EP3559185B1 - Clear-rinse formulation - Google Patents
Clear-rinse formulation Download PDFInfo
- Publication number
- EP3559185B1 EP3559185B1 EP17825162.5A EP17825162A EP3559185B1 EP 3559185 B1 EP3559185 B1 EP 3559185B1 EP 17825162 A EP17825162 A EP 17825162A EP 3559185 B1 EP3559185 B1 EP 3559185B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- agent
- agent according
- carbon atoms
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000009472 formulation Methods 0.000 title description 11
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- 239000004094 surface-active agent Substances 0.000 claims description 40
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- 239000002736 nonionic surfactant Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
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- 230000007797 corrosion Effects 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
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- 150000002978 peroxides Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- FJGQHLDAFYBROH-UHFFFAOYSA-N propane-1,2,3-triol;sulfo hydrogen sulfate Chemical compound OCC(O)CO.OS(=O)(=O)OS(O)(=O)=O FJGQHLDAFYBROH-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to agents with improved rinsing performance in dishwashing, the use of these agents and a method for machine dishwashing using these agents.
- Machine-washed dishes are often subject to higher requirements today than hand-washed dishes. Dishes that have been completely cleaned of food residues are also rated as imperfect if, after machine dishwashing, they still show whitish stains caused by water hardness or other mineral salts, which originate from dried water droplets due to a lack of wetting agent. Such staining and streaking can be observed in principle on all types of surfaces (porcelain, glass, plastic, stainless steel), but especially on glass surfaces. This crockery is post-treated by the consumer, often by hand, which is not very user-friendly. There is therefore a need for machine dishwashing detergents which reduce the formation of so-called spotting and filming stains and deposits.
- Rinse aid agents are used in dishwashing formulations to obtain sparkling, spotless dishes. Film formation on the dishes mediated by these agents is intended to allow the water to drain off the items to be washed as completely as possible, so that the surfaces are residue-free and immaculately shiny at the end of the washing program. Although the use of such rinse aids is known in the prior art, there is still a need for dishwashing detergents that exhibit improved rinse-aid performance.
- dishwashing detergents currently on the market have poor drying performance, particularly when used on plastic items to be washed.
- An improvement in drying on plastic would be an advantageous property of a new dishwashing detergent.
- dishwashing detergents can lead to heavy foam formation, which can be limited without the use of additional antifoam inhibitors is desirable.
- the phase stability of dishwashing detergents under different storage conditions can also be problematic. Therefore, it would be desirable for the consumer to have a composition that exhibits increased phase stability, particularly when stored at elevated temperatures.
- WO 92/14808 A1 and EP 2 963 100 A1 disclose a rinse aid for automatic dishwashing, containing a mixture of at least two alkoxylated alcohols and nonionic surfactants.
- the object on which the present invention is based was therefore to provide an agent which solves the problems mentioned above.
- the formulations according to the invention have improved storage stability, in particular when they are used in relation to one another according to the invention.
- the present invention also relates to the use of an agent according to the invention in an automatic dishwashing process, in particular the use to improve the rinsing performance when cleaning dishes in an automatic dishwashing machine.
- a further object of the invention is an automatic dishwashing process in which an agent according to the invention is used in particular for the purpose of improving the rinsing performance.
- the present invention also relates to the use of the surfactant mixture used according to the invention to improve the rinsing performance in machine dishwashing.
- At least one as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
- the information refers to the type of ingredient and not to the absolute number of molecules.
- At least one nonionic surfactant thus means, for example, at least one type of nonionic surfactant, ie one type of nonionic surfactant or a mixture of several different nonionic surfactants can be meant.
- the information relates to all compounds of the specified type that are contained in the composition/mixture, ie the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
- compositions described herein are preferably phosphate-free.
- Phosphate-free as used herein means that the composition in question is essentially free of phosphates, i.e. phosphates are not intentionally added, in particular phosphates in amounts less than 1% by weight, preferably less than 0.1% by weight. based on the total composition.
- free from means that the relevant substance is present in amounts of less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, based on the total composition is included. In particular, this also means that the substance in question is not deliberately added.
- alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient for charge equalization - as the anion.
- the agents described herein are dishwashing agents in the broadest sense, in particular those which are used in machine dishwashing in automatic dishwashing machines.
- the term "dishwashing detergent” as used herein also includes rinse aid formulations that are used in addition to the actual detergent formulation.
- the agents of the invention are such rinse aids.
- these may also contain other surfactants and typically fragrances and preservatives.
- compositions of the invention contain a surfactant mixture which comprises at least two low-foaming nonionic surfactants from the group of polyoxyalkylated nonionic surfactants, as defined above.
- the first surfactant is at least one nonionic fatty alcohol alkoxylate of the formula R 1 O[CH 2 CHR 3 O] x H, where R 1 is a linear or branched, saturated alkyl radical having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, more preferably 13 bis 15 carbon atoms, each R 3 is independently -H or -CH 2 CH 3 and x is 10-20, wherein at least one, preferably at least 5, more preferably at least 9 or 10 R 3 are H and at least one or two R 3 are CH 2 CH 3 .
- the first surfactant is an ethoxylated/butoxylated fatty alcohol with 10 to 18 carbon atoms in the alkyl group.
- Nonionic surfactants with EO-BO blocks are preferred, in which case one to ten EO or 1-2 BO groups are bonded to one another before a block of the other groups follows.
- Nonionic surfactants of the general formula R 1 O[CH 2 CH 2 O] x [CH 2 CH(CH 2 CH 3 )O] z H are particularly preferred wherein R 1 is as defined above but is preferably linear, x is 9-15, and z is 1-5, preferably 1-2.
- nonionic surfactants are particularly preferred which have a C 13-15 alkyl radical containing 9 to 15 ethylene oxide units followed by 1 to 5, preferably 1 to 2, butylene oxide units.
- Such surfactants are available, for example, from BASF under the trade name Plurafac® .
- a preferred surfactant is Plurafac® LF220 (BASF SE).
- the surfactant mixture also includes at least one second nonionic surfactant of the formula R 2 O[CH 2 CH 2 O] y H, where R 2 is a linear or branched, preferably linear, saturated alkyl radical having 10 to 16 carbon atoms, preferably 12 to 16 or 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms, and y is an integer between 3 and 8, preferably between 4 and 7, more preferably 6.
- the group of these nonionic surfactants includes, for example, C 12-14 fatty alcohols with (EO) 4-7 , in particular C 12-14 fatty alcohol (EO) 6 .
- Such surfactants are commercially available from BASF under the trade names Dehydol® LT and Dehydol® LS.
- Dehydol® LS6 (BASF SE) is particularly preferably used.
- the mass ratio of the at least one nonionic ethoxylated/butoxylated surfactant to the at least one nonionic ethoxylated surfactant, ie surfactant (i) to surfactant (ii), is in the range from 1:10 to 2:1, preferably in the range from 1:5 to 1:1, more preferably 1:4 to 7:8, especially at 2:3.
- the amount based on the total weight of the composition is for the surfactant (i) preferably 1 to 10% by weight, preferably 3 to 5% by weight and for the surfactant (ii) preferably 1 to 10% by weight, preferably 5 up to 7% by weight.
- a combination of nonionic surfactants according to i) is particularly preferred, preferably such
- Fatty alcohol alkoxylates which have a C 13-15 alkyl radical with 9 to 15 ethylene oxide units, followed by 1 to 5, preferably 1 to 2, butylene oxide units, with nonionic surfactants according to ii), preferably C 12-14 fatty alcohols with (EO) 4-7 , in particular C 12-14 fatty alcohol (EO) 6 in a mass ratio of preferably 1:4 to 7:8, in particular 2:3.
- the amount, based on the total weight of the composition is preferably 1 to 10% by weight, preferably 3 to 5% by weight, for the surfactant (i) and preferably 1 to 10% by weight for the surfactant (ii). 5 to 7% by weight.
- the detergents according to the invention can contain other surfactants in the surfactant mixture, in particular other nonionic or else anionic surfactants, but also cationic or amphoteric surfactants.
