EP1036157B1 - Dish washing detergent with a specific viscosity profile - Google Patents
Dish washing detergent with a specific viscosity profile Download PDFInfo
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- EP1036157B1 EP1036157B1 EP98963466A EP98963466A EP1036157B1 EP 1036157 B1 EP1036157 B1 EP 1036157B1 EP 98963466 A EP98963466 A EP 98963466A EP 98963466 A EP98963466 A EP 98963466A EP 1036157 B1 EP1036157 B1 EP 1036157B1
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- European Patent Office
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- viscosity
- mpa
- surfactants
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the invention relates to dishwashing detergents with a specific viscosity profile, containing one thickened surfactant mixture that is not caused by liquid crystalline structures.
- the object of the invention was to formulate a hand dishwashing detergent, in addition to the usual surfactant mixtures for this product group a component for setting a specific viscosity profile.
- Thickened cleaning agents are known in the prior art. Among other things, polymers Silicas, clays and silicates as well as other ingredients are used.
- WO 95/20027 describes liquid or gel-like hand dishwashing detergents which are thickened by adding amine oxide.
- WO 95/07971 describes gel-like dishwashing detergents containing protease enzyme, which is intended to ensure hand mildness.
- WO 95/06108 describes concentrated or gel dishwashing detergents which are thickened by adding calcium salts and xylene sulfonates.
- the addition of divalent ions to surfactants often leads to dimerization of surfactants and thus to the formation of liquid-crystalline structures in hand dishwashing detergents.
- GB 2280682 describes gel-like compositions containing urea which are present in the hexagonal liquid-crystalline phase. The viscosity of such liquid-crystalline compositions in production, storage and use is very difficult to control.
- WO 94/09100 proposes to stabilize gel-like hand dishwashing detergents based on polyhydroxy fatty acid amides by adding boric acid.
- nonionic surfactants such as alkyl polyglycoside and zwitterionic surfactants, e.g. Betaines
- soaps in hand dishwashing liquid, so you get - probably because of the formation of liquid crystalline phases - often highly viscous, bad dosed and poorly soluble products.
- additional solvents Ensuring a lowering of viscosity, on the one hand, worsens in some If the storage stability of the agents, on the other hand, a low-viscosity product is less precisely dosed. Even with dried burnt dirt can be very targeted Stains are treated. Here a thickened product has clear advantages in the Application.
- compositions proposed in the prior art is suitable as precisely metered, excellent cleaning, hand-compatible, temperature and storage stable, pourable and ecologically particularly compatible hand dishwashing liquid specific viscosity profile.
- the present invention relates to a pourable, storage-stable hand dishwashing detergent, containing a surfactant mixture of anionic surfactants and / or nonionic surfactants and / or betaine surfactants containing between 0.01 and 5% by weight of polymers contains and has a specific viscosity profile.
- fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably having 6 to 22 carbon atoms.
- the former are preferred for ecological reasons, in particular because of their vegetable basis than based on renewable raw materials, but without restricting the teaching according to the invention to them.
- the rule for example after the Roelen oxo process available Oxo-alcohols or their derivatives are used accordingly.
- surfactant mixtures are those made from anionic and nonionic surfactants. But also the use of betaine surfactants in a mixture, especially in combination with anionic and nonionic surfactants, can be very useful for many applications his. Overall, the surfactants are used in amounts of 0.2 to 60% by weight, preferably from 1 to 55% by weight, particularly preferably 3 to 50% by weight and extremely preferably 5 up to 45% by weight.
- Polymers in the sense of the present invention are polycarboxylates or carboxyvinyl polymers, preferably homo- and copolymers of acrylic acid, especially acrylic acid polymers and acrylic acid-methacrylic acid copolymers, heteropolysaccharides (xanthan, guar, propoxylated guar) and somewhat less preferred other polymeric thickeners known in the market.
- Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n- alkyl ether sulfonates, ester sulfonates and lingin sulfonates.
- aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n- alkyl ether sulfon
- Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
- the fatty alcohol ether sulfates are particularly preferred in the context of the present invention.
- Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated Alcohols.
- alkoxylated alcohols generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, for the purposes of the present Invention preferred with longer-chain alcohols. Usually arises from n moles Ethylene oxide and a mole of alcohol, depending on the reaction conditions, a complex Mixture of addition products of different degrees of ethoxylation.
- Another The alkoxylation is carried out using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
- lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.
- the anionic surfactants are preferably used in amounts between 0.2 and 49.8% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight.
- compositions contain 0.5 to 15% by weight.
- Fatty alcohol sulfates In a preferred embodiment of the invention, the compositions contain 0.5 to 15% by weight.
- Nonionic surfactants in the context of the present invention can be alkoxylates such as Polyglycol ether, fatty alcohol polyglycol ether, alkylphenol polyglycol ether, end group capped Polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides can also be used and fatty acid polyglycol ether.
- An important class of nonionic surfactants, the can be used according to the invention are the polyol surfactants and here in particular Glucose surfactants such as alkyl polyglycosides and fatty acid glucamides. Those are particularly preferred Alkylpolyglucosides.
- Alkyl polyglycosides are surfactants which can be obtained by the reaction of, sugars and alcohols according to the relevant methods of preparative organic chemistry, which, depending on the type of production, results in a mixture of monoalkylated, oligomeric or polymeric sugars.
- Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 to C 18 alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, is in particular 1.1 to 3, most preferably 1.1 to 1.7.
- the alkyl polyglycosides are preferably used in amounts between 0.1 to 14.9% by weight, in particular 1 to 8% by weight and extremely preferably 1 to 5% by weight.
- zwitterionic surfactants or amphoteric surfactants used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the aminopropionates as well as the amino oxides, sulfobetaines and biosurfactants.
- alkylamidobetaine is one preferred ingredient here.
- These zwitterionic surfactants are preferably used in amounts between 0.1 to 14.9% by weight, in particular between 0.5 to 10% by weight, extremely preferably between 1 to 8% by weight.
- solubilizers for example for dyes and perfume oils, for example alkanolamines, Polyols such as ethylene glycol, 1,2-propylene glycol, glycerin and other mono- and polyvalent Alcohols and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical are used.
