before a block from the other groups follows. Here are nonionic surfactants of the general formula<chemistry id="chem0001" num="0001"><img file="EP2118255B2_D0001.tif" /></chemistry>preferred, in the R<sup>1</sup> for a straight-chain or branched, saturated or mono- or polyunsaturated C<sub>6-24</sub>-alkyl or -alkenyl radical; any group R<sup>2</sup> or R<sup>3</sup> is independently selected from -CH<sub>3</sub>, -CH<sub>2</sub>Ch<sub>3</sub>, -CH<sub>2</sub>Ch<sub>2</sub>-CH<sub>3</sub>, CH(CH<sub>3</sub>)<sub>2</sub> and the indices w, x, y, z independently represent integers from 1 to 6.
0081The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R<sup>1</sup>-OH and produce ethylene or alkylene oxide. The rest R<sup>1</sup> in the above formula may vary depending on the origin of the alcohol. If native sources are used, the remainder has R<sup>1</sup> has an even number of carbon atoms and is generally unbranched, with the linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, being preferred. Alcohols available from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched residues in the 2-position in a mixture, as are usually present in oxo alcohol residues. Regardless of the type of alcohol used to produce the nonionic surfactants contained in the agents, preference is given to nonionic surfactants in which R<sup>1</sup> in the above formula represents an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
0082As an alkylene oxide unit, which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in addition to propylene oxide, butylene oxide in particular comes into consideration. But also other alkylene oxides in which R<sup>2</sup> or R<sup>3</sup> are independently selected from -CH<sub>2</sub>Ch<sub>2</sub>-CH<sub>3</sub> or -CH(CH<sub>3</sub>)<sub>2</sub> are suitable. Preference is given to using nonionic surfactants of the above formula in which R<sup>2</sup> or R<sup>3</sup> for a remainder -CH<sub>3</sub>, w and x independently stand for values of 3 or 4 and y and z independently stand for values of 1 or 2.
0083In summary, nonionic surfactants which have a C are particularly preferred<sub>9-15</sub>-Alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.
0084Surfactants of the general formula R<sup>1</sup>-CH(OH)CH<sub>2</sub>O-(AO)<sub>w</sub>-(A'O)<sub>x</sub>-(A"O)<sub>y</sub>-(A"'O)<sub>e.g</sub>-R<sup>2</sup>, in which R<sup>1</sup> and R<sup>2</sup> independently for a straight-chain or branched, saturated or mono- or polyunsaturated C<sub>2-40</sub>-alkyl or -alkenyl radical; A, A', A" and A'" independently represent a residue from the group -CH<sub>2</sub>Ch<sub>2</sub>, -CH<sub>2</sub>Ch<sub>2</sub>-CH<sub>2</sub>, -CH<sub>2</sub>-CH(CH<sub>3</sub>), -CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>, -CH<sub>2</sub>-CH(CH<sub>3</sub>)-CH<sub>2</sub>-, -CH<sub>2</sub>-CH(CH<sub>2</sub>-CH<sub>3</sub>) stands; and w, x, y and z represent values between 0.5 and 90, where x, y and/or z can also be 0 and are preferred according to the invention.
0085Particular preference is given to those end-capped poly(oxyalkylated) nonionic surfactants which, according to the formula R<sup>1</sup>O[CH<sub>2</sub>Ch<sub>2</sub>O]<sub>x</sub>Ch<sub>2</sub>CH(OH)R<sup>2</sup>, next to a remainder R<sup>1</sup>, which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R<sup>2</sup> with 1 to 30 carbon atoms, where x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
0086Surfactants of the formula R are particularly preferred<sup>1</sup>O[CH<sub>2</sub>CH(CH<sub>3</sub>)O]<sub>x</sub>[CH<sub>2</sub>Ch<sub>2</sub>O]<sub>y</sub>Ch<sub>2</sub>CH(OH)R<sup>2</sup>, in which R<sup>1</sup> represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R<sup>2</sup> denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
0087Particular preference is also given to such end-capped poly(oxyalkylated) nonionic surfactants of the formula R<sup>1</sup>O[CH<sub>2</sub>Ch<sub>e.g</sub>O]<sub>x</sub>[CH<sub>2</sub>CH(R<sup>3</sup>)O]<sub>y</sub>Ch<sub>2</sub>CH(OH)R<sup>2</sup>, in which R<sup>1</sup> and R<sup>2</sup> independently represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical with 2 to 26 carbon atoms, R<sup>3</sup> is independently selected from -CH<sub>3</sub>, -CH<sub>2</sub>Ch<sub>3</sub>, -CH<sub>2</sub>Ch<sub>2</sub>-CH<sub>3</sub>, -CH(CH<sub>3</sub>)<sub>2</sub>, but preferably for -CH<sub>3</sub> stands, and x and y independently stand for values between 1 and 32, where nonionic surfactants with R<sup>3</sup> = -CH<sub>3</sub> and values for x from 15 to 32 and y from 0.5 and 1.5 are particularly preferred.
0088By using the non-ionic surfactants described above with a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in automatic dishwashing can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
0089Other nonionic surfactants that can preferably be used are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R<sup>1</sup>O[CH<sub>2</sub>CH(R<sup>3</sup>)O]<sub>x</sub>[CH<sub>2</sub>]<sub>k</sub>CH(OH)[CH<sub>2</sub>]<sub>j</sub>OR<sup>2</sup>, in which R<sup>1</sup> and R<sup>2</sup> represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R<sup>3</sup> represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values between 1 and 30, k and j represent Values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, any R can<sup>3</sup> in the formula R above<sup>1</sup>O[CH<sub>2</sub>CH(R<sup>3</sup>)O]<sub>x</sub>[CH<sub>2</sub>]<sub>k</sub>CH(OH)[CH<sub>2</sub>]<sub>j</sub>OR<sup>2</sup> be different. R<sup>1</sup> and R<sup>2</sup> are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 6 to 22 carbon atoms, with radicals with 8 to 18 carbon atoms being particularly preferred. For the rest R<sup>3</sup> are H, -CH<sub>3</sub> or -CH<sub>2</sub>Ch<sub>3</sub> particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
0090As described above, any R<sup>3</sup> in the above formula be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the remainder can be R<sup>3</sup> be selected to produce ethylene oxide (R<sup>3</sup> = H) or propylene oxide (R<sup>3</sup> = CH<sub>3</sub>) to form units that can be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO) (PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x was chosen as an example and can certainly be larger, with the range of variation increasing with increasing x values and, for example, including a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
0091Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula becomes R<sup>1</sup>O[CH<sub>2</sub>CH(R<sup>3</sup>)O]<sub>x</sub>Ch<sub>2</sub>CH(OH)CH<sub>2</sub>OR<sup>2</sup> simplified. In the latter formula, R<sup>1</sup>, R<sup>2</sup> and R<sup>3</sup> as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R<sup>1</sup> and R<sup>2</sup> Have 9 to 14 carbon atoms, R<sup>3</sup> stands for H and x takes values from 6 to 15.