- nonionic surfactants are, for example, alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, but also nonionic surfactants of the amine oxide type.
- the amount of these nonionic surfactants is preferably not more than that of the alkoxylated fatty alcohols, in particular not more than half of it.
- the compositions of the invention contain no nonionic surfactants apart from the surfactants (i) and (ii) described according to the invention.
- anionic surface-active substances are suitable as anionic surfactants.
- Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates.
- compositions of the invention are free from anionic surfactants.
- the pH of the composition * below 7, preferably between 2 and 5, more preferably between 3 and 4.5.
- the pH value of the agent can be adjusted using standard pH regulators.
- Acids and/or alkalis are used as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
- Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
- they can also Mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof are used.
- Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred.
- alkali metal hydroxides of which potassium hydroxide and especially sodium hydroxide are preferred.
- volatile alkali for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule.
- the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
- the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2H 2 O and tripotassium citrate H 2 O.
- ICI buffering agents buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred.
- Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2H 2 O and tripotassium citrate H 2 O.
- the agents according to the invention can contain at least one, preferably two or more other components, preferably selected from the group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaching agents, bleaching activators, foam inhibitors, dyes, fragrances , bitter substances and antimicrobial agents.
- Suitable ingredients are known to those skilled in the art.
- Customary components of rinse aid formulations are, in particular, fragrances and antimicrobial active ingredients (preservatives) and optionally soluble builders, in particular organic builders.
- Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these.
- the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH in the dishwashing detergents.
- an acidifying component particularly well as citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.
- Another important class of phosphate-free builders are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycine diacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts ethylene diamine diacetic acid (EDDS) or its salts. GLDA or its salts are very particularly preferred.
- Automatic dishwashing detergents are therefore preferred according to the invention, characterized in that the detergent contains citric acid or a salt of citric acid and the proportion by weight of the citric acid or the salt of citric acid is preferably 0.5 to 20% by weight, preferably 1 to 15% by weight and in particular between 1 and 10% by weight.
- Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
- preservatives can be contained in the agents.
- preservatives from the groups of alcohols, aldehydes, antimicrobial acids and/or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butylcarbamate, iodine, iodophors and peroxides.
- Preferred antimicrobial agents are preferably selected from the group consisting of ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-( 3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)bis(1-octanamine)dihydrochloride, N,N'-bis(4- chlorophenyl)-3,12-diimino-2,4,
- particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
- Solvents suitable for the compositions used according to the invention are generally water-miscible organic solvents such as, without limitation, ethanol, propanol, 1,2-propanediol and glycerol.
- the agents can be presented in solid or liquid form or as a combination of solid and liquid forms. Powders, granules, extrudates, compacts, in particular tablets, are particularly suitable as solid supply forms.
- the liquid supply forms based on water and/or organic solvents can be thickened and in the form of gels.
- the agents can be packaged in the form of single-phase or multi-phase products. The individual phases of multi-phase agents can have the same or different states of aggregation.
- Liquid as used herein in relation to the agent according to the invention, therefore includes all free-flowing compositions and in particular also includes gels and pasty compositions.
- compositions described herein are preferably rinse aids for machine dishwashing and are in liquid form.
- the amount of a dosage unit of the agent is between 0.1 and 10 ml, preferably between 0.1 and 5 ml, more preferably 3 ml. Accordingly, the preferred total amount of surfactants used in the rinse cycle of a dishwasher is from 0 .05 to 1 g/job, preferably 0.1 to 0.8 g/job, in particular 0.2 to 0.4 g/job, for example 0.3 g/job.
- compositions described herein can be preformulated into dosage units. These dosing units preferably include the amount of cleaning-active substances required for one cleaning cycle.
- the volume of the dosage unit is preferably between 0.1 and 10 ml, preferably between 0.1 and 5 ml and particularly preferably 3 ml.
- the prefabricated dosage unit can have a water-soluble cover made of a water-soluble film material. It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility. Suitable water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer and are known in the prior art.
- the invention also relates to the use of the agents according to the invention in machine dishwashing.
- the use to improve the rinsing performance when cleaning dishes in an automatic dishwasher is recorded.
- the invention also relates to a dishwashing method, in particular an automatic dishwashing method, in which an agent according to the invention is used, in particular for the purpose of improving the rinsing performance.
- the subject matter of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while a dishwashing program is being run through.
- the agent according to the invention can be dosed or 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.
- the present invention also relates to the use of the surfactant mixture used according to the invention to improve the rinsing performance in machine dishwashing.
- a particularly preferred embodiment is an automatic dishwashing process, characterized in that an agent according to any one of claims 1 to 7 with a total surfactant amount of 0.05 to 1 g/job, preferably 0.1 to 0.8 g/job, in particular 0 2 to 0.4 g/job, for example 0.3 g/job, preferably in the rinse cycle, is used.
- Example 1 Drying formulations: Citric Acid Monohydrate: 1.6% Surfactant: according to the results table preservative: 0.05% Perfume: 0.1% Water: rest
- composition containing 8% LS 6 + 2% LF 220 foams more.
- the formulation with 6% Dehydol LS 6 and 4% Plurafac LF220 delivers comparable drying values, but hardly foams.
- the machine (Miele GSL 2, program 50 °C, 8 min holding time, 65 °C final rinse temperature) was fully opened for 30 minutes after the end of the washing cycle and then placed in the black inspection room (assessment room that is painted matt black or lined and shielded from light). and visually determined with artificial lighting with 2 fluorescent tubes (Philips TLD 36W/965 Natural Daylight 6500).
- the results for the formulations tested are listed in Table 3 as arithmetic mean values. Higher values mean less dripping, ie better rinsing performance.
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Description
Die vorliegende Erfindung betrifft Mittel mit verbesserter Klarspülleistung beim Geschirrspülen, die Verwendung dieser Mittel sowie ein Verfahren zum maschinellen Geschirrspülen unter Verwendung dieser Mittel.The present invention relates to agents with improved rinsing performance in dishwashing, the use of these agents and a method for machine dishwashing using these agents.
An maschinell gespültes Geschirr werden heute häufig höhere Anforderungen gestellt als an manuell gespültes Geschirr. So wird auch ein von Speiseresten völlig gereinigtes Geschirr dann als nicht einwandfrei bewertet, wenn es nach dem maschinellen Geschirrspülen noch weißliche, auf Wasserhärte oder anderen mineralischen Salzen beruhende Flecken aufweist, die mangels Netzmittel aus eingetrockneten Wassertropfen stammen. Derartige Flecken- und Schlierenbildung ist prinzipiell auf Oberflächen aller Art (Porzellan, Glas, Kunststoff, Edelstahl), insbesondere jedoch auf Glasoberflächen beobachtbar. Dieses Geschirr wird vom Verbraucher - oftmals per Hand - nachbehandelt, was wenig anwenderfreundlich ist. Deshalb besteht ein Bedarf an maschinellen Geschirrspülmitteln, die die Bildung von sogenannten spotting und filming Flecken und Belägen mindern.Machine-washed dishes are often subject to higher requirements today than hand-washed dishes. Dishes that have been completely cleaned of food residues are also rated as imperfect if, after machine dishwashing, they still show whitish stains caused by water hardness or other mineral salts, which originate from dried water droplets due to a lack of wetting agent. Such staining and streaking can be observed in principle on all types of surfaces (porcelain, glass, plastic, stainless steel), but especially on glass surfaces. This crockery is post-treated by the consumer, often by hand, which is not very user-friendly. There is therefore a need for machine dishwashing detergents which reduce the formation of so-called spotting and filming stains and deposits.