- the agents according to the invention have a Brookfield viscosity (measured with the spindle recommended for the respective viscosity range) at 20 ° C. and a shear rate of 10 s -1 between 1,000 and 10,000 mPa ⁇ s, preferably between 1,300 and 9,000 mPa ⁇ s and particularly preferred between 1,500 and 7,000 mPas or at 20 ° C. and a shear rate of 30 s -1 between 500 and 8,000 mPas, preferably between 900 and 7,000 mPas and particularly preferably between 1,100 and 6,000 mPas.
- Preferred zero shear viscosity values ⁇ 0 for favorable storage properties are between 1,000 and 10,000 Pa ⁇ s, preferably between 1,000 and 5,000 Pa ⁇ s.
- the viscosity of the agents according to the invention can be between 0.01 and 5% by weight, preferably between 0.02 and 4% by weight, particularly preferably between 0.05 and 3% by weight, in particular between 0.1 and 1.5% by weight and very preferably between 0.2 and 0.9 wt .-%, are set.
- the amounts can vary from polymer to polymer his.
- the surfactant composition used also plays a role in the choice of quantity a role. Methacrylic acid-acrylic acid copolymers have been found to be particularly suitable as well as acrylic acid polymers.
- Clarity is of particular importance here - especially from the point of view of the user of the products. Deposition of phases or ingredients as well as a cloudy appearance is usually not desired.
- one or more dicarboxylic acids and / or their salts are added to the thickened mixtures, alone or in a mixture, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described, for example, under the trade name Sokalan ® DSC Na is available.
- 0.1 to 8 wt.% Preferably 0.5 to 7 wt.%, Particularly preferably 0.8 to 6 wt.% And extremely preferably 1 to 4 wt. %, shown.
- a change in the dicarboxylic acid (salt) content can - especially in amounts above 2% by weight - contribute to a clear solution of the ingredients. Is also within The viscosity of the mixture can be influenced by this agent within certain limits. This component also influences the solubility of the mixture.
- Salts are advantageously used individually or in mixtures, such as sodium formate, Sodium acetate, sodium tartrate, sodium chloride and magnesium chloride or else Salts of the aforementioned anions with other alkali or alkaline earth metals.
- the dicarboxylic acid or salt component serves to achieve clear, homogeneous formulations and influences the viscosity as well as the cold and dissolving behavior. Without these Auxiliary component, the agents can show an opaque to slightly cloudy appearance.
- the Combination of polymer with this auxiliary component enables the production of clear gel-like agents with good cold and dissolving behavior.
- solvents e.g. Alcohols, especially low molecular weight alcohols such as ethanol. You contribute to the familiarization of perfume and dye, prevent the formation of liquid crystalline phases and have Share in the formation of clear products. However, too much solvent causes too much solvent Decrease in viscosity. Therefore, according to the invention, between 3 and 12% by weight of one or contain several solvents, preferably between 4 and 10 wt .-%, particularly preferred between 5 and 10% by weight.
- the amount of solvent also has an influence on the homogeneity and the viscosity of the agents according to the invention. At low levels of solvent, especially below 3% by weight, inhomogeneities can occur depending on the composition of the agent.
- the Viscosity can be reduced by increasing the amount of solvent.
- Agents according to the invention naturally have a different dissolving behavior than conventional hand dishwashing detergents. Enough for one fast dissolution time must therefore be observed.
- Agents according to the invention dissolve in the usual dilution in the hand-rinse basin between 10 and 240 seconds, preferably between 15 and 120 seconds, particularly preferably between 20 and 100 seconds.
- the dissolution time is from the thickening and depending on the selected surfactant combinations.
- the lightfastness of the products is a particularly important factor.
- the consumer prefers colored - i.e. dye-containing products in translucent bottles. This results in high demands on the lightfastness of the agents.
- the is particularly suitable here Use of acrylic acid polymers as well as acrylic acid-methacrylic acid copolymers.
- UV stabilizers can also be used according to the invention respectively. From the point of view of production costs, however, a waiver is particularly favorable such agents, since they often do not contribute to cleaning performance.
- a further improved cleaning performance especially with burnt-on dirt when using abrasives, preferably water-soluble abrasives, especially alkali metal bicarbonate, alkali metal sulfate and the like.
- ingredients common in hand dishwashing detergents such as defoamers, Structuring agents, perfumes, dyes, corrosion inhibitors and preservatives, be contained in amounts of up to 5 wt .-%.
- the pH of the agents according to the invention can be adjusted using conventional pH regulators, for example Citric acid or NaOH, are set, whereby - essentially because of required hand tolerance - a range from 5.5 to 8, preferably 6 to 7.5, in particular 6.5 to 7.1 is preferred.
- pH regulators for example Citric acid or NaOH
- the hand dishwashing detergents according to the invention can be stirred together of the individual components in any order and leave the mixture to produce for freedom from bubbles.
- the order of preparation is not for the preparation of the agent crucial.
- Agents E1 to E30 according to the invention were prepared as described above and their pH, viscosity, cold cloud or clear point and dissolution time were determined.
- compositions of the agents E1 to E30 according to the invention in% by weight and the specific properties are shown in Tables 1 to 4.
- agents E1 to E30 according to the invention contained traces of dye.
- the pH of the agents E1 to E30 according to the invention was adjusted to between 6.5 and 7.1 using citric acid.
- the viscosity was determined at 20 ° C according to Brookfield ( Brookfield LV DV II + viscometer; spindle 25; shear rate 30 min -1 ).
- the cold cloud point was determined by cooling a sample in the cryostat with a cooling rate of 0.2 ° C.min -1 , the cold cloud point being the temperature at which a slight cloudiness was first detected. After the sample was completely cloudy, the mixture was heated at a heating rate of 0.2 ° C.min -1 . The temperature at which the sample is completely clear for the first time is given as the clear point.