0092The specified C chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical average values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which means that both the C chain lengths and the degrees of ethoxylation or Alkoxylation degrees mean values and resulting fractional numbers can result.
0093Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. The term surfactant mixtures does not refer to mixtures of nonionic surfactants which, in their entirety, fall under one of the general formulas mentioned above, but rather to mixtures which contain two, three, four or more nonionic surfactants which can be described by different ones of the general formulas mentioned above .
0094Phosphate-free automatic dishwashing detergent, containing builder, bleach, nonionic surfactant in amounts of 1 to 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight, as well as further<ol id="ol0018" compact="compact"><li>a) Copolymer containing<ol id="ol0019" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> for a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or for an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid. are preferred according to the invention.</li></ol>
0095Some exemplary recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the table below:<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="45mm" /><colspec colnum="2" colname="col2" colwidth="32mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><colspec colnum="5" colname="col5" colwidth="32mm" /><thead valign="top"><row><entry>ingredient</entry><entry>Recipe 5 [% by weight]</entry><entry>Recipe 6 [% by weight]</entry><entry>Recipe7 [wt.%]</entry><entry>Recipe 8 [% by weight]</entry></row></thead><tbody><row><entry>Citrate</entry><entry>5 up to 60</entry><entry>10 up to 55</entry><entry>15 until 50</entry><entry>15 until 50</entry></row><row><entry>Sodium percarbonate</entry><entry>1 until 20</entry><entry>2 to 15</entry><entry>4 until 10</entry><entry>4 until 10</entry></row><row><entry>bleach catalyst</entry><entry>0.01 to 3</entry><entry>0.02 to 2</entry><entry>0.02 to 2</entry><entry>. 0.02 to 1</entry></row><row><entry>Non-ionic surfactant</entry><entry>1 until 10</entry><entry>1 until 10</entry><entry>2 till 8</entry><entry>3 until 6</entry></row><row><entry>Copoylmer<sup>1</sup></entry><entry>0.1 to 30</entry><entry>0.5 to 25</entry><entry>1.0 to 20</entry><entry>1.0 to 20</entry></row><row><entry>MGDA</entry><entry>0.5 to 20</entry><entry>0.5 to 20</entry><entry>0.5 to 10</entry><entry>0.5 to 8</entry></row><row><entry>Misc</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry></row><row rowsep="0"><entry namest="col1" nameend="col5" align="justify"><sup>1</sup> Copolymer containing</entry></row><row rowsep="0"><entry namest="col1" nameend="col5" align="justify">i) Monomers containing sulfonic acid groups</entry></row><row><entry namest="col1" nameend="col5" align="justify">ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or - C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</entry></row></tbody></tgroup></table></tables>
0096Further preferred embodiments are: Phosphate-free automatic dishwashing detergent, containing builder, bleach, 2 to 8% by weight of nonionic surfactant, and further<ol id="ol0020" compact="compact"><li>a) Copolymer containing<ol id="ol0021" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>
0097If anionic surfactants are used as components of automatic dishwashing detergents, their content, based on the total weight of the detergents, is preferably less than 4% by weight, preferably less than 2% by weight and most preferably less than 1% by weight. Machine dishwashing detergents that do not contain anionic surfactants are particularly preferred.
0098Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in conjunction with them.
0099In summary, the following basic recipes are particularly preferred due to their outstanding cleaning and rinsing results: Phosphate-free automatic dishwashing detergents containing builder, 2 to 15% by weight of sodium percarbonate, 2 to 8% by weight of nonionic surfactant, and further<ol id="ol0022" compact="compact"><li>a) Copolymer containing<ol id="ol0023" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>as well as
0100Phosphate-free automatic dishwashing detergents containing 10 to 50% by weight of citrate, 2 to 15% by weight of sodium percarbonate, 2 to 8% by weight of nonionic surfactant, and further<ol id="ol0024" compact="compact"><li>a) Copolymer containing<ol id="ol0025" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>
0101Preferred automatic dishwashing agents according to the invention have proven to be particularly effective with regard to optimal cleaning and rinsing results, in which the weight proportion of the copolymer a) is 4 to 18% by weight, preferably 6 to 15 and in particular 6 to 12% by weight.
0102Automatic dishwashing detergents in which the proportion by weight of methylglycinediacetic acid b) is 0.5 to 20% by weight, preferably 0.5 to 10% by weight and in particular 0.5 to 8% by weight, also have particularly good cleaning properties. , rinse and coating results and are preferred according to the invention for this reason.
0103Phosphate-free automatic dishwashing detergents containing are therefore particularly preferred<ol id="ol0026" compact="compact"><li>a) 6 to 15% by weight of copolymer<ol id="ol0027" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) 0.5 to 10% by weight of methylglycinediacetic acid</li><li>c) 10 to 50% by weight of citrate</li><li>d) 2 to 15% by weight of sodium percarbonate</li><li>e) 2 to 8% by weight of nonionic surfactant</li></ol>
0104In a further preferred embodiment, the copolymers a) also contain ionic monomers in addition to the monomers containing sulfonic acid groups and monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or - C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms.
0105Phosphate-free automatic dishwashing detergent, containing builder, bleach, non-ionic surfactant, and more<ol id="ol0028" compact="compact"><li>a) Copolymer, comprising<ol id="ol0029" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) other ionic monomers</li><li>iii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>are preferred according to the invention.
0106These terpolymers particularly preferably contain monomers containing carboxyl groups.