Um glanzklares und fleckenloses Geschirr zu erhalten, werden in Geschirrspülrezepturen Klarspüleragenzien verwendet. Durch eine durch diese Agenzien vermittelte Filmbildung auf dem Geschirr soll das Wasser möglichst vollständig vom Spülgut ablaufen, so dass die Oberflächen am Ende des Spülprogramms rückstandsfrei und makellos glänzend sind. Obwohl die Verwendung derartiger Klarspüler im Stand der Technik bekannt ist, besteht weiterhin Bedarf an Geschirrspülmitteln, die eine verbesserte Klarspülleistung zeigen.Rinse aid agents are used in dishwashing formulations to obtain sparkling, spotless dishes. Film formation on the dishes mediated by these agents is intended to allow the water to drain off the items to be washed as completely as possible, so that the surfaces are residue-free and immaculately shiny at the end of the washing program. Although the use of such rinse aids is known in the prior art, there is still a need for dishwashing detergents that exhibit improved rinse-aid performance.
Des Weiteren zeigen die meisten der derzeit auf dem Markt befindlichen Geschirrspülmittel schwache Trocknungsleistung, insbesondere bei der Anwendung auf Plastik-Spülgut. Eine Verbesserung der Trocknung an Kunststoff wäre insofern eine vorteilhafte Eigenschaft eines neuen Geschirrspülmittels.Furthermore, most of the dishwashing detergents currently on the market have poor drying performance, particularly when used on plastic items to be washed. An improvement in drying on plastic would be an advantageous property of a new dishwashing detergent.
Ferner kann es bei der Anwendung von handelsüblichen Geschirrspülmitteln zu einer starken Schaumbildung kommen, deren Begrenzung ohne die Verwendung zusätzlicher Anti-Schauminhibitoren wünschenswert ist. Auch die Phasenstabilität von Geschirrspülmitteln unter verschiedenen Lagerbindungen kann problematisch sein. Daher stellt wäre es für den Verbraucher wünschenswert ein Mittel zu haben, dass eine erhöhte Phasenstabilität, insbesondere bei der Lagerung bei erhöhten Temperaturen zeigt.Furthermore, the use of commercially available dishwashing detergents can lead to heavy foam formation, which can be limited without the use of additional antifoam inhibitors is desirable. The phase stability of dishwashing detergents under different storage conditions can also be problematic. Therefore, it would be desirable for the consumer to have a composition that exhibits increased phase stability, particularly when stored at elevated temperatures.
Die der vorliegenden Erfindung zugrunde liegende Aufgabe bestand daher darin, ein Mittel bereitzustellen, das die oben genannten Probleme löst.The object on which the present invention is based was therefore to provide an agent which solves the problems mentioned above.
Es wurde nun überraschenderweise gefunden, dass die erfindungsgemäß eingesetzte Kombination von nichtionischen Tensiden in Klarspülerformulierungen, die beim Geschirrspülen eingesetzt werden, eine verbesserte Filmbildung auf Spülgutoberflächen herbeiführen, wodurch das Wasser in einem dünnen, zusammenhängenden Film vom Spülgut ablaufen kann, so dass beim anschließenden Trocknungsvorgang keine Wassertropfen, Streifen oder Filme zurückbleiben.It has now surprisingly been found that the combination of nonionic surfactants used according to the invention in rinse aid formulations that are used in dishwashing bring about improved film formation on the surfaces of items to be washed, as a result of which the water can run off the items to be washed in a thin, coherent film, so that no Drops of water, streaks, or films remain.
Dadurch wird die Schlierenbildung auf Spülgut unterdrückt und die Trocknungs- und Klarspülleistung deutlich verbessert. Des Weiteren weisen die erfindungsgemäßen Formulierungen eine verbesserte Lagerstabilität auf, insbesondere wenn sie im erfindungsgemäßen Verhältnis zueinander verwendet werden. Durch einen geringen Anteil an eingesetzten Tensiden in den erfindungsgemäßen Mitteln und durch die Anwendung des erfindungsgemäßen Verhältnisses der Tenside zueinander ist es möglich die Menge des sich bildenden Schaums während des Waschvorgangs signifikant zu begrenzen.This suppresses the formation of streaks on the items to be washed and significantly improves the drying and rinsing performance. Furthermore, the formulations according to the invention have improved storage stability, in particular when they are used in relation to one another according to the invention. By using a small proportion of surfactants in the detergents according to the invention and by using the ratio of surfactants to one another according to the invention, it is possible to significantly limit the amount of foam that forms during the washing process.
Ein erster Aspekt der vorliegenden Erfindung betrifft daher ein Mittel, insbesondere einen Klarspüler wie er beim maschinellen Geschirrspülen eingesetzt wird, enthaltend, bezogen auf das Gesamtgewicht des Geschirrspülmittels, 5,0 bis 20,0 Gew.-%, vorzugsweise 6,0 bis 15,0 Gew.-%, noch bevorzugter 7,0 bis 12,0 Gew.-% einer Tensidmischung umfassend:
- (i) mindestens ein nichtionisches Fettalkoholalkoxylat der Formel R1O[CH2CHR3O]xH, wobei R1 für einen linearen oder verzweigten, gesättigten Alkylrest mit 10 bis 18 Kohlenstoffatomen, vorzugsweise 12 bis 16 Kohlenstoffatomen, noch bevorzugter 13 bis 15 Kohlenstoffatomen steht, jedes R3 unabhängig für -H oder -CH2CH3 steht und x für 10-20 steht, wobei mindestens ein, vorzugsweise mindestens 5, noch bevorzugter mindestens 9 oder 10 R3 H und mindestens ein oder zwei R3 CH2CH3 sind; und
- (ii) mindestens ein nichtionisches Fettalkoholethoxylat der Formel R2O[CH2CH2O]yH, wobei R2 für einen linearen oder verzweigten, gesättigten Alkylrest mit 10 bis 16 Kohlenstoffatomen, vorzugsweise 12 bis 16 oder 10 bis 14 Kohlenstoffatomen, noch bevorzugter 12 bis 14 Kohlenstoffatomen steht, und y für eine ganze Zahl zwischen 3 und 8, bevorzugt zwischen 4 und 7, noch bevorzugt 6 steht,
- (i) at least one nonionic fatty alcohol alkoxylate of the formula R 1 O[CH 2 CHR 3 O] x H, where R 1 is a linear or branched, saturated alkyl radical having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, more preferably 13 to 15 carbon atoms, each R 3 is independently -H or -CH 2 CH 3 and x is 10-20, with at least one, preferably at least 5, more preferably at least 9 or 10 R 3 H and at least one or two R 3 CH 2 are CH 3 ; and
- (ii) at least one nonionic fatty alcohol ethoxylate of the formula R 2 O[CH 2 CH 2 O] y H, where R 2 is a linear or branched, saturated alkyl radical having 10 to 16 carbon atoms, preferably 12 to 16 or 10 to 14 carbon atoms more preferably 12 to 14 carbon atoms, and y is an integer between 3 and 8, preferably between 4 and 7, more preferably 6,
Ebenfalls Gegenstand der vorliegenden Erfindung ist die Verwendung eines erfindungsgemäßen Mittels in einem maschinellen Geschirrspülverfahren, insbesondere die Verwendung zur Verbesserung der Klarspülleistung bei der Reinigung von Geschirr in einer automatischen Geschirrspülmaschine.The present invention also relates to the use of an agent according to the invention in an automatic dishwashing process, in particular the use to improve the rinsing performance when cleaning dishes in an automatic dishwashing machine.
Noch ein weiterer Gegenstand der Erfindung ist ein maschinelles Geschirrspülverfahren, bei dem ein erfindungsgemäßes Mittel insbesondere zu dem Zweck, die Klarspülleistung zu verbessern, zum Einsatz kommt.A further object of the invention is an automatic dishwashing process in which an agent according to the invention is used in particular for the purpose of improving the rinsing performance.
Schließlich ist ebenso die Verwendung der erfindungsgemäß eingesetzten Tensidmischung zur Verbesserung der Klarspülleistung beim maschinellen Geschirrspülen Gegenstand der vorliegenden Erfindung.Finally, the present invention also relates to the use of the surfactant mixture used according to the invention to improve the rinsing performance in machine dishwashing.