- the rinsing performance of the recipes according to the invention was also largely determined. The determination was carried out in a semi-automatic plate test apparatus using two different pure grease stains (the average is indicated) and a greasy mixed stain. Plates soiled with the test soiling at a constant temperature of 40 or 45 ° C in 5 l of water with a hardness of 16 ° under constant conditions compared to a high-quality classic hand dishwashing liquid as a laboratory standard until the foam - which was formed before the start of the test - was destroyed was and the plates were no longer clean. The concentration of the agent was 2 ml per 5 l of water or, in the case of agents E25 to E28, 4 ml per 5 l of water.
- the polymers used were acrylic acid polymer, acrylic acid-methacrylic acid copolymer and carboxyvinyl polymer used.
- the viscosity of the mixture can also be influenced by this agent within certain limits. Another influence of the Sokalan DSC ® was found on the solubility of the mixture.
- the amount of ethanol also has an influence on the homogeneity and the viscosity.
- the amount of solvent in the above recipe shows an inhomogeneity below 4% by weight. However, this can differ from recipe to recipe.
- the viscosity can be influenced (reduced) by increasing the amount of solvent.
- the viscosity was 3500 to 4000 m ⁇ Pas, the dissolution time between 45 to 70 seconds.
- the cleaning performance of dirt was very good, the cleaning performance of grease was above average good, the foaming power with and without oil was good, as was the emulsifying power.
- the thickened product therefore has a stronger effect than comparable hand dishwashing detergents.
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Abstract
Description
Die Erfindung betrifft Geschirrspülmittel mit spezifischem Viskositätsprofil, enthaltend eine verdickten Tensidmischung, die nicht durch flüssigkristalline Strukturen hervorgerufen wird.The invention relates to dishwashing detergents with a specific viscosity profile, containing one thickened surfactant mixture that is not caused by liquid crystalline structures.
Versucht man, mit herkömmlichen Mitteln ein genau dosierbares, ausgezeichnet reinigendes, handverträgliches, temperatur- und lagerstabiles, gießfähiges und ökologisch besonders verträgliches Handgeschirrspülmittel herzustellen, stößt man schnell an die Leistungsgrenze der Produkte. Aufgabe der Erfindung war es nun, ein Handgeschirrspülmittel zu formulieren, das neben der sonst für diese Produktgruppe üblichen Tensidmischungen eine Komponente zur Einstellung eines spezifischen Viskositätsprofils enthält.If you try to use conventional means to precisely dose, clean, easy to handle, temperature and storage stable, pourable and ecologically special Making compatible hand dishwashing detergents quickly reaches the performance limit of the products. The object of the invention was to formulate a hand dishwashing detergent, in addition to the usual surfactant mixtures for this product group a component for setting a specific viscosity profile.
Verdickte Reinigungsmittel sind im Stand der Technik bekannt. Es werden u.a. Polymere, Kieselsäuren, Tone und Silikate sowie andere Inhaltsstoffe verwendet.Thickened cleaning agents are known in the prior art. Among other things, polymers Silicas, clays and silicates as well as other ingredients are used.
Die WO 95/20027 beschreibt flüssige oder gelförmige Handgeschirrspülmittel, die durch Zugabe von Aminoxid verdickt sind. WO 95/20027 describes liquid or gel-like hand dishwashing detergents which are thickened by adding amine oxide.
Die WO 95/07971 beschreibt gelförmige Geschirrspülmittel mit einem Gehalt an Proteaseenzym, welches die Handmildheit sicherstellen soll. WO 95/07971 describes gel-like dishwashing detergents containing protease enzyme, which is intended to ensure hand mildness.
Die WO 95/06108 beschreibt konzentrierte oder gelförmige Geschirrspülmittel, die durch Zusatz von Calciumsalzen und Xylolsulfonaten verdickt werden. Der Zusatz von zweiwertigen Ionen zu Tensiden führt häufig zur Dimerisierung von Tensiden und damit zur Ausbildung flüssigkristalliner Strukturen in Handgeschirrspülmitteln. WO 95/06108 describes concentrated or gel dishwashing detergents which are thickened by adding calcium salts and xylene sulfonates. The addition of divalent ions to surfactants often leads to dimerization of surfactants and thus to the formation of liquid-crystalline structures in hand dishwashing detergents.
Die GB 2280682 beschreibt Harnstoff enthaltende gelförmige Mittel, die in der hexagonal flüssigkristallinen Phase vorliegen. Die Viskosität solcher flüssigkristallinen Zusammensetzungen in der Produktion, Lagerung und Anwendung ist aber nur sehr schwer zu kontrollieren. GB 2280682 describes gel-like compositions containing urea which are present in the hexagonal liquid-crystalline phase. The viscosity of such liquid-crystalline compositions in production, storage and use is very difficult to control.
In der WO 94/09100 wird vorgeschlagen, durch Zusatz von Borsäure gelförmige Handgeschirrspülmittel auf Basis von Polyhydroxyfettsäureamiden zu stabilisieren. WO 94/09100 proposes to stabilize gel-like hand dishwashing detergents based on polyhydroxy fatty acid amides by adding boric acid.
Die in vielen Publikationen erwähnten gelförmigen Maschinengeschirrspülmittel aus Builder (wie Phosphat), Alkali (wie Soda), wenig (in der Regel bis 5 Gew.-%) Tensid sind u.a. wegen des hohen Alkalianteils für Handgeschirrspülmittel nicht geeignet.The gel-type dishwasher detergents from Builder mentioned in many publications (like phosphate), alkali (like soda), little (usually up to 5% by weight) because of the high proportion of alkali is not suitable for hand dishwashing detergents.