0107A particularly preferred subject of the present application is therefore a phosphate-free automatic dishwashing detergent containing builder, bleach, nonionic surfactant, and more<ol id="ol0030"><li>a) Copolymer containing<ol id="ol0031" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) monomers containing carboxyl groups</li><li>iii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub>, represents, X represents an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid.</li></ol>
0108In a last preferred embodiment, the copolymers contain, in addition to at least one monomer containing sulfonic acid groups, a monomer containing carboxyl groups and, as nonionic monomers, corresponding monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms.
0109In summary, phosphate-free automatic dishwashing detergents are preferred, as well as builders, bleaches and non-ionic surfactants<ol id="ol0032" compact="compact"><li>a) Copolymer containing<ol id="ol0033" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) monomers containing carboxyl groups</li><li>iii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O-and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) Methylglycinediacetic acid</li></ol>contain.
0110Preferred automatic dishwashing detergents that contain terpolymers are in particular: Phosphate-free automatic dishwashing detergent containing<ol id="ol0034" compact="compact"><li>a) 6 to 15% by weight of copolymer<ol id="ol0035" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) monomers containing carboxyl groups</li><li>iii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) 0.5 to 10% by weight of methylglycinediacetic acid</li><li>c) 10 to 50% by weight of citrate</li><li>d) 2 to 15% by weight of sodium percarbonate</li><li>e) 2 to 8% by weight of nonionic surfactant</li></ol>
0111In addition to the ingredients described above, such as the builder, the bleach, the non-ionic surfactant, the copolymer a) and the methyl glycine diacetic acid, preferred automatic dishwashing detergents contain other ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.
0112The group of washing or cleaning-active polymers includes, for example, rinse aid polymers and/or polymers that act as softeners. In general, in addition to nonionic polymers, cationic, anionic and amphoteric polymers can also be used in detergents or cleaning agents.
0113“Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain. Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, and copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
0114“Amphoteric polymers” in the sense of the present invention have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
0115Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which contains monomer units of the formula R<sup>1</sup>R<sup>2</sup>C=CR<sup>3</sup>R<sup>4</sup> in which every residue R<sup>1</sup>, R<sup>2</sup>, R<sup>3</sup>, R<sup>4</sup> is independently selected from hydrogen, derivatized hydroxy group, C<sub>1-30</sub> linear or branched alkyl groups, aryl, aryl substituted C<sub>1-30</sub> linear or branched alkyl groups, polyalkoylxylated alkyl groups, heteroatomic organic groups with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge in part of the pH range from 2 to 11, or salts thereof with the proviso that at least one residue R<sup>1</sup>, R<sup>2</sup>, R<sup>3</sup>, R<sup>4</sup> is a heteroatomic organic group with at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge.
0116Cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a compound of the general formula as the monomer unit<chemistry id="chem0002" num="0002"><img file="EP2118255B2_D0002.tif" /></chemistry>at the R<sup>1</sup> and R<sup>4</sup> independently represents H or a linear or branched hydrocarbon radical with 1 to 6 carbon atoms; R<sup>2</sup> and R<sup>3</sup> independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, which is preferably a methyl group; x and y independently represent integers between 1 and 3. The
0117Preferred residues R<sup>1</sup> and R<sup>4</sup> in the above formula are selected from -CH<sub>3</sub>, -CH<sub>2</sub>-CH<sub>3</sub>, -CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>3</sub>, -CH(CH<sub>3</sub>)-CH<sub>3</sub>, -CH<sub>2</sub>-OH, -CH<sub>2</sub>-CH<sub>2</sub>-OH, -CH(OH)-CH<sub>3</sub>, -CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-OH, -CH<sub>2</sub>-CH(OH)-Ch<sub>3</sub>, -CH(OH)-CH<sub>2</sub>-CH<sub>3</sub>, and -(CH<sub>2</sub>Ch<sub>2</sub>-O)<sub>n</sub>H.
0118Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R<sup>1</sup> and R<sup>4</sup> stand for H, R<sup>2</sup> and R<sup>3</sup> represent methyl and x and y are each 1. The corresponding monomer unit of the formula H<sub>2</sub>C=CH-(CH<sub>2</sub>)-N<sup>+</sup>(CH<sub>3</sub>)<sub>2</sub>-(CH<sub>2</sub>)-CH=CH<sub>2</sub> X<sup>-</sup>are in the case of X<sup>-</sup>= Chloride also known as DADMAC (diallyldimethylammonium chloride).
0119Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula R<sup>1</sup>HC=CR<sup>2</sup>-C(O)-NH-(CH<sub>2</sub>)-N<sup>+</sup>R<sup>3</sup>R<sup>4</sup>R<sup>5</sup> X<sup>-</sup>in the R<sup>1</sup>, R<sup>2</sup>, R<sup>3</sup>, R<sup>4</sup> and R<sup>5</sup> independently of each other for a linear or branched, saturated or unsaturated alkyl, or hydroxyalkyl radical with 1 to 6 carbon atoms, preferably for a linear or branched alkyl radical selected from -CH<sub>3</sub>, -CH<sub>2</sub>-CH<sub>3</sub>, -CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>3</sub>, -CH(CH<sub>3</sub>)CH<sub>3</sub>, -CH<sub>2</sub>-OH, -CH<sub>2</sub>-CH<sub>2</sub>-OH, -CH(OH)-CH<sub>3</sub>, -CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-OH, -CH<sub>2</sub>-CH(OH)-CH<sub>3</sub>, -CH(OH)-CH<sub>2</sub>-CH<sub>3</sub>, and -(CH<sub>2</sub>Ch<sub>2</sub>-O)<sub>n</sub>H stands and x stands for an integer between 1 and 6.
0120Very particularly preferred in the context of the present application are polymers which have a cationic monomer unit of the above general formula, in which R<sup>1</sup> for H and R<sup>2</sup>, R<sup>3</sup>, R<sup>4</sup> and R<sup>5</sup> represents methyl and x represents 3. The corresponding monomer units of the formula H<sub>2</sub>C=C(CH<sub>3</sub>)-C(O)-NH-(CH<sub>2</sub>)<sub>x</sub>-N<sup>+</sup>(CH<sub>3</sub>)<sub>3</sub> X<sup>-</sup>are in the case of X<sup>-</sup>= Chloride also known as MAPTAC (methyacrylamidopropyl trimethylammonium chloride).
0121According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and/or acrylamidopropyltrimethylammonium salts as monomer units.