Diese und weitere Aspekte, Merkmale und Vorteile der Erfindung werden für den Fachmann aus dem Studium der folgenden detaillierten Beschreibung und Ansprüche ersichtlich. Dabei kann jedes Merkmal aus einem Aspekt der Erfindung in jedem anderen Aspekt der Erfindung eingesetzt werden. Ferner ist es selbstverständlich, dass die hierin enthaltenen Beispiele die Erfindung beschreiben und veranschaulichen sollen, diese aber nicht einschränken und insbesondere die Erfindung nicht auf diese Beispiele beschränkt ist. Numerische Bereiche, die in dem Format "von x bis y" angegeben sind, schließen die genannten Werte ein. Wenn mehrere bevorzugte numerische Bereiche in diesem Format angegeben sind, ist es selbstverständlich, dass alle Bereiche, die durch die Kombination der verschiedenen Endpunkte entstehen, ebenfalls erfasst werden.These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.
"Mindestens ein", wie hierin verwendet, bedeutet 1 oder mehr, d.h. 1, 2, 3, 4, 5, 6, 7, 8, 9 oder mehr. Bezogen auf einen Inhaltsstoff bezieht sich die Angabe auf die Art des Inhaltsstoffs und nicht auf die absolute Zahl der Moleküle. "Mindestens ein nichtionisches Tensid" bedeutet somit beispielsweise mindestens eine Art von nichtionischem Tensid, d.h. dass eine Art von nichtionischem Tensid oder eine Mischung mehrerer verschiedener nichtionischer Tenside gemeint sein kann. Zusammen mit Gewichtsangaben bezieht sich die Angabe auf alle Verbindungen der angegebenen Art, die in der Zusammensetzung/Mischung enthalten sind, d.h. dass die Zusammensetzung über die angegebene Menge der entsprechenden Verbindungen hinaus keine weiteren Verbindungen dieser Art enthält."At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. “At least one nonionic surfactant” thus means, for example, at least one type of nonionic surfactant, ie one type of nonionic surfactant or a mixture of several different nonionic surfactants can be meant. Together with weight information, the information relates to all compounds of the specified type that are contained in the composition/mixture, ie the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
Die hierin beschriebenen Mittel sind vorzugsweise phosphatfrei. "Phosphatfrei", wie hierin verwendet, bedeutet, dass die betreffende Zusammensetzung im Wesentlichen frei von Phosphaten ist, d.h. Phosphate nicht bewusst zugesetzt sind, insbesondere Phosphate in Mengen kleiner als 1 Gew.-%, vorzugsweise kleiner als 0,1 Gew.-% bezogen auf die Gesamtzusammensetzung enthalten sind. Dementsprechend heißt "frei von", wie hierin verwendet, dass der entsprechende Stoff in Mengen kleiner als 1 Gew.-%, vorzugsweise kleiner als 0,1 Gew.%, noch bevorzugter kleiner als 0,01 Gew.-% bezogen auf die Gesamtzusammensetzung enthalten ist. Insbesondere ist damit aber auch gemeint, dass der entsprechende Stoff nicht bewusst zugesetzt wird.The compositions described herein are preferably phosphate-free. "Phosphate-free" as used herein means that the composition in question is essentially free of phosphates, i.e. phosphates are not intentionally added, in particular phosphates in amounts less than 1% by weight, preferably less than 0.1% by weight. based on the total composition. Accordingly, "free from", as used herein, means that the relevant substance is present in amounts of less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, based on the total composition is included. In particular, this also means that the substance in question is not deliberately added.
Alle Prozentangaben, die im Zusammenhang mit den hierin beschriebenen Zusammensetzungen gemacht werden, beziehen sich, sofern nicht explizit anders angegeben auf Gew.-%, jeweils bezogen auf die betreffende Zusammensetzung.Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to % by weight, based in each case on the composition in question.
"Ungefähr" oder "ca.", wie hierin im Zusammenhang mit einem Zahlenwert verwendet bezieht sich auf den Zahlenwert ±10 %, vorzugsweise ±5%."About" or "about" as used herein in connection with a numerical value refers to the numerical value ±10%, preferably ±5%.
Wann immer im Folgenden Erdalkalimetalle als Gegenionen für einwertige Anionen genannt sind, so bedeutet das, dass das Erdalkalimetall natürlich nur in der halben - zum Ladungsausgleich ausreichenden - Stoffmenge wie das Anion vorliegt.Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient for charge equalization - as the anion.
Die hierin beschriebenen Mittel sind Geschirrspülmittel im weitesten Sinne, insbesondere solche, die beim maschinellen Geschirrspülen in automatischen Geschirrspülmaschinen eingesetzt werden. Der Begriff "Geschirrspülmittel", wie hierin verwendet, erfasst somit auch Klarspülerformulierungen, die zusätzlich zu der eigentlichen Reinigerformulierung eingesetzt werden. Tatsächlich handelt es sich, in verschiedenen Ausführungsformen, bei den Mitteln der Erfindung um derartige Klarspüler. Diese enthalten neben Wasser als Hauptlösungsmittel und wesentlichem Bestandteil ggf. weitere Tenside sowie typischerweise Duft- und Konservierungsstoffe.The agents described herein are dishwashing agents in the broadest sense, in particular those which are used in machine dishwashing in automatic dishwashing machines. The term "dishwashing detergent" as used herein also includes rinse aid formulations that are used in addition to the actual detergent formulation. In fact, in various embodiments, the agents of the invention are such rinse aids. In addition to water as the main solvent and an essential component, these may also contain other surfactants and typically fragrances and preservatives.
Die Mittel der Erfindung enthalten eine Tensidmischung, die mindestens zwei schwachschäumende nichtionische Tenside aus der Gruppe der polyoxyalkylierten Niotenside, wie oben definiert, umfasst.The compositions of the invention contain a surfactant mixture which comprises at least two low-foaming nonionic surfactants from the group of polyoxyalkylated nonionic surfactants, as defined above.
Das erste Tensid ist mindestens ein nichtionisches Fettalkoholalkoxylat der Formel R1O[CH2CHR3O]xH, wobei R1 für einen linearen oder verzweigten, gesättigten Alkylrest mit 10 bis 18 Kohlenstoffatomen, vorzugsweise 12 bis 16 Kohlenstoffatomen, noch bevorzugter 13 bis 15 Kohlenstoffatomen steht, jedes R3 unabhängig für -H oder -CH2CH3 steht und x für 10-20 steht, wobei mindestens ein, vorzugsweise mindestens 5, noch bevorzugter mindestens 9 oder 10 R3 H und mindestens ein oder zwei R3 CH2CH3 sind. Dies bedeutet, dass es sich bei dem ersten Tensid um einen ethoxylierten/butoxylierten Fettalkohol mit 10 bis 18 Kohlenstoffatomen im Alkylrest handelt. Unter diesen sind wiederum Tenside mit EO-BO-Blöcken bevorzugt, wobei jeweils eine bis zehn EO- bzw. 1-2 BO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Besonders bevorzugt sind nichtionische Tenside der allgemeinen Formel R1O[CH2CH2O]x[CH2CH(CH2CH3)O]zH
in der R1 wie oben definiert ist, aber vorzugsweise linear ist, x für 9 bis 15, und z für 1 bis 5, vorzugsweise 1 bis 2 steht. Somit sind insbesondere nichtionische Tenside bevorzugt, die einen C13-15-Alkylrest mit 9 bis 15 Ethylenoxideinheiten, gefolgt von 1 bis 5, vorzugsweise 1 bis 2 Butylenoxideinheiten aufweisen.The first surfactant is at least one nonionic fatty alcohol alkoxylate of the formula R 1 O[CH 2 CHR 3 O] x H, where R 1 is a linear or branched, saturated alkyl radical having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, more preferably 13 bis 15 carbon atoms, each R 3 is independently -H or -CH 2 CH 3 and x is 10-20, wherein at least one, preferably at least 5, more preferably at least 9 or 10 R 3 are H and at least one or two R 3 are CH 2 CH 3 . This means that the first surfactant is an ethoxylated/butoxylated fatty alcohol with 10 to 18 carbon atoms in the alkyl group. Among these, surfactants with EO-BO blocks are preferred, in which case one to ten EO or 1-2 BO groups are bonded to one another before a block of the other groups follows. Nonionic surfactants of the general formula R 1 O[CH 2 CH 2 O] x [CH 2 CH(CH 2 CH 3 )O] z H are particularly preferred
wherein R 1 is as defined above but is preferably linear, x is 9-15, and z is 1-5, preferably 1-2. Thus, nonionic surfactants are particularly preferred which have a C 13-15 alkyl radical containing 9 to 15 ethylene oxide units followed by 1 to 5, preferably 1 to 2, butylene oxide units.