Arbeitet man hohe Mengen typischer Tensidmischungen aus anionischen Tendsiden, wie Fettalkoholethersulfat oder Fettalkoholsulfat, nichtionischen Tensiden, wie Alkylpolyglykosid und zwitterionischen Tensiden, wie z.B. Betaine, in Handgeschirrspülmittel ein, so erhält man - vermutlich wegen der Bildung flüssigkristalliner Phasen - häufig hochviskose, schlecht dosierbare und schlecht lösliche Produkte. Versucht man, mit zusätzlichen Lösemitteln die Erniedrigung der Viskosität zu gewährleisten, so verschlechtert sich zum einen in manchen Fällen die Lagerstabilität der Mittel, zum anderen ist ein niedrigviskoses Produkt weniger genau dosierbar. Auch können bei getrocknetem angebranntem Schmutz sehr gezielt Schmutzflecken behandelt werden. Hier hat ein verdicktes Produkt deutliche Vorteile in der Anwendung.If you work high amounts of typical surfactant mixtures from anionic tenders, such as Fatty alcohol ether sulfate or fatty alcohol sulfate, nonionic surfactants such as alkyl polyglycoside and zwitterionic surfactants, e.g. Betaines, in hand dishwashing liquid, so you get - probably because of the formation of liquid crystalline phases - often highly viscous, bad dosed and poorly soluble products. If you try using additional solvents Ensuring a lowering of viscosity, on the one hand, worsens in some If the storage stability of the agents, on the other hand, a low-viscosity product is less precisely dosed. Even with dried burnt dirt can be very targeted Stains are treated. Here a thickened product has clear advantages in the Application.
Keine im Stand der Technik vorgeschlagenen Zusammensetzungen eignet sich aber als genau dosierbares, ausgezeichnet reinigendes, handverträgliches, temperatur- und lagerstabiles, gießfähiges und ökologisch besonders verträgliches Handgeschirrspülmittel mit spezifischem Viskositätsprofil.However, none of the compositions proposed in the prior art is suitable as precisely metered, excellent cleaning, hand-compatible, temperature and storage stable, pourable and ecologically particularly compatible hand dishwashing liquid specific viscosity profile.
Genau dosierbare, lichtechte, ausgezeichnet reinigende, handverträgliche, temperatur- und lagerstabile, gießfähige und ökologisch besonders verträgliche Produkte mit guten Gießeigenschaften und hervorragenden Reinigungsleistungen erhält man, wenn man ein Gemisch aus Fettalkoholethersulfat, ggf. Fettalkoholsulfat, Alkylpolyglykosid und Betain zusammen mit einem Polymer bereitstellt.Precisely metered, lightfast, excellent cleaning, hand-compatible, temperature and storage-stable, pourable and ecologically particularly compatible products with good casting properties and excellent cleaning performance you get when you mix from fatty alcohol ether sulfate, possibly fatty alcohol sulfate, alkyl polyglycoside and betaine together with provides a polymer.
Gegenstand der vorliegenden Erfindung ist ein gießfähiges lagerstabiles Handgeschirrspülmittel, enthaltend eine Tensidmischung aus anionischen Tensiden und/oder nichtionischen Tensiden und/oder Betaintensiden, das zwischen 0,01 und 5 Gew.-% Polymere enthält und ein spezifisches Viskositätsprofil aufweist.The present invention relates to a pourable, storage-stable hand dishwashing detergent, containing a surfactant mixture of anionic surfactants and / or nonionic surfactants and / or betaine surfactants containing between 0.01 and 5% by weight of polymers contains and has a specific viscosity profile.
Im Rahmen der vorliegenden Erfindung stehen Fettsäuren bzw. Fettalkohole bzw. deren Derivate - soweit nicht anders angegeben - stellvertretend für verzweigte oder unverzweigte Carbonsäuren bzw. Alkohole bzw. deren Derivate mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Erstere sind insbesondere wegen ihrer pflanzlicher Basis als auf nachwachsenden Rohstoffen basierend aus ökologischen Gründen bevorzugt, ohne jedoch die erfindungsgemäße Lehre auf sie zu beschränken. Insbesondere sind auch die beispielsweise nach der ROELENschen Oxo-Synthese erhältlichen Oxo-Alkohle bzw. deren Derivate entsprechend einsetzbar.In the context of the present invention, unless otherwise stated, fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably having 6 to 22 carbon atoms. The former are preferred for ecological reasons, in particular because of their vegetable basis than based on renewable raw materials, but without restricting the teaching according to the invention to them. In particular, the rule for example after the Roelen oxo process available Oxo-alcohols or their derivatives are used accordingly.
Als Tensidmischungen eignen sich besonders jene aus anionischen und nichtionischen Tensiden. Aber auch die Verwendung von Betaintensiden im Gemisch, insbesondere in Kombination mit anionischen und nichtionischen Tensiden, kann für viele Anwendungen sehr sinnvoll sein. Insgesamt verwendet man die Tenside in Mengen von 0,2 bis 60 Gew.-%, bevorzugt von 1 bis 55 Gew.-%, besonders bevorzugt 3 bis 50 Gew.-% und äußerst bevorzugt 5 bis 45 Gew.-%.Particularly suitable surfactant mixtures are those made from anionic and nonionic surfactants. But also the use of betaine surfactants in a mixture, especially in combination with anionic and nonionic surfactants, can be very useful for many applications his. Overall, the surfactants are used in amounts of 0.2 to 60% by weight, preferably from 1 to 55% by weight, particularly preferably 3 to 50% by weight and extremely preferably 5 up to 45% by weight.
Polymere im Sinne der vorliegenden Erfindung sind Polycarboxylate bzw. Carboxyvinylpolymere, vorzugsweise Homo- und Copolymerisate der Acrylsäure, insbeondere Acrylsäure-Polymere und Acrylsäure-Methacrylsäure-Copolymere, Heteropolysaccaride (Xanthan, Guar, propoxyliertes Guar) und etwas weniger bevorzugt andere im Markt bekannte polymere Verdicker.Polymers in the sense of the present invention are polycarboxylates or carboxyvinyl polymers, preferably homo- and copolymers of acrylic acid, especially acrylic acid polymers and acrylic acid-methacrylic acid copolymers, heteropolysaccharides (xanthan, guar, propoxylated guar) and somewhat less preferred other polymeric thickeners known in the market.
Anionische Tenside gemäß der vorliegenden Erfindung können aliphatische Sulfate wie Fettalkoholsulfate, Fettalkoholethersulfate, Dialkylethersulfate, Monoglyceridsulfate und aliphatische Sulfonate wie Alkansulfonate, Olefinsulfonate, Ethersulfonate, n-Alkylethersulfonate, Estersulfonate und Lingninsulfonate sein. Ebenfalls im Rahmen der vorliegenden Erfindung verwendbar sind Fettsäurecyanamide, Sulfobernsteinsäureester, Fettsäureisethionate, Acylaminoalkansulfonate (Fettsäuretauride), Fettsäuresarcosinate, Ethercarbonsäuren und Alkyl(ether)phosphate.Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n- alkyl ether sulfonates, ester sulfonates and lingin sulfonates. Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.