0122The amphoteric polymers mentioned above have not only cationic groups, but also anionic groups or monomer units. Such anionic monomer units come, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth)acrylic acid, (dimethyl)acrylic acid, (ethyl)acrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids , such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
0123Preferred used amphoters of polymers come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic copolymere, the alkylacrylamide/methylmethacrylic Copolymere Meth) acrylic acid copolymere, the alkylacrylamide/methacrylic acid/alkylami alkyl (meth )-acrylic acid copolymers, the alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, the alkylacrylamide/alkymethacrylate/alkylaminoethyl methacrylate/alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
0124Zwitterionic polymers that can preferably be used come from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali and ammonium salts and methacroylethyl betaine/methacrylate copolymers. Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, include methacrylamidoalkyl-trialkyl ammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.
0125Particularly preferred amphoteric polymers come from the group of methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/methacrylic acid copolymers and methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid. Copolymers and their alkali and ammonium salts.
0126Particular preference is given to amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth) acrylic acid copolymers and their alkali and ammonium salts.
0127In a particularly preferred embodiment of the present invention, the polymers are in pre-assembled form. Suitable options for packaging the polymers include:<ul id="ul0001" list-style="dash" compact="compact"><li>the encapsulation of the polymers using water-soluble or water-dispersible coating agents, preferably using water-soluble or water-dispersible natural or synthetic polymers;</li><li>the encapsulation of the polymers using water-insoluble, meltable coating agents, preferably using water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C;</li><li>the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.</li></ul>
0128Detergents or cleaning agents contain the aforementioned cationic and/or amphoteric polymers preferably in amounts between 0.01 and 10% by weight, based on the total weight of the detergent or cleaning agent. However, in the context of the present application, preference is given to detergents or cleaning agents in which the weight proportion of the cationic and/or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, particularly preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, in each case based on the total weight of the automatic dishwashing detergent.
0129Enzymes can be used to increase the washing or cleaning performance of detergents or cleaning agents. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents and are therefore preferred. Detergents or cleaning agents preferably contain enzymes in total amounts of 1 x 10<sup>-6</sup> up to 5% by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
0130Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN' and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease<i>Bacillus lentus</i>, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which can be assigned to the subtilases but no longer to the subtilisins in the narrower sense.
0131Examples of amylases that can be used according to the invention are the α-amylases<i>Bacillus licheniformis</i>, out of<i>B. amyloliquefaciens</i>, out of<i>B. stearothermophilus</i>, out of<i>Aspergillus niger</i> and<i>A. oryzae</i> as well as the further developments of the aforementioned amylases that have been improved for use in detergents and cleaning agents. Furthermore, α-amylase is used for this purpose<i>Bacillus sp.</i> A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase).<i>B. agaradherens</i> (DSM 9948).
0132Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-splitting activities, but also to obtain suitable precursors<i>in situ</i> To produce peracids. These include, for example, those originally from<i>Humicola lanuginosa</i> (<i>Thermomyces lanuginosus</i>) available or further developed lipases, especially those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which originally come from<i>Fusarium solani pisi</i> and<i>Humicola insolens</i> have been isolated. Lipases or cutinases, whose starting enzymes originally come from, can also be used<i>Pseudomonas mendocina</i> and<i>Fusarium solanii</i> have been isolated.
0133Furthermore, enzymes can be used which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectin esterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases.
0134To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of very different redox potentials between the oxidizing enzymes and the soils (mediators).
0135The enzymes can be used in any form established in the state of the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or containing stabilizers.
0136Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, Air and/or chemical impermeable protective layer is covered. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
0137Furthermore, it is possible to assemble two or more enzymes together so that a single granulate has several enzyme activities.
0138A protein and/or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation or decay caused by physical influences, oxidation or proteolytic cleavage. When the proteins and/or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
0139One or more enzymes and/or enzyme preparations, preferably solid protease preparations and/or amylase preparations, are preferred in amounts of 0.1 to 5% by weight, preferably of 0.2 to 5% by weight and in particular of 0.4 to 5% by weight, based on the total enzyme-containing agent, is used.
0140Phosphate-free automatic dishwashing detergents containing are therefore particularly preferred<ol id="ol0036" compact="compact"><li>a) 6 to 15% by weight of copolymer<ol id="ol0037" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) 0.5 to 10% by weight of methylglycinediacetic acid</li><li>c) 10 to 50% by weight of citrate</li><li>d) 2 to 15% by weight of sodium percarbonate</li><li>e) 2 to 8% by weight of nonionic surfactant</li><li>f) 1.0 to 6% by weight of enzyme.</li></ol>or.