Derartige Tenside sind beispielsweise von BASF unter dem Handelsnamen Plurafac® erhältlich.Such surfactants are available, for example, from BASF under the trade name Plurafac® .
Ein bevorzugt eingesetztes Tensid ist Plurafac® LF220 (BASF SE).A preferred surfactant is Plurafac® LF220 (BASF SE).
Die Tensidmischung umfasst daneben mindestens ein zweites nichtionisches Tensid der Formel R2O[CH2CH2O]yH, wobei R2 für einen linearen oder verzweigten, vorzugsweise linearen, gesättigten Alkylrest mit 10 bis 16 Kohlenstoffatomen, vorzugsweise 12 bis 16 oder 10 bis 14 Kohlenstoffatomen, noch bevorzugter 12 bis 14 Kohlenstoffatomen steht, und y für eine ganze Zahl zwischen 3 und 8, bevorzugt zwischen 4 und 7, noch bevorzugt 6 steht.The surfactant mixture also includes at least one second nonionic surfactant of the formula R 2 O[CH 2 CH 2 O] y H, where R 2 is a linear or branched, preferably linear, saturated alkyl radical having 10 to 16 carbon atoms, preferably 12 to 16 or 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms, and y is an integer between 3 and 8, preferably between 4 and 7, more preferably 6.
Zur Gruppe dieser nichtionischen Tenside zählen beispielsweise C12-14 Fettalkohole mit (EO)4-7, insbesondere C12-14 Fettalkohol-(EO)6.The group of these nonionic surfactants includes, for example, C 12-14 fatty alcohols with (EO) 4-7 , in particular C 12-14 fatty alcohol (EO) 6 .
Derartige Tenside sind unter den Handelsnamen Dehydol® LT und Dehydol® LS von BASF kommerziell erhältlich. Besonders bevorzugt wird Dehydol® LS6 (BASF SE) eingesetzt.Such surfactants are commercially available from BASF under the trade names Dehydol® LT and Dehydol® LS. Dehydol® LS6 (BASF SE) is particularly preferably used.
Das Massenverhältnis des mindestens einen nichtionischen ethoxylierten/butoxylierten Tensids zu dem mindestens einen nichtionischen ethoxylierten Tensid, d.h. von dem Tensid (i) zu dem Tensid (ii) liegt Bereich von 1:10 bis 2:1, vorzugsweise im Bereich von 1:5 bis 1:1, noch bevorzugter 1:4 bis 7:8, insbesondere bei 2:3. Die Menge bezogen auf das Gesamtgewicht der Zusammensetzung beträgt für das Tensid (i) vorzugsweise 1 bis 10 Gew.-%, vorzugsweise 3 bis 5 Gew.-% und für das Tensid (ii) vorzugsweise 1 bis 10 Gew.-%, vorzugsweise 5 bis 7 Gew.%.The mass ratio of the at least one nonionic ethoxylated/butoxylated surfactant to the at least one nonionic ethoxylated surfactant, ie surfactant (i) to surfactant (ii), is in the range from 1:10 to 2:1, preferably in the range from 1:5 to 1:1, more preferably 1:4 to 7:8, especially at 2:3. The amount based on the total weight of the composition is for the surfactant (i) preferably 1 to 10% by weight, preferably 3 to 5% by weight and for the surfactant (ii) preferably 1 to 10% by weight, preferably 5 up to 7% by weight.
Fettalkoholalkoxylate, die einen C13-15-Alkylrest mit 9 bis 15 Ethylenoxideinheiten, gefolgt von 1 bis 5, vorzugsweise 1 bis 2 Butylenoxideinheiten aufweisen, mit nichtionischen Tensiden gemäß ii), bevorzugt C12-14 Fettalkohole mit (EO)4-7, insbesondere C12-14 Fettalkohol-(EO)6 in einem Masseverhältnis von bevorzugt 1:4 bis 7:8, insbesondere von 2:3. Die Menge bezogen auf das Gesamtgewicht der Zusammensetzung beträgt dabei für das Tensid (i) vorzugsweise 1 bis 10 Gew.-%, vorzugsweise 3 bis 5 Gew.-% und für das Tensid (ii) vorzugsweise 1 bis 10 Gew.-%, vorzugsweise 5 bis 7 Gew.%.Fatty alcohol alkoxylates which have a C 13-15 alkyl radical with 9 to 15 ethylene oxide units, followed by 1 to 5, preferably 1 to 2, butylene oxide units, with nonionic surfactants according to ii), preferably C 12-14 fatty alcohols with (EO) 4-7 , in particular C 12-14 fatty alcohol (EO) 6 in a mass ratio of preferably 1:4 to 7:8, in particular 2:3. The amount, based on the total weight of the composition, is preferably 1 to 10% by weight, preferably 3 to 5% by weight, for the surfactant (i) and preferably 1 to 10% by weight for the surfactant (ii). 5 to 7% by weight.
Die erfindungsgemäßen Mittel können in der Tensidmischung neben den vorstehend genannten nichtionischen Tensiden weitere Tenside, insbesondere weitere nichtionische oder auch anionische Tenside, aber auch kationische oder amphotere Tenside enthalten.In addition to the nonionic surfactants mentioned above, the detergents according to the invention can contain other surfactants in the surfactant mixture, in particular other nonionic or else anionic surfactants, but also cationic or amphoteric surfactants.
Als weitere nichtionische Tenside eignen sich beispielsweise Alkylglykoside, alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, aber auch nichtionische Tenside vom Typ der Aminoxide. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der alkoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. In verschiedenen Ausführungsformen enthalten die Mittel der Erfindung aber keine nichtionischen Tenside außer den erfindungsgemäß beschriebenen Tensiden (i) und (ii).Other suitable nonionic surfactants are, for example, alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, but also nonionic surfactants of the amine oxide type. The amount of these nonionic surfactants is preferably not more than that of the alkoxylated fatty alcohols, in particular not more than half of it. In various embodiments, however, the compositions of the invention contain no nonionic surfactants apart from the surfactants (i) and (ii) described according to the invention.