Besonders bevorzugt im Rahmen der vorliegenden Erfindung sind die Fettalkoholethersulfate. Fettalkoholethersulfate sind Produkte von Sulfatierreaktionen an alkoxylierten Alkoholen. Dabei versteht der Fachmann allgemein unter alkoxylierten Alkoholen die Reaktionsprodukte von Alkylenoxid, bevorzugt Ethylenoxid, mit Alkoholen, im Sinne der vorliegenden Erfindung bevorzugt mit längerkettigen Alkoholen. In der Regel ensteht aus n Molen Ethylenoxid und einem Mol Alkohol, abhängig von den Reaktionsbedingungen, ein komplexes Gemisch von Additionsprodukten unterschiedlicher Ethoxylierungsgrade. Eine weitere Ausführungsform der Alkoxylierung besteht im Einsatz von Gemischen der Alkylenoxide, bevorzugt des Gemisches von Ethylenoxid und Propylenoxid. Ganz besonders bevorzugt im Sinne der vorliegenden Erfindung sind niederethoxylierte Fettalkohole mit 1 bis 4 Ethylenoxideinheiten (EO), insbesondere 1 bis 2 EO, beispielsweise 1,3 EO. The fatty alcohol ether sulfates are particularly preferred in the context of the present invention. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated Alcohols. The person skilled in the art generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, for the purposes of the present Invention preferred with longer-chain alcohols. Usually arises from n moles Ethylene oxide and a mole of alcohol, depending on the reaction conditions, a complex Mixture of addition products of different degrees of ethoxylation. Another The alkoxylation is carried out using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Very particularly preferred in For the purposes of the present invention, lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.
Bevorzugt werden die anionischen Tenside in Mengen zwischen 0,2 und 49,8 Gew.-% eingesetzt, bevorzugt 5 bis 45 Gew.-%, besonders bevorzugt 10 bis 40 Gew.-%.The anionic surfactants are preferably used in amounts between 0.2 and 49.8% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight.
In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel 0,5 bis 15 Gew.-% Fettalkoholsulfate.In a preferred embodiment of the invention, the compositions contain 0.5 to 15% by weight. Fatty alcohol sulfates.
Nichtionische Tenside im Rahmen der vorliegenden Erfindung können Alkoxylate sein wie Polyglycolether, Fettalkoholpolygycolether, Alkylphenolpolyglycolether, endgruppenverschlossene Polyglycolether, Mischether und Hydroxymischether und Fettsäurepolyglycolester. Ebenfalls verwendbar sind Ethylenoxid, Propylenoxid, Blockpolymere und Fettsäurealkanolamide und Fettsäurepolyglycolether. Eine wichtige Klasse nichtionischer Tenside, die erfindungsgemäß verwendet werden kann, sind die Polyol-Tenside und hier besonders die Glucotenside, wie Alkylpolyglykoside und Fettsäureglucamide. Besonders bevorzugt sind die Alkylpolyglucoside.Nonionic surfactants in the context of the present invention can be alkoxylates such as Polyglycol ether, fatty alcohol polyglycol ether, alkylphenol polyglycol ether, end group capped Polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides can also be used and fatty acid polyglycol ether. An important class of nonionic surfactants, the can be used according to the invention are the polyol surfactants and here in particular Glucose surfactants such as alkyl polyglycosides and fatty acid glucamides. Those are particularly preferred Alkylpolyglucosides.
Alkylpolyglykoside sind Tenside, die durch die Reaktion von, Zuckern und Alkoholen nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können, wobei es je nach Art der Herstellung zu einem Gemisch monoalkylierter, oligomerer oder polymerer Zucker kommt. Bevorzugte Alkylpolyglykoside können Alkylpolyglucoside sein, wobei besonders bevorzugt der Alkohol ein langkettiger Fettalkohol oder ein Gemisch langkettiger Fettalkohole mit verzweigten oder unverzweigten C8- bis C18-Alkylketten ist und der Oligomerisierungsgrad (DP) der Zucker zwischen 1 und 10, vorzugsweise 1 bis 6, insbesondere 1,1 bis 3, äußerst bevorzugt 1,1 bis 1,7, beträgt.Alkyl polyglycosides are surfactants which can be obtained by the reaction of, sugars and alcohols according to the relevant methods of preparative organic chemistry, which, depending on the type of production, results in a mixture of monoalkylated, oligomeric or polymeric sugars. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 to C 18 alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, is in particular 1.1 to 3, most preferably 1.1 to 1.7.
Vorzugsweise verwendet man die Alkylpolyglykoside in Mengen zwischen 0,1 bis 14,9 Gew.-%, insbesondere 1 bis 8 Gew.-% und äußerst bevorzugt 1 bis 5 Gew.-%.The alkyl polyglycosides are preferably used in amounts between 0.1 to 14.9% by weight, in particular 1 to 8% by weight and extremely preferably 1 to 5% by weight.
Zu den zwitterionischen Tensiden oder Amphotensiden, die erfindungsgemäß eingesetzt werden können, zählen die Alkylbetaine, die Alkylamidobetaine, die Imidazoliniumbetaine und die Aminopropionate genauso wie die Aminooxide, Sulfobetaine und Biotenside. Ein bevorzugter Inhaltsstoff ist hierbei Alkylamidobetain.To the zwitterionic surfactants or amphoteric surfactants used according to the invention include the alkyl betaines, the alkyl amido betaines, the imidazolinium betaines and the aminopropionates as well as the amino oxides, sulfobetaines and biosurfactants. On the preferred ingredient here is alkylamidobetaine.