0141Phosphate-free automatic dishwashing detergent containing<ol id="ol0038" compact="compact"><li>a) 6 to 15% by weight of copolymer<ol id="ol0039" compact="compact"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Carboxyl group-containing monomers of the formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)COOH, in the R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub>, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with -NH<sub>2</sub>, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR<sup>4</sup> stands, where R<sup>4</sup> is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms</li><li>iii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms</li></ol></li><li>b) 0.5 to 10% by weight of methylglycinediacetic acid</li><li>c) 10 to 50% by weight of citrate</li><li>d) 2 to 15% by weight of sodium percarbonate</li><li>e) 2 to 8% by weight of nonionic surfactant</li><li>f) 1.0 to 6% by weight of enzyme.</li></ol>
0142Some exemplary recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the following tables:<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="32mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><colspec colnum="4" colname="col4" colwidth="32mm" /><colspec colnum="5" colname="col5" colwidth="32mm" /><thead valign="top"><row><entry>ingredient</entry><entry>Recipe 9 [% by weight]</entry><entry>Recipe 10 [% by weight]</entry><entry>Recipe 11 [% by weight]</entry><entry>Recipe 12 [% by weight]</entry></row></thead><tbody><row><entry>Citrate</entry><entry>5 up to 60</entry><entry>10 up to 55</entry><entry>15 until 50</entry><entry>15 until 50</entry></row><row><entry>Sodium percarbonate</entry><entry>1 until 20</entry><entry>2 to 15</entry><entry>4 until 10</entry><entry>4 until 10</entry></row><row><entry>Non-ionic surfactant</entry><entry>1 until 10</entry><entry>2 till 8</entry><entry>2 till 8</entry><entry>3 until 6</entry></row><row><entry>enzyme</entry><entry>0.1 to 6</entry><entry>0.2 to 5</entry><entry>0.4 to 5</entry><entry>0.4 to 5</entry></row><row><entry>Copoylmer<sup>1</sup></entry><entry>0.1 to 30</entry><entry>0.5 to 25</entry><entry>1.0 to 20</entry><entry>1.0 to 20</entry></row><row><entry>MGDA</entry><entry>0.5 to 20</entry><entry>0.5 to 20</entry><entry>0.5 to 10</entry><entry>0.5 to 8</entry></row><row><entry>Misc</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry></row></tbody></tgroup><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="32mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><colspec colnum="4" colname="col4" colwidth="32mm" /><colspec colnum="5" colname="col5" colwidth="32mm" /><thead valign="top"><row><entry>ingredient</entry><entry>Recipe 13 [% by weight]</entry><entry>Recipe 14 [% by weight]</entry><entry>Recipe 15 [% by weight]</entry><entry>Recipe 16 [% by weight]</entry></row></thead><tbody><row><entry>Citrate</entry><entry>5 up to 60</entry><entry>10 up to 55</entry><entry>15 until 50</entry><entry>15 until 50</entry></row><row><entry>Carbonate/bicarbonate</entry><entry>2 until 40</entry><entry>2 until 40</entry><entry>2 until 40</entry><entry>2 until 40</entry></row><row><entry>silicate</entry><entry>0 to 15</entry><entry>0 to 15</entry><entry>0 to 15</entry><entry>0.1 to 10</entry></row><row><entry>Sodium percarbonate</entry><entry>1 until 20</entry><entry>2 to 15</entry><entry>4 until 10</entry><entry>4 until 10</entry></row><row><entry>bleach catalyst</entry><entry>0.01 to 3</entry><entry>0.02 to 2</entry><entry>0.02 to 2</entry><entry>0.02 to 1</entry></row><row><entry>Non-ionic surfactant</entry><entry>1 until 10</entry><entry>2 till 8</entry><entry>2 till 8</entry><entry>3 until 6</entry></row><row><entry>enzyme</entry><entry>0.1 to 6</entry><entry>0.2 to 5</entry><entry>0.4 to 5</entry><entry>0.4 to 5</entry></row><row><entry>Copoylmer<sup>1</sup></entry><entry>0.1 to 30</entry><entry>0.5 to 25</entry><entry>1.0 to 20</entry><entry>1.0 to 20</entry></row><row><entry>MGDA</entry><entry>0.5 to 20</entry><entry>0.5 to 20</entry><entry>0.5 to 10</entry><entry>0.5 to 8</entry></row><row><entry>Misc</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry></row></tbody></tgroup></table></tables><ul id="ul0002" list-style="none" compact="compact"><li><sup>1</sup>a) Copolymer containing<ol id="ol0040"><li>i) Monomers containing sulfonic acid groups</li><li>ii) Monomers of the general formula R<sup>1</sup>(R<sup>2</sup>)C=C(R<sup>3</sup>)-XR<sup>4</sup>, in which R<sup>1</sup> to R<sup>3</sup> independently for -H, -CH<sub>3</sub> or -C<sub>2</sub>H<sub>5</sub> stands, X stands for an optional spacer group selected from -CH<sub>2</sub>-, -C(O)O- and -C(O)-NH-, and R<sup>4</sup> represents a straight-chain or branched saturated alkyl radical with 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical with 6 to 22 carbon atoms,</li></ol></li><li>b) Methylglycinediacetic acid.</li></ul>
0143Glass corrosion inhibitors prevent the appearance of clouding, streaks and scratches as well as iridescence on the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts as well as magnesium and zinc complexes.
0144The spectrum of zinc salts preferred according to the invention, preferably organic acids, particularly preferably organic carboxylic acids, ranges from salts that are sparingly or insoluble in water, i.e. a solubility below 100 mg/l, preferably below 10 mg/l, in particular below 0.01 mg/l, up to those salts which have a solubility in water above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
0145It is particularly preferred to use at least one zinc salt of an organic carboxylic acid as the glass corrosion inhibitor, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
0146In the context of the present invention, the zinc salt content in detergents or cleaning agents is preferably between 0.1 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight. , or the content of zinc in oxidized form (calculated as Zn<sup>2+</sup>) between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.5% by weight, in each case based on the total weight of the agent containing glass corrosion inhibitor.
0147Corrosion inhibitors serve to protect the items to be washed or the machine, with silver protection agents being particularly important in the area of automatic dishwashing. The known substances from the prior art can be used. In general, silver protective agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and/or alkylaminotriazole are particularly preferred. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, with particular preference for these substances in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 % by weight, particularly preferably 0.01 to 0.04% by weight.
0148In order to facilitate the disintegration of prefabricated molded bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, into these agents in order to shorten the disintegration times.
0149These substances, which are also referred to as "explosive" agents because of their effect, increase their volume when water enters, on the one hand increasing the volume (swelling), and on the other hand, the release of gases can also create a pressure that breaks the tablet into smaller particles allows it to disintegrate. Well-known disintegration aids include, for example, carbonate/citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
0150Disintegration aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based on the total weight of the agent containing disintegration aids.
0151The preferred disintegrating agents used are cellulose-based disintegrating agents, so that preferred detergents or cleaning agents contain such a cellulose-based disintegrating agent in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. % contain. The cellulose used as a disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being mixed into the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 µm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm.
0152Preferred disintegration aids, preferably a cellulose-based disintegration aid, preferably in granular, co-granulated or compacted form, are in the disintegration agent-containing agents in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based on the total weight of the agent containing the disintegrating agent.
0153According to the invention, gas-evolving effervescent systems can also preferably be used as tablet disintegration aids. The gas-evolving shower system can consist of a single substance that releases a gas when it comes into contact with water. Particularly noteworthy among these compounds is magnesium peroxide, which releases oxygen when it comes into contact with water. However, preferred effervescent systems consist of at least two components which react with one another to form gas, for example alkali metal carbonate and/or bicarbonate and an acidification agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution. Boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts, for example, can be used as acidification agents which release carbon dioxide from the alkali metal salts in aqueous solution. However, organic acidification agents are preferably used, with citric acid being a particularly preferred acidification agent. Acidifying agents in the effervescent system are preferred from the group of organic di-, tri- and oligocarboxylic acids or mixtures.