Als anionische Tenside eignen sich alle anionischen oberflächenaktiven Stoffe. Bevorzugte anionische Tenside sind Fettalkoholsulfate, Fettalkoholethersulfate, Dialkylethersulfate, Monoglyceridsulfate, Alkylbenzolsulfonate, Olefinsulfonate, Alkansulfonate, Ethersulfonate, n-Alkylethersulfonate, Estersulfonate und Ligninsulfonate. Ebenfalls verwendbar sind Fettsäurecyanamide, Sulfosuccinate (Sulfobernsteinsäureester), insbesondere Sulföbernsteinsäuremono- und -di-Alkylester mit 8 bis 18 C-Atomen, Sulfosuccinamate, Sulfosuccinamide, Fettsäureisethionate, Acylaminoalkansulfonate (Fettsäuretauride), Fettsäuresarcosinate, Ethercarbonsäuren und Alkyl(ether)phosphate sowie α-Sulfofettsäuresalze, Acylglutamate, Monoglyceriddisulfate und Alkylether des Glycerindisulfats. In bevorzugten Ausführungsformen sind die Mittel der Erfindung allerdings frei von anionischen Tensiden. Der pH-Wert des Mittels* unter 7, bevorzugt zwischen 2 und 5, noch bevorzugter zwischen 3 und 4,5. Generell *liegt kann der pH-Wert des Mittels mittels üblicher pH-Regulatoren eingestellt werden. Als pH-Stellmittel dienen Säuren und/oder Alkalien. Geeignete Säuren sind insbesondere organische Säuren wie die Essigsäure, Zitronensäure, Glycolsäure, Milchsäure, Bernsteinsäure, Adipinsäure, Äpfelsäure, Weinsäure und Gluconsäure oder auch Amidosulfonsäure. Daneben können aber auch die Mineralsäuren Salzsäure, Schwefelsäure und Salpetersäure bzw. deren Mischungen eingesetzt werden. Geeignete Basen stammen aus der Gruppe der Alkali- und Erdalkalimetallhydroxide und -carbonate, insbesondere der Alkalimetallhydroxide, von denen Kaliumhydroxid und vor allem Natriumhydroxid bevorzugt ist. Besonders bevorzugt ist allerdings flüchtiges Alkali, beispielsweise in Form von Ammoniak und/oder Alkanolaminen, die bis zu 9 C-Atome im Molekül enthalten können. Das Alkanolamin ist hierbei vorzugsweise ausgewählt aus der Gruppe bestehend aus Mono-, Di-, Triethanol- und -Propanolamin und deren Mischungen.All anionic surface-active substances are suitable as anionic surfactants. Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-alkyl esters having 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts can also be used , acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate. In preferred embodiments, however, the compositions of the invention are free from anionic surfactants. The pH of the composition * below 7, preferably between 2 and 5, more preferably between 3 and 4.5. In general *is the pH value of the agent can be adjusted using standard pH regulators. Acids and/or alkalis are used as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, they can also Mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof are used. Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred. However, particular preference is given to volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
Zur Einstellung und/oder Stabilisierung des pH-Werts kann das erfindungsgemäße Mittel auch ein oder mehrere Puffersubstanzen (INCI Buffering Agents) enthalten, üblicherweise in Mengen von 0,001 bis 5 Gew.-%. Bevorzugt sind Puffersubstanzen, die zugleich Komplexbildner oder sogar Chelatbildner (Chelatoren, INCI Chelating Agents) sind. Besonders bevorzugte Puffersubstanzen sind die Citronensäure bzw. die Citrate, insbesondere die Natrium- und Kaliumcitrate, beispielsweise Trinatriumcitrat 2H2O und Trikaliumcitrat-H2O.To adjust and/or stabilize the pH, the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2H 2 O and tripotassium citrate H 2 O.
Die erfindungsgemäßen Mittel können mindestens einen, vorzugsweise zwei oder mehr weitere Bestandteile enthalten, vorzugsweise ausgewählt aus der Gruppe bestehend aus Gerüststoffen, Enzymen, Verdickern, Sequestrierungsmitteln, Elektrolyten, Korrosionsinhibitoren, insbesondere Silberschutzmitteln, Glaskorrosionsinhibitoren, Polymeren, Bleichmitteln, Bleichaktivatoren, Schauminhibitoren, Farbstoffen, Duftstoffen, Bitterstoffen und antimikrobiellen Wirkstoffen. Geeignete Bestandteile sind dem Fachmann bekannt. Übliche Bestandteile von Klarspülerformulieren sind insbesondere Duftstoffe und antimikrobielle Wirkstoffe (Konservierungsmittel) sowie ggf. lösliche Gerüststoffe, insbesondere organische Builder.The agents according to the invention can contain at least one, preferably two or more other components, preferably selected from the group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, polymers, bleaching agents, bleaching activators, foam inhibitors, dyes, fragrances , bitter substances and antimicrobial agents. Suitable ingredients are known to those skilled in the art. Customary components of rinse aid formulations are, in particular, fragrances and antimicrobial active ingredients (preservatives) and optionally soluble builders, in particular organic builders.
Falls Gerüststoffe eingesetzt werden, werden insbesondere lösliche organische Builder eingesetzt. Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes der Geschirrspülmittel. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen. Eine weitere bedeutende Klasse der phosphatfreien Gerüststoffe stellen Aminocarbonsäuren und/oder ihre Salze dar. Besonders bevorzugte Vertreter dieser Klasse sind Methylglycindiessigsäure (MGDA) oder ihre Salze sowie Glutamindiessigsäure (GLDA) oder ihre Salze oder Ethylendiamindiessigsäure (EDDS) oder ihre Salze. Ganz besonders bevorzugt ist GLDA bzw. dessen Salze.If builders are used, soluble organic builders are used in particular. Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which 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, saccharic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder action, the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH in the dishwashing detergents. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these. Another important class of phosphate-free builders are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycine diacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts ethylene diamine diacetic acid (EDDS) or its salts. GLDA or its salts are very particularly preferred.
Als besonders vorteilhaft für die Reinigungs- und Klarspülleistung hat sich der Einsatz von Citronensäure und/oder Citraten erwiesen. Erfindungsgemäß bevorzugt werden daher maschinelle Geschirrspülmittel, dadurch gekennzeichnet, dass das Mittel Citronensäure oder ein Salz der Citronensäure enthält und das der Gewichtsanteil der Citronensäure oder des Salzes der Citronensäure vorzugsweise 0,5 bis 20 Gew.-%, vorzugsweise 1 bis 15 Gew.-% und insbesondere zwischen 1 und 10 Gew.-% beträgt.The use of citric acid and/or citrates has proven to be particularly advantageous for the cleaning and rinsing performance. Automatic dishwashing detergents are therefore preferred according to the invention, characterized in that the detergent contains citric acid or a salt of citric acid and the proportion by weight of the citric acid or the salt of citric acid is preferably 0.5 to 20% by weight, preferably 1 to 15% by weight and in particular between 1 and 10% by weight.
Als Parfümöle bzw. Duftstoffe können im Rahmen der vorliegenden Erfindung einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pinien-, Citrus-, Jasmin-, Patchouli-, Rosen- oder Ylang-Ylang-Öl.Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
Weiterhin können Konservierungsmittel in den Mitteln enthalten sein. Geeignet sind beispielsweise Konservierungsmittel aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren und/oder deren Salze, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1,2-Dibrom-2,4-dicyanobutan, lodo-2-propynyl-butylcarbamat, Iod, lodophore und Peroxide. Bevorzugte antimikrobielle Wirkstoffe werden vorzugsweise ausgewählt aus der Gruppe umfassend Ethanol, n-Propanol, i-Propanol, 1,3-Butandiol, Phenoxyethanol, 1,2-Propylenglykol, Glycerin, Undecylensäure, Zitronensäure, Milchsäure, Benzoesäure, Salicylsäure, Thymol, 2-Benzyl-4-chlorphenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 2,4,4'-Trichlor-2'-hydroxydiphenylether, N-(4-Chlorphenyl)-N-(3,4-dichlorphenyl)-harnstoff, N,N'-(1,10-decandiyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydrochlorid, N,N'-Bis-(4-Chlorphenyl)-3,12-diimino-2,4,11,13-tetraazatetradecandiimidamid, antimikrobielle quaternäre oberflächenaktive Verbindungen, Guanidine. Besonders bevorzugte Konservierungsmittel sind jedoch ausgewählt aus der Gruppe umfassend Salicylsäure, quaternäre Tenside, insbesondere Benzalkoniumchlorid und Isothiazole und deren Derivate wie Isothiazoline und Isothiazolinone.Furthermore, preservatives can be contained in the agents. For example, preservatives from the groups of alcohols, aldehydes, antimicrobial acids and/or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butylcarbamate, iodine, iodophors and peroxides. Preferred antimicrobial agents are preferably selected from the group consisting of ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-( 3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)bis(1-octanamine)dihydrochloride, N,N'-bis(4- chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
Lösemittel, die für die erfindungsgemäß eingesetzten Zusammensetzungen geeignet sind, sind neben Wasser als bevorzugtes Lösemittel generell mit Wasser mischbare organische Lösemittel, wie beispielsweise, ohne Einschränkung, Ethanol, Propanol, 1,2-Propandiol und Glycerin.Solvents suitable for the compositions used according to the invention, in addition to water as the preferred solvent, are generally water-miscible organic solvents such as, without limitation, ethanol, propanol, 1,2-propanediol and glycerol.