Vorzugsweise werden diese zwitterionischen Tenside in Mengen zwischen 0,1 bis 14,9 Gew.-%, insbesondere zwischen 0,5 bis 10 Gew.-%, äußerst bevorzugt zwischen 1 bis 8 Gew.-%, eingesetzt.These zwitterionic surfactants are preferably used in amounts between 0.1 to 14.9% by weight, in particular between 0.5 to 10% by weight, extremely preferably between 1 to 8% by weight.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Handgeschirrspülmittels
enthält die Tensidmischung
Als Lösungsvermittler, etwa für Farbstoffe und Parfümöle können beispielsweise Alkanolamine, Polyole wie Ethylenglycol, 1,2-Propylenglycol, Glycerin und andere ein- und mehrwertige Alkohole sowie Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest dienen.As solubilizers, for example for dyes and perfume oils, for example alkanolamines, Polyols such as ethylene glycol, 1,2-propylene glycol, glycerin and other mono- and polyvalent Alcohols and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical are used.
Die erfindungsgemäßen Mittel haben eine Viskosität nach Brookfield (mit der für den jeweiligen Viskositätsbereich empfohlenen Spindel gemessen) bei 20 °C und einer Scherrate von 10 s-1 zwischen 1.000 und 10.000 mPa·s, vorzugsweise zwischen 1.300 und 9.000 mPa·s und besonders bevorzugt zwischen 1.500 und 7.000 mPa·s bzw. bei 20 °C und einer Scherrate von 30 s-1 zwischen 500 und 8.000 mPa·s, vorzugsweise zwischen 900 und 7.000 mPa·s und besonders bevorzugt zwischen 1.100 und 6.000 mPa·s.The agents according to the invention have a Brookfield viscosity (measured with the spindle recommended for the respective viscosity range) at 20 ° C. and a shear rate of 10 s -1 between 1,000 and 10,000 mPa · s, preferably between 1,300 and 9,000 mPa · s and particularly preferred between 1,500 and 7,000 mPas or at 20 ° C. and a shear rate of 30 s -1 between 500 and 8,000 mPas, preferably between 900 and 7,000 mPas and particularly preferably between 1,100 and 6,000 mPas.
Für günstige Lagereigenschaften bevorzugte Werte der Nullscherviskosität η0 liegen zwischen 1.000 bis 10.000 Pa·s, bevorzugt zwischen 1.000 und 5.000 Pa·s.Preferred zero shear viscosity values η 0 for favorable storage properties are between 1,000 and 10,000 Pa · s, preferably between 1,000 and 5,000 Pa · s.
Die Viskosität der erfindungsgemäßen Mittel kann durch Polymermengen zwischen 0,01 und 5 Gew.-%, vorzugsweise zwischen 0,02 und 4 Gew.-%, besonders bevorzugt zwischen 0,05 und 3 Gew.-%, insbesondere zwischen 0,1 und 1,5 Gew.-% und äußerst bevorzugt zwischen 0,2 und 0,9 Gew.-%, eingestellt werden. Die Mengen können von Polymer zu Polymer unterschiedlich sein. Auch die verwendete Tensidzusammensetzung spielt in der Mengenwahl eine Rolle. Als besonders geeignet haben sich hierbei Methacrylsäure-Acrylsäure-Copolymere wie auch Acrylsäure-Polymere erwiesen.The viscosity of the agents according to the invention can be between 0.01 and 5% by weight, preferably between 0.02 and 4% by weight, particularly preferably between 0.05 and 3% by weight, in particular between 0.1 and 1.5% by weight and very preferably between 0.2 and 0.9 wt .-%, are set. The amounts can vary from polymer to polymer his. The surfactant composition used also plays a role in the choice of quantity a role. Methacrylic acid-acrylic acid copolymers have been found to be particularly suitable as well as acrylic acid polymers.
Es wurde überaschend gefunden, daß besonders geeignete Polymere insondere ein Acrylsäurepolymer der Fa. Goodrich (Carbopol® EX 473), ein Acrylsäurecopolymer der Fa. 3V Sigma (Polygel® W30) und ein Methacrylsäure-Acrylsäure-Copolymer der Fa. Polymer Latex (Rohagit® SD 15) sind. Natürliche Polymere, wie Guar oder Xanthan, befriedigen nicht in allen Punkten die hohen Anforderungen an Löslichkeit und Lagerstabilität, die der Verbraucher heute an ein modemes Handgeschirrspülmittel stellt und sind deshalb weniger bevorzugt. It was surprisingly found that particularly suitable polymers, in particular an acrylic acid polymer from Goodrich ( Carbopol® EX 473), an acrylic acid copolymer from 3V Sigma ( Polygel® W30 ) and a methacrylic acid-acrylic acid copolymer from Polymer Latex ( Rohagit® SD 15 ) are. Natural polymers, such as guar or xanthan, do not meet all of the high requirements for solubility and storage stability that consumers now place on modern hand dishwashing detergents and are therefore less preferred.
Besonders ins Gewicht fällt hierbei - insbesondere aus der Sicht des Anwenders - die Klarheit der Produkte. Ein Absetzen von Phasen oder Inhaltsstoffen sowie ein trübes Aussehen ist in der Regel nicht erwünscht.Clarity is of particular importance here - especially from the point of view of the user of the products. Deposition of phases or ingredients as well as a cloudy appearance is usually not desired.
Diesbezüglich besondere Vorteile erhält man, wenn man den verdickten Mischungen eine oder mehrere Dicarbonsäuren und/oder deren Salze, allein oder in Mischung, insbesondere eine Zusammensetzung aus Na-Salzen der Adipin-, Bernstein- und Glutarsäure beimengt, wie sie z.B. unter dem Handelsnamen Sokalan® DSC Na erhältlich ist. Als besonders günstig hat sich hierbei der Einsatz von 0,1 bis 8 Gew.-%, bevorzugt 0,5 bis 7 Gew.-%, besonders bevorzugt 0,8 bis 6 Gew.-% und äußerst bevorzugt 1 bis 4 Gew.-%, gezeigt.In this regard, particular advantages are obtained if one or more dicarboxylic acids and / or their salts are added to the thickened mixtures, alone or in a mixture, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described, for example, under the trade name Sokalan ® DSC Na is available. The use of 0.1 to 8 wt.%, Preferably 0.5 to 7 wt.%, Particularly preferably 0.8 to 6 wt.% And extremely preferably 1 to 4 wt. %, shown.