0154In the context of the present invention, individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. However, mixtures of different fragrances are preferably used, which together produce an appealing scent. Such perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, for example Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
0155The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting scent through a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other auxiliary substances.
0156Preferred dyes, the selection of which poses no difficulty for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the agents and to light, as well as no pronounced substantivity compared to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware not to stain them.
0157The automatic dishwashing detergents according to the invention can be formulated in solid or liquid form but can also be available, for example, as a combination of solid and liquid forms.
0158Powders, granules, extrudates or compacts, especially tablets, are particularly suitable as solid forms. The liquid forms based on water and/or organic solvents can be thickened and in the form of gels.
0159Agents according to the invention can be manufactured as single-phase or multi-phase products. Machine dishwashing detergents with one, two, three or four phases are particularly preferred. Machine dishwashing detergents, characterized in that they are in the form of a prefabricated metering unit with two or more phases, are particularly preferred.
0160The individual phases of multi-phase agents can have the same or different physical states. Machine dishwashing detergents which have at least two different solid phases and/or at least two liquid phases and/or at least one solid and at least one liquid phase are particularly preferred.
0161Machine dishwashing detergents according to the invention are preferably pre-assembled into dosage units. These dosing units preferably include the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosage units have a weight of between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
0162The volume of the aforementioned dosing units and their spatial shape are particularly preferably chosen so that the pre-assembled units can be dosed via the dosing chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
0163The automatic dishwashing detergents according to the invention, in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
0164The subject of the present application is also a method for cleaning dishes in a dishwasher, using machine dishwashing agents according to the invention, the machine dishwashing agents preferably being metered into the interior of a dishwasher while running through a dishwashing program, before the start of the main wash cycle or in the course of the main wash cycle. The dosage or The agent according to the invention can be introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber of the dishwasher. During the cleaning process, no additional water softener and no additional rinse aid are preferably dosed into the interior of the dishwasher.
0165As described at the beginning, agents according to the invention are characterized by an improved rinsing effect compared to conventional automatic dishwashing agents. The use of a machine dishwashing agent according to the invention as a rinse aid in machine dishwashing is therefore a further subject of the present application.
Examples
0166In a first cleaning attempt, soiled dishes were washed in a dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the three phosphate-free machine dishwashing detergents V2, V3 and E1 at a water hardness of 21 °dH.
0167The composition of the dishwashing detergents used can be found in the table below:<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="36mm" /><colspec colnum="2" colname="col2" colwidth="17mm" align="center" /><colspec colnum="3" colname="col3" colwidth="17mm" align="center" /><colspec colnum="4" colname="col4" colwidth="17mm" align="center" /><colspec colnum="5" colname="col5" colwidth="17mm" align="center" /><thead valign="top"><row><entry align="center">raw material</entry><entry>V1</entry><entry>V2</entry><entry>V3</entry><entry>E1</entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>phosphate</entry><entry>33</entry><entry>--</entry><entry>--</entry><entry>--</entry></row><row rowsep="0"><entry>Citrate</entry><entry>--</entry><entry>23</entry><entry>23</entry><entry>23</entry></row><row rowsep="0"><entry>MGDA</entry><entry>--</entry><entry>--</entry><entry>8,0</entry><entry>8,0</entry></row><row rowsep="0"><entry>Copolymer<sup>1</sup></entry><entry>12,0</entry><entry>12,0</entry><entry>--</entry><entry>12,0</entry></row><row rowsep="0"><entry>HEDP</entry><entry>2,0</entry><entry>2,0</entry><entry>2,0</entry><entry>2,0</entry></row><row rowsep="0"><entry>soda</entry><entry>28,0</entry><entry>28,0</entry><entry>28,0</entry><entry>28,0</entry></row><row rowsep="0"><entry>Sodium percarbonate</entry><entry>10,0</entry><entry>10,0</entry><entry>10,0</entry><entry>10,0</entry></row><row rowsep="0"><entry>TAED</entry><entry>2,4</entry><entry>2,4</entry><entry>2,4</entry><entry>2,4</entry></row><row rowsep="0"><entry>Protease/amylase</entry><entry>4,0</entry><entry>4,0</entry><entry>4,0</entry><entry>4,0</entry></row><row rowsep="0"><entry>Non-ionic surfactant</entry><entry>5,0</entry><entry>5,0</entry><entry>5,0</entry><entry>5,0</entry></row><row><entry>Misc</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry><entry>Add 100</entry></row><row><entry namest="col1" nameend="col5" align="left"><sup>1</sup> Copolymer containing sulfonic acid groups</entry></row></tbody></tgroup></table></tables>
0168The overall appearance of the items to be washed was assessed using the rating scale listed below. The results are given in the table below (the values given are the average values of 3 tests):<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="34mm" /><colspec colnum="2" colname="col2" colwidth="10mm" align="center" /><colspec colnum="3" colname="col3" colwidth="10mm" align="center" /><colspec colnum="4" colname="col4" colwidth="10mm" align="center" /><colspec colnum="5" colname="col5" colwidth="10mm" align="center" /><thead valign="middle"><row><entry /><entry>V1</entry><entry>V2</entry><entry>V3</entry><entry>E1</entry></row></thead><tbody valign="middle"><row><entry align="center">Cleaning result</entry><entry>8,1</entry><entry>7,1</entry><entry>7,5</entry><entry>8,2</entry></row></tbody></tgroup></table></tables>
0169Cleaning evaluation scale: 10 = no contamination to 0 = severe contamination (average value over seven specific soilings)
0170In a second experiment to determine the formation of deposits, unsoiled dishes were washed in a continuously operated dishwasher with 21 g of a commercially available phosphate-containing machine dishwashing detergent V1 or 21 g of the three phosphate-free machine dishwashing detergents V2, V3 and E1 at a water hardness of 21°dH .