Generell kann die Konfektionierung hierin beschriebener Mittel in unterschiedlicher Weise erfolgen. Die Mittel können in fester oder flüssiger sowie als Kombination fester und flüssiger Angebotsformen vorliegen. Als feste Angebotsformen eignen sich insbesondere Pulver, Granulate, Extrudate, Kompaktate, insbesondere Tabletten. Die flüssigen Angebotsformen auf Basis von Wasser und/oder organischen Lösungsmitteln können verdickt, in Form von Gelen vorliegen. Die Mittel können in Form einphasiger oder mehrphasiger Produkte konfektioniert werden. Die einzelnen Phasen mehrphasiger Mittel können gleiche oder unterschiedliche Aggregatzustände aufweisen.In general, the preparations described here can take place in different ways. The agents can be presented in solid or liquid form or as a combination of solid and liquid forms. Powders, granules, extrudates, compacts, in particular tablets, are particularly suitable as solid supply forms. The liquid supply forms based on water and/or organic solvents can be thickened and in the form of gels. The agents can be packaged in the form of single-phase or multi-phase products. The individual phases of multi-phase agents can have the same or different states of aggregation.
"Flüssig", wie hierin in Bezug auf das erfindungsgemäße Mittel verwendet, schließt daher alle fließfähigen Zusammensetzungen ein und erfasst insbesondere auch Gele und pastöse Zusammensetzungen."Liquid", as used herein in relation to the agent according to the invention, therefore includes all free-flowing compositions and in particular also includes gels and pasty compositions.
Die hierin beschriebenen Mittel sind vorzugsweise Klarspüler für das maschinelle Geschirrspülen und liegen in flüssiger Form vor.The compositions described herein are preferably rinse aids for machine dishwashing and are in liquid form.
In weiteren bevorzugten Ausführungsformen beträgt die Menge einer Dosierungseinheit des Mittels zwischen 0,1 und 10 ml, bevorzugt zwischen 0,1 und 5 ml, noch bevorzugter 3 ml. Dementsprechend beträgt die bevorzugte Gesamttensidmenge, die im Klarspülgang einer Geschirrspülmaschine, eingesetzt wird, von 0,05 bis 1 g/job, bevorzugt 0,1 bis 0,8 g/job, insbesondere 0,2 bis 0,4 g/job, beispielsweise 0,3 g/job.In further preferred embodiments, the amount of a dosage unit of the agent is between 0.1 and 10 ml, preferably between 0.1 and 5 ml, more preferably 3 ml. Accordingly, the preferred total amount of surfactants used in the rinse cycle of a dishwasher is from 0 .05 to 1 g/job, preferably 0.1 to 0.8 g/job, in particular 0.2 to 0.4 g/job, for example 0.3 g/job.
Obwohl nicht bevorzugt, können die hierin beschriebenen Mittel zu Dosiereinheiten vorkonfektioniert werden. Diese Dosiereinheiten umfassen vorzugsweise die für einen Reinigungsgang notwendige Menge an reinigungsaktiven Substanzen. Das Volumen der Dosiereinheit beträgt bevorzugt zwischen 0,1 und 10 ml, vorzugsweise zwischen 0,1 und 5 ml und besonders bevorzugt 3 ml. In solchen Ausführungsformen kann die vorgefertigte Dosiereinheit eine wasserlösliche Umhüllung aus einem wasserlöslichen Folienmaterial aufweisen. Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält. Wasserlösliche Umhüllungen, die Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthalten, weisen eine gute Stabilität bei einer ausreichend hohen Wasserlöslichkeit, insbesondere Kaltwasserlöslichkeit, auf. Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer und sind im Stand der Technik bekannt.Although not preferred, the compositions described herein can be preformulated into dosage units. These dosing units preferably include the amount of cleaning-active substances required for one cleaning cycle. The volume of the dosage unit is preferably between 0.1 and 10 ml, preferably between 0.1 and 5 ml and particularly preferably 3 ml. In such embodiments, the prefabricated dosage unit can have a water-soluble cover made of a water-soluble film material. It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility. Suitable water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer and are known in the prior art.
Die Verwendung der erfindungsgemäßen Mittel beim maschinellen Geschirrspülen ist ebenfalls Gegenstand der Erfindung. Dabei wird insbesondere die Verwendung zur Verbesserung der Klarspülleistung bei der Reinigung von Geschirr in einer automatischen Geschirrspülmaschine erfasst.The invention also relates to the use of the agents according to the invention in machine dishwashing. In particular, the use to improve the rinsing performance when cleaning dishes in an automatic dishwasher is recorded.
Ebenso betrifft die Erfindung ein Geschirrspülverfahren, insbesondere maschinelles Geschirrspülverfahren, bei welchem ein Mittel gemäß der Erfindung eingesetzt wird, insbesondere zu dem Zweck, die Klarspülleistung zu verbessern. Gegenstand der vorliegenden Anmeldung ist daher weiterhin ein Verfahren zur Reinigung von Geschirr in einer Geschirrspülmaschine, bei welchem das erfindungsgemäße Mittel während des Durchlaufens eines Geschirrspülprogramms in den Innenraum einer Geschirrspülmaschine eindosiert wird. Die Eindosierung bzw. der Eintrag des erfindungsgemäßen Mittels in den Innenraum der Geschirrspülmaschine kann manuell erfolgen, vorzugsweise wird das Mittel jedoch mittels der Dosierkammer in den Innenraum der Geschirrspülmaschine dosiert.The invention also relates to a dishwashing method, in particular an automatic dishwashing method, in which an agent according to the invention is used, in particular for the purpose of improving the rinsing performance. The subject matter of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while a dishwashing program is being run through. The agent according to the invention can be dosed or 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.
Schließlich ist ebenso die Verwendung der erfindungsgemäß eingesetzten Tensidmischung zur Verbesserung der Klarspülleistung beim maschinellen Geschirrspülen Gegenstand der vorliegenden Erfindung.Finally, the present invention also relates to the use of the surfactant mixture used according to the invention to improve the rinsing performance in machine dishwashing.
Eine besonders bevorzugte Ausführungsform ist ein maschinelles Geschirrspülverfahren, dadurch gekennzeichnet, dass ein Mittel nach einem der Ansprüche 1 bis 7 mit einer Gesamttensidmenge von 0,05 bis 1 g/job, bevorzugt 0,1 bis 0,8 g/job, insbesondere 0,2 bis 0,4 g/job, beispielsweise 0,3 g/job, bevorzugt im Klarspülgang, zum Einsatz kommt.A particularly preferred embodiment is an automatic dishwashing process, characterized in that an agent according to any one of claims 1 to 7 with a total surfactant amount of 0.05 to 1 g/job, preferably 0.1 to 0.8 g/job, in particular 0 2 to 0.4 g/job, for example 0.3 g/job, preferably in the rinse cycle, is used.
Die im Kontext mit den erfindungsgemäßen Mitteln beschriebenen Ausführungsformen sind ohne Weiteres auch auf die erfindungsgemäßen Verfahren und Verwendungen übertragbar und umgekehrt.The embodiments described in the context of the agents according to the invention can also be readily transferred to the methods and uses according to the invention and vice versa.
Bei der Trocknung (getestet in einer Bosch SMS 68 M 62 mit dem Programm ECO 50°C Variospeed) wird die Anzahl der Tropfen beurteilt. Höhere Werte zeigen eine höhere Tropfenzahl an und damit ein schlechteres Trocknungsergebnis. Von einem signifikanten Unterschied ist ab einer Differenz von 0,5 oder größer auszugehen.
Bei der Untersuchung wurde zusätzlich festgestellt, dass die Zusammensetzung enthaltend 8% LS 6 + 2 % LF 220 stärker schäumt. Die Rezeptur mit 6% Dehydol LS 6 und 4% Plurafac LF220 liefert vergleichbare Trocknungswerte, schäumt aber kaum.During the investigation, it was also found that the composition containing 8% LS 6 + 2% LF 220 foams more. The formulation with 6% Dehydol LS 6 and 4% Plurafac LF220 delivers comparable drying values, but hardly foams.