Eine Veränderung des Dicarbonsäure(salz)-Gehaltes kann - insbesondere in Mengen oberhalb 2 Gew.-% - zu einer klaren Lösung der Inhaltsstoffe beitragen. Ebenfalls ist innerhalb gewisser Grenzen eine Beeinflussung der Viskosität der Mischung durch dieses Mittel möglich. Weiterhin beeinflußt diese Komponente die Löslichkeit der Mischung.A change in the dicarboxylic acid (salt) content can - especially in amounts above 2% by weight - contribute to a clear solution of the ingredients. Is also within The viscosity of the mixture can be influenced by this agent within certain limits. This component also influences the solubility of the mixture.
Anstelle oder zusätzlich zu den Dicarbonsäuren und/oder deren Salzen können auch andere Salze einzeln oder in Mischungen vorteilhaft eingesetzt werden, wie beispielsweise NatriumFormiat, Natrium-Acetat, Natrium-Tartrat, Natrium-Chlorid und Magnesium-Chlorid oder auch Salze der vorgenannten Anionen mit anderen Alkali- bzw. Erdalkalimetallen.Instead of or in addition to the dicarboxylic acids and / or their salts, others can also Salts are advantageously used individually or in mixtures, such as sodium formate, Sodium acetate, sodium tartrate, sodium chloride and magnesium chloride or else Salts of the aforementioned anions with other alkali or alkaline earth metals.
Die Dicarbonsäure- bzw. Salzkomponente dient dem Erreichen klarer, homogener Formulierungen und beeinflußt die Viskosität sowie das Kälte- und Auflöseverhalten. Ohne diese Hilfskomponente können die Mittel ein opakes bis leicht getrübtes Aussehen zeigen. Die Kombination von Polymer mit dieser Hilfskomponente ermöglicht die Herstellung von klaren gelförmigen Mitteln mit gutem Kälte- und Auflöseverhalten.The dicarboxylic acid or salt component serves to achieve clear, homogeneous formulations and influences the viscosity as well as the cold and dissolving behavior. Without these Auxiliary component, the agents can show an opaque to slightly cloudy appearance. The Combination of polymer with this auxiliary component enables the production of clear gel-like agents with good cold and dissolving behavior.
Eine weitere günstige Komponente der erfindungsgemäßen Mittel sind Lösungsmittel (z.B. Alkohole, insbesondere niedermolekulare Alkohole wie Ethanol). Sie tragen zur Einarbeitung von Parfum und Farbstoff bei, verhindern die Ausbildung flüssigkristalliner Phasen und haben Anteil an der Bildung klarer Produkte. Zuviel Lösungsmittel bewirkt jedoch ein zu starkes Absinken der Viskosität. Daher sind erfindungsgemäß zwischen 3 und 12 Gew.-% eines oder mehrerer Lösungsmittel enthalten, bevorzugt zwischen 4 und 10 Gew.-%, besonders bevorzugt zwischen 5 und 10 Gew.-%.Another cheap component of the agents according to the invention are solvents (e.g. Alcohols, especially low molecular weight alcohols such as ethanol). You contribute to the familiarization of perfume and dye, prevent the formation of liquid crystalline phases and have Share in the formation of clear products. However, too much solvent causes too much solvent Decrease in viscosity. Therefore, according to the invention, between 3 and 12% by weight of one or contain several solvents, preferably between 4 and 10 wt .-%, particularly preferred between 5 and 10% by weight.
Auch die Lösungsmittelmenge hat einen Einfluß auf die Homogenität und die Viskosität der erfindungsgemäßen Mittel. Bei niedrigen Mengen an Lösungsmittel, insbesondere unterhalb 3 Gew.-%, können je nach Zusammensetzung des Mittels Inhomogenitäten auftreten. Die Viskosität kann gesenkt werden, indem man die Lösemittelmenge erhöht.The amount of solvent also has an influence on the homogeneity and the viscosity of the agents according to the invention. At low levels of solvent, especially below 3% by weight, inhomogeneities can occur depending on the composition of the agent. The Viscosity can be reduced by increasing the amount of solvent.
Ein entscheidender Faktor ist die Löslichkeit. Erfindungsgemäße Mittel haben naturgemäß ein anderes Löseverhalten als herkömmliche Handgeschirrspülmittel. Auf eine genügend schnelle Auflösezeit muß daher geachtet werden.A key factor is solubility. Agents according to the invention naturally have a different dissolving behavior than conventional hand dishwashing detergents. Enough for one fast dissolution time must therefore be observed.
Erfindungsgemäße Mittel lösen sich in üblicher Verdünnung im Handgeschirrspülbecken zwischen 10 und 240 Sekunden, vorzugsweise zwischen 15 und 120 Sekunden, besonders bevorzugt zwischen 20 und 100 Sekunden, auf. Die Auflösezeit ist von der Verdickung und den gewählten Tensidkombinationen abhängig.Agents according to the invention dissolve in the usual dilution in the hand-rinse basin between 10 and 240 seconds, preferably between 15 and 120 seconds, particularly preferably between 20 and 100 seconds. The dissolution time is from the thickening and depending on the selected surfactant combinations.
Die Lichtechtheit der Produkte ist ein besonders wichtiger Faktor. Der Verbraucher bevorzugt farbige - d.h. farbstoffhaltige - Produkte in durchscheinenden Flaschen. Dadurch ergeben sich hohe Anforderungen an die Lichtechtheit der Mittel. Besonders geeignet ist hierbei die Verwendung von Acrylsäure-Polymeren wie auch von Acrylsäure-Methacrylsäure-Copolymeren.The lightfastness of the products is a particularly important factor. The consumer prefers colored - i.e. dye-containing products in translucent bottles. This results in high demands on the lightfastness of the agents. The is particularly suitable here Use of acrylic acid polymers as well as acrylic acid-methacrylic acid copolymers.