0171The overall appearance of the items to be washed was assessed using the rating scale listed below. The results are given in the table below (the values given are the average values of 3 tests):<tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="26mm" align="center" /><colspec colnum="2" colname="col2" colwidth="24mm" align="center" /><colspec colnum="3" colname="col3" colwidth="24mm" align="center" /><colspec colnum="4" colname="col4" colwidth="24mm" align="center" /><colspec colnum="5" colname="col5" colwidth="24mm" align="center" /><thead valign="top"><row><entry /><entry>V1</entry><entry>V2</entry><entry>V3</entry><entry>E1</entry></row></thead><tbody valign="middle"><row rowsep="0"><entry>Plaster formation</entry><entry>Porcelain 3.5</entry><entry>Porcelain 1.5</entry><entry>Porcelain 2.5</entry><entry>Porcelain 3.0</entry></row><row><entry /><entry>Plastic 4.2</entry><entry>Plastic 1.0</entry><entry>Plastic 3.0</entry><entry>Plastic 4.5</entry></row></tbody></tgroup></table></tables>
0172Rating scale for deposit formation: 10 = no deposit formation to 0 = heavy deposit formation
7 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO0220708A1 | Cites | World Intellectual Property Organization (WIPO) | Opposition |
| EP0851022A2 | Cites | European Patent Office (EPO) | Opposition |
| US2004072716A1 | Cites | United States of America | Opposition |
| US2004116319A1 | Cites | United States of America | Opposition |
| WO2006029806A1 | Cites | World Intellectual Property Organization (WIPO) | Opposition |
| WO2008017620A1 | Cites | World Intellectual Property Organization (WIPO) | Opposition |
| WO2008028896A2 | Cites | World Intellectual Property Organization (WIPO) | Opposition |
| CA2258218A1 | Cites | Canada | Opposition |
| US5547612A | Cites | United States of America | Opposition |
| US5998346A | Cites | United States of America | Opposition |
| WO9500624A1 | Cites | World Intellectual Property Organization (WIPO) | Opposition |
| WO9749792A1 | Cites | World Intellectual Property Organization (WIPO) | Opposition |
| EP1721962A | Cites | European Patent Office (EPO) | – |
| EP0851022A2 | Cites | European Patent Office (EPO) | – |
| WO2005090541A | Cites | World Intellectual Property Organization (WIPO) | – |
| WO2006106332A | Cites | World Intellectual Property Organization (WIPO) | – |
| WO2007052064A | Cites | World Intellectual Property Organization (WIPO) | – |
| WO0220708A1 | Cites | World Intellectual Property Organization (WIPO) | – |
| WO9500624A1 | Cites | World Intellectual Property Organization (WIPO) | – |
| WO9749792A1 | Cites | World Intellectual Property Organization (WIPO) | – |
| WO2006029806A1 | Cites | World Intellectual Property Organization (WIPO) | – |
| WO2008017620A1 | Cites | World Intellectual Property Organization (WIPO) | – |
| WO2008028896A2 | Cites | World Intellectual Property Organization (WIPO) | – |
| CA2258218A1 | Cites | Canada | – |
| US5308532A | Cites | United States of America | – |
| US5547612A | Cites | United States of America | – |
| US5998346A | Cites | United States of America | – |
| US2004072716A1 | Cites | United States of America | – |
| US2004116319A1 | Cites | United States of America | – |
| POTTHOFF-KARL B ET AL: "SYNTHESE ABBAUBARER KOMPLEXBILDNER UND IHRE ANWENDUNG IN WASCHMITTEL- UND REINIGERFORMULIERUNGEN" SOFW-JOURNAL SEIFEN, OELE, FETTE, WACHSE, VERLAG FUR CHEMISCHE INDUSTRIE, AUGSBURG, DE, Bd. 122, Nr. 6, 1. Mai 1996 (1996-05-01), Seiten 392-394,396, XP000587160 ISSN: 0942-7694 | Non-patent | – | – |
62 members in 7 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 102007006628 | Germany | – | |
| 102007006628 | Germany | A | |
| 2007063326 | European Patent Office (EPO) | W |
Members62
| Document | Office | Kind | |
|---|---|---|---|
| WO2008028896A2 | World Intellectual Property Organization (WIPO) | A2 | |
| DE102006042797A1 | Germany | A1 | |
| WO2008028896A3 | World Intellectual Property Organization (WIPO) | A3 | |
| DE102007006627A1 | Germany | A1 | |
| DE102007006628A1 | Germany | A1 | |
| DE102007006629A1 | Germany | A1 | |
| DE102007006630A1 | Germany | A1 | |
| WO2008095554A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2008095560A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2008095561A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2008095562A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2008095563A1 | World Intellectual Property Organization (WIPO) | A1 | |
| WO2008095561A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2008095554A3 | World Intellectual Property Organization (WIPO) | A3 | |
| DE102007029643A1 | Germany | A1 | |
| DE102007044417A1 | Germany | A1 | |
| DE102007044418A1 | Germany | A1 | |
| WO2009037012A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2009037013A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2009037012A3 | World Intellectual Property Organization (WIPO) | A3 | |
| WO2009037013A3 | World Intellectual Property Organization (WIPO) | A3 | |
| EP2059582A2 | European Patent Office (EPO) | A2 | |
| EP2115109A2 | European Patent Office (EPO) | A2 | |
| EP2115112A2 | European Patent Office (EPO) | A2 | |
| EP2115113A1 | European Patent Office (EPO) | A1 | |
| EP2118254A1 | European Patent Office (EPO) | A1 | |
| EP2118255A1 | European Patent Office (EPO) | A1 | |
| US2010024846A1 | United States of America | A1 | |
| US2010029536A1 | United States of America | A1 | |
| US2010031976A1 | United States of America | A1 | |
| US2010041575A1 | United States of America | A1 | |
| US2010093588A1 | United States of America | A1 | |
| EP2188361A2 | European Patent Office (EPO) | A2 | |
| US7879154B2 | United States of America | B2 | |
| EP2118254B1 | European Patent Office (EPO) | B1 | |
| AT517975T | Austria | T | |
| ATE517975T1 | Austria | T1 | |
| US8303721B2 | United States of America | B2 | |
| EP2115113B1 | European Patent Office (EPO) | B1 | |
| ES2396568T3 | Spain | T3 | |
| PL2115113T3 | Poland | T3 | |
| EP2059582B1 | European Patent Office (EPO) | B1 | |