Formulierungen: wie Bsp. 1, nur die Tensidmenge wurde entsprechend den Versuchsangaben geändert.Formulations: as Ex. 1, only the amount of surfactant was changed according to the experimental data.
Für die Reinigung im Hauptspülgang wurde eine handelsübliche klassische Reinigungsmitteltablette, welche kein Kombinationsprodukt inkl. Klarspüler darstellt, eingesetzt.For cleaning in the main wash cycle, a commercially available classic detergent tablet, which is not a combination product including rinse aid, was used.
Dazu wurde die Maschine (Miele GSL 2, Programm 50 °C, 8 min Haltezeit, 65 °C Klarspültemperatur) nach Beendigung des Spülzyklus 30 Minuten vollständig geöffnet und anschließend im Schwarzen Abmusterungsraum (Beurteilungsraum, der matt-schwarz gestrichen oder ausgekleidet und lichtdicht abgeschirmt ist und mit einer künstlichen Beleuchtung mit 2 Leuchtstoffröhren (Philips TLD 36W/965 Natural Daylight 6500 ausgestattet ist) visuell bestimmt.For this purpose, the machine (Miele GSL 2, program 50 °C, 8 min holding time, 65 °C final rinse temperature) was fully opened for 30 minutes after the end of the washing cycle and then placed in the black inspection room (assessment room that is painted matt black or lined and shielded from light). and visually determined with artificial lighting with 2 fluorescent tubes (Philips TLD 36W/965 Natural Daylight 6500).
Als Kenngrößen wurden Klarspülnoten auf Basis des optischen Erscheinungsbilds des trockenen Spülguts vergeben (Wert (1) = schlechtestes Ergebnis - hohe Anzahl von Tropfen, hohe Intensität von Tropfen bis Wert (5)= bestes Ergebnis - keine Tropfen). Die Ergebnisse für die getesteten Rezepturen sind in der Tabelle 3 als arithmetische Mittelwerte aufgelistet. Höhere Werte bedeuten geringere Tropfenbildung, d.h. eine bessere Klarspülleistung.
Claims (10)
- An agent, in particular a rinse aid for automatic dishwashing, containing, based on the total weight of the dishwashing agent, 5.0 to 20.0 wt.%, preferably 6.0 to 15.0 wt.%, more preferably 7.0 to 12.0 wt.%, of a surfactant mixture comprising:(i) at least one non-ionic fatty alcohol alkoxylate of the formula R1O[CH2CHR3O]xH, where R1 is a linear or branched, saturated alkyl functional group having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, more preferably 13 to 15 carbon atoms, each R3 independently represents -H or -CH2CH3 and x represents 10-20, where at least one, preferably at least 5, more preferably at least 9 or 10 instances of R3 are H and at least one or two instances of R3 are CH2CH3; and(ii) at least one non-ionic fatty alcohol ethoxylate of the formula R2O[CH2CH2O]yH, where R2 is a linear or branched, saturated alkyl functional group having 10 to 16 carbon atoms, preferably 12 to 16 or 10 to 14 carbon atoms, more preferably 12 bis 14 carbon atoms, and y is an integer between 3 and 8, preferably between 4 and 7, more preferably 6,wherein the mass ratio of the at least one non-ionic surfactant (i) to the at least one non-ionic surfactant (ii) is in the range from 1:10 to 2:1, preferably in the range from 1:5 to 1:1, more preferably 1:4 to 7:8, for example 2:3, and the pH of the agent is below 7.
- The agent according to claim 1, characterized in that surfactant (i) is a compound of the formula R1O[CH2CH2O]x[CH2CH(CH2CH3)O]zH, in which R1 is defined as above, in particular is a C13-15 alkyl functional group, x represents 9 to 15, and z represents 1 to 5, preferably 1 to 2.
- The agent according to claim 1 or 2, characterized in that surfactant (ii) is a C12-14 fatty alcohol with (EO)4-7, in particular a C12-14 fatty alcohol-(EO)6.
- The agent according to one of claims 1 to 3, characterized in that the pH of the agent is between 2 and 5, more preferably between 3 and 4.5.
- The agent according to one of claims 1 to 4, characterized in that a dosage unit of the agent is between 0.1 and 10 ml, preferably between 0.1 and 5 ml, more preferably 3 ml.
- The agent according to one of claims 1 to 5, characterized in that, in each case based on the total weight of the composition, the surfactant (i) is contained in an amount of 1 to 10 wt.%, preferably 3 to 5 wt.%, and/or the surfactant (ii) is contained in an amount of 1 to 10 wt.%, preferably 5 to 7 wt.%.
- The agent according to one of claims 1 to 6, characterized in that the surfactant mixture contains further surfactants, in particular further non-ionic, anionic, cationic and/or amphoteric surfactants, and/or the agent contains at least one further constituent, preferably at least two further components, selected from the group consisting of builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protecting agents, glass corrosion inhibitors, polymers, bleaching agents, bleach activators, suds suppressors, dyes, fragrances, bitterns and antimicrobial active ingredients.
- The use of an agent according to one of claims 1 to 7 in a dishwashing method, in particular an automatic dishwashing method.
- A dishwashing method, in particular an automatic dishwashing method, characterized in that an agent according to one of claims 1 to 7 is used.
- The automatic dishwashing method according to claim 9, characterized in that an agent according to one of claims 1 to 7 that has a total surfactant amount of 0.05 to 1 g/job, preferably 0.1 to 0.8 g/job, in particular 0.2 to 0.4 g/job, for example 0.3 g/job, is used, preferably in a rinse cycle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016225904.0A DE102016225904A1 (en) | 2016-12-21 | 2016-12-21 | rinse aid |
| PCT/EP2017/082557 WO2018114508A1 (en) | 2016-12-21 | 2017-12-13 | Clear-rinse formulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3559185A1 EP3559185A1 (en) | 2019-10-30 |
| EP3559185B1 true EP3559185B1 (en) | 2022-08-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17825162.5A Active EP3559185B1 (en) | 2016-12-21 | 2017-12-13 | Clear-rinse formulation |
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| Country | Link |
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| EP (1) | EP3559185B1 (en) |
| DE (1) | DE102016225904A1 (en) |
| ES (1) | ES2928866T3 (en) |
| PL (1) | PL3559185T3 (en) |
| WO (1) | WO2018114508A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4105602A1 (en) * | 1991-02-22 | 1992-08-27 | Basf Ag | USE OF A MIXTURE OF AT LEAST TWO ALCOXYLATED ALCOHOLS AS A FOAM-ABSORBING SURFACTANT ADDITIVE IN CLEANING AGENTS FOR MAINTENANCE CLEANING PROCESSES |
| RO112759B1 (en) * | 1996-11-20 | 1997-12-30 | Sc Dmk Srl | Cleaning products for special and universal application |
| EP1270711A1 (en) * | 2001-06-28 | 2003-01-02 | Givaudan SA | Fabric-cleaning compositions |
| EP2963100B1 (en) * | 2014-07-04 | 2018-09-19 | Kolb Distribution Ltd. | Liquid rinse aid compositions |
| EP3015540B1 (en) * | 2014-10-29 | 2022-02-16 | The Procter & Gamble Company | Hard surface cleaners comprising ethoxylated alkoxylated nonionic surfactants |
-
2016
- 2016-12-21 DE DE102016225904.0A patent/DE102016225904A1/en not_active Withdrawn
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2017
- 2017-12-13 PL PL17825162.5T patent/PL3559185T3/en unknown
- 2017-12-13 EP EP17825162.5A patent/EP3559185B1/en active Active
- 2017-12-13 ES ES17825162T patent/ES2928866T3/en active Active
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Also Published As
| Publication number | Publication date |
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| ES2928866T3 (en) | 2022-11-23 |
| PL3559185T3 (en) | 2022-12-19 |
| WO2018114508A1 (en) | 2018-06-28 |
| EP3559185A1 (en) | 2019-10-30 |
| DE102016225904A1 (en) | 2018-06-21 |
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