| ES2411731T3 | Spain | T3 | |
| PL2059582T3 | Poland | T3 | |
| EP2118255B1 | European Patent Office (EPO) | B1 | |
| ES2448515T3 | Spain | T3 | |
| PL2118255T3 | Poland | T3 | |
| EP2188361B1 | European Patent Office (EPO) | B1 | |
| ES2523920T3 | Spain | T3 | |
| PL2188361T3 | Poland | T3 | |
| DE202007019720U1 | Germany | U1 | |
| US9752100B2 | United States of America | B2 | |
| EP2115112B1 | European Patent Office (EPO) | B1 | |
| EP3567094A1 | European Patent Office (EPO) | A1 | |
| PL2115112T3 | Poland | T3 | |
| ES2743235T3 | Spain | T3 | |
| EP2118255B2This record | European Patent Office (EPO) | B2 | |
| PL2118255T5 | Poland | T5 | |
| ES2448515T5 | Spain | T5 | |
| EP3567094B1 | European Patent Office (EPO) | B1 | |
| ES3015544T3 | Spain | T3 | |
| PL3567094T3 | Poland | T3 |
108 legal events, as 11 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Patent modifiedDC2A | DC2A | ES | |
| Patent maintained in amended form27A | 27A | EP | |
| Designated contracting statesAK | AK | EP | |
| Epo decision maintaining patent in amended form now finalR102 | R102 | DE | |
| Patent maintained in amended formORIGINAL CODE: 0009272PUAH | PUAH | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: PATENT MAINTAINED AS AMENDEDSTAA | STAA | EP | |
| Opt-out of the competence of the unified patent court (upc) registeredP01 | P01 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Examination report in opposition despatched + time limitOppositionORIGINAL CODE: EPIDOSNORE2PLAY | PLAY | EP | |
| Reply to examination report in opposition receivedOppositionORIGINAL CODE: EPIDOSNORE3PLBC | PLBC | EP | |
| Information related to despatch of examination report in opposition + time limit modifiedOppositionORIGINAL CODE: EPIDOSCORE2PLAH | PLAH | EP | |
| Opposition filed (corrected)OppositionR26 | R26 | EP | |
| Opposition data, opponent's data or that of the opponent's representative modifiedOppositionORIGINAL CODE: 0009299OPPOPLAB | PLAB | EP | |
| Examination report in opposition despatched + time limitOppositionORIGINAL CODE: EPIDOSNORE2PLAY | PLAY | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapse because of not paying annual feesLapsedMM01 | MM01 | AT | |
| Appeal procedure closedAppealORIGINAL CODE: EPIDOSNNOA9OAPBU | APBU | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Date of receipt of statement of grounds of appeal recordedAppealORIGINAL CODE: EPIDOSNNOA3OAPBQ | APBQ | EP | |
| Opposition filed (corrected)OppositionR26 | R26 | EP | |
| Appeal reference recordedAppealORIGINAL CODE: EPIDOSNREFNOAPBM | APBM | EP | |
| Date of receipt of notice of appeal recordedAppealORIGINAL CODE: EPIDOSNNOA2OAPBP | APBP | EP | |
| Date of receipt of notice of appeal modifiedAppealORIGINAL CODE: EPIDOSCNOA2OAPAJ | APAJ | EP | |
| Appeal reference recordedAppealORIGINAL CODE: EPIDOSNREFNOAPBM | APBM | EP | |
| Date of receipt of notice of appeal recordedAppealORIGINAL CODE: EPIDOSNNOA2OAPBP | APBP | EP | |
| Opposition data, opponent's data or that of the opponent's representative modifiedOppositionORIGINAL CODE: 0009299OPPOPLAB | PLAB | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Appeal reference modifiedAppealORIGINAL CODE: EPIDOSCREFNOAPAH | APAH | EP | |
| Appeal reference recordedAppealORIGINAL CODE: EPIDOSNREFNOAPBM | APBM | EP | |
| Date of receipt of notice of appeal recordedAppealORIGINAL CODE: EPIDOSNNOA2OAPBP | APBP | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Opposition withdrawnWithdrawnORIGINAL CODE: 0009264PLBP | PLBP | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Opposition filed (corrected)OppositionR26 | R26 | EP | |
| Opposition data, opponent's data or that of the opponent's representative modifiedOppositionORIGINAL CODE: 0009299OPPOPLAB | PLAB | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent lapsedLapsedMM4A | MM4A | IE | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Reply of patent proprietor to notice(s) of opposition receivedOppositionORIGINAL CODE: EPIDOSNOBS3PLBB | PLBB | EP | |
| Opposition filed against patentOppositionR026 | R026 | DE | |
| Notice of opposition and request to file observation + time limit sentOppositionORIGINAL CODE: EPIDOSNOBS2PLAX | PLAX | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Opposition filedOpposition26 | 26 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Opposition filedOppositionORIGINAL CODE: 0009260PLBI | PLBI | EP | |
| Opposition filedOppositionORIGINAL CODE: 0009260PLBI | PLBI | EP | |
| Opposition filed against patentOppositionR026 | R026 | DE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Translation of ep patentT3 | T3 | PL | |
| Invalidated european patentMG4D | MG4D | LT | |
| Discontinued in the netherlands as no translation has been filedVDEP | VDEP | NL | |
| Definitive protectionFG2A | FG2A | ES | |
| Dpma publication of mentioned ep patent grantGrantedR096 | R096 | DE | |
| European patents granted designating irelandGrantedLANGUAGE OF EP DOCUMENT: GERMANFG4D | FG4D | IE | |
| Reference to at number (ep patent validated in austria)REF | REF | AT | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| European patent grantedGrantedNOT ENGLISHFG4D | FG4D | GB | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS | GRAS | EP | |
| Observations filed by third partiesORIGINAL CODE: EPIDOSNTIPATPAC | TPAC | EP | |
| Intention to grant announcedINTG | INTG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP | GRAP | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for extension of the european patent (deleted)DAX | DAX | EP | |
| Information on inventor provided before grant (corrected)RIN1 | RIN1 | EP |
Numbers
- Publication
- 2118255
- Application
- 78478237
Titles3
- German
- REINIGUNGSMITTEL
- English
- DETERGENTt COMPOSITION
- French
- COMPOSITION DETERGENTE
Classification
- CPC, 10
- C11D3/33
- C11D3/378
- C11D3/075
- C11D1/72
- C11D3/3757
- C11D3/3902
- C11D3/042
- C11D3/3942
- C11D1/722
- C11D3/361
- IPC, 2
- C11D3 33
- C11D3 37
Designated states1
- Contracting states, 1
- Türkiye