In diesem Zusammenhang kann erfindungsgemäß auch der Einsatz von UV-Stabilisatoren erfolgen. Besonders günstig vom Standpunkt der Produktionskosten ist aber ein Verzicht auf derartige Mittel, da sie häufig zur Reinigungsleistung nicht beitragen.In this context, the use of UV stabilizers can also be used according to the invention respectively. From the point of view of production costs, however, a waiver is particularly favorable such agents, since they often do not contribute to cleaning performance.
Viele der erfindungsgemäß untersuchten Mischungen zeigen ein zeitlich veränderliches Viskositätsprofil. Dies ist besonders wünschenswert, da beim Produktionsprozeß eine dünnflüssigere Masse bevorzugt wird, im Punkte Lagerstabilität und Verwendungskomfort aber auf höherviskose Produkte Wert gelegt wird.Many of the mixtures investigated according to the invention show a viscosity profile that changes over time. This is particularly desirable because the production process uses a thinner fluid Mass is preferred, but in terms of storage stability and ease of use more viscous products.
Eine weiterhin verbesserte Reinigungsleistung, besonders bei angebranntem Schmutz, erhält man bei der Verwendung von Abrasivstoffen, bevorzugt wasserlöslichen Abrasivstoffen, insbesondere Alkalimetallbicarbonat, Alkalimetallsulfat u.ä.A further improved cleaning performance, especially with burnt-on dirt when using abrasives, preferably water-soluble abrasives, especially alkali metal bicarbonate, alkali metal sulfate and the like.
Daneben können noch weitere in Handgeschirrspülmitteln übliche Inhaltsoffe, wie z.B. Entschäumer, Strukturierungsmittel, Parfumstoffe, Farbstoffe, Korrosionsinhibitoren sowie Konservierungsmittel, in Mengen von bis zu 5 Gew.-% enthalten sein.In addition, other ingredients common in hand dishwashing detergents, such as defoamers, Structuring agents, perfumes, dyes, corrosion inhibitors and preservatives, be contained in amounts of up to 5 wt .-%.
Der pH-Wert der erfindungsgemäßen Mittel kann mittels üblicher pH-Regulatoren, beispielsweise Citronensäure oder NaOH, eingestellt werden, wobei - im wesentlichen wegen der geforderten Handverträglichkeit - ein Bereich von 5,5 bis 8, vorzugsweise 6 bis 7,5, insbesondere 6,5 bis 7,1, bevorzugt ist.The pH of the agents according to the invention can be adjusted using conventional pH regulators, for example Citric acid or NaOH, are set, whereby - essentially because of required hand tolerance - a range from 5.5 to 8, preferably 6 to 7.5, in particular 6.5 to 7.1 is preferred.
Die erfindungsgemäßen Handgeschirrspülmittel lassen sich durch durch Zusammenrühren der einzelnen Bestandteile in beliebiger Reihenfolge und Stehenlassen des Gemisches bis zur Blasenfreiheit herstellen. Die Ansatzreihenfolge ist für die Herstellung des Mittels nicht entscheidend.The hand dishwashing detergents according to the invention can be stirred together of the individual components in any order and leave the mixture to produce for freedom from bubbles. The order of preparation is not for the preparation of the agent crucial.
Vorzugsweise werden hierbei Wasser, Tenside und gegebenenfalls weitere der zuvor genannten Inhaltsstoffe zusammengerührt. Insofern Parfüm und/oder Farbstoff eingesetzt werden, erfolgt anschließend deren Zugabe zur erhaltenen Lösung. Schließlich wird das Polymer zugegeben, gegebenenfalls in Form einer wäßrigen Lösung, um dessen homogenes Auflösen zu erleichtern. Zuletzt wird der pH-Wert wie zuvor beschrieben eingestellt. Water, surfactants and optionally further ones of the aforementioned are preferably used here Ingredients stirred together. Insofar as perfume and / or dye are used, it is then added to the solution obtained. Eventually the polymer added, optionally in the form of an aqueous solution, to make it homogeneous Facilitate dissolving. Finally, the pH is adjusted as previously described.
Die erfindungsgemäßen Mittel E1 bis E30 wurden wie zuvor beschrieben hergestellt und ihr pH-Wert, ihre Viskosität, ihr Kältetrübungs- bzw. Klarpunkt sowie ihre Auflösezeit bestimmt.Agents E1 to E30 according to the invention were prepared as described above and their pH, viscosity, cold cloud or clear point and dissolution time were determined.
Die Zusammensetzungen der erfindungsgemäßen Mittel E1 bis E30 in Gew.-% sowie die bestimmten Eigenschaften sind in den Tabellen 1 bis 4 wiedergegeben. Zusätzlich enthielten die erfindungsgemäßen Mittel E1 bis E30 Spuren von Farbstoff. Der pH-Wert der erfindungsgemäßen Mittel E1 bis E30 wurde mit Citronensäure auf Werte zwischen 6,5 und 7,1 eingestellt.The compositions of the agents E1 to E30 according to the invention in% by weight and the specific properties are shown in Tables 1 to 4. In addition, agents E1 to E30 according to the invention contained traces of dye. The pH of the agents E1 to E30 according to the invention was adjusted to between 6.5 and 7.1 using citric acid.
Die Viskosität wurde bei 20 °C nach Brookfield bestimmt (Viskosimeter Brookfield LV DV II+; Spindel 25; Scherrate 30 min-1).The viscosity was determined at 20 ° C according to Brookfield ( Brookfield LV DV II + viscometer; spindle 25; shear rate 30 min -1 ).
Der Kältetrübungspunkt wurde durch Abkühlung einer Probe im Kryostaten mit einer Abkühlrate von 0,2 °C·min-1 bestimmt, wobei als Kältetrübungspunkt die Temperatur angegeben ist, bei der zuerst eine leichte Trübung erkannt wurde. Nachdem die Probe völlig ausgetrübt war, wurde mit einer Aufheizrate von 0,2 °C·min-1 erwärmt. Als Klarpunkt wird die Temperatur angegeben, bei der die Probe erstmals völlig klar vorliegt.The cold cloud point was determined by cooling a sample in the cryostat with a cooling rate of 0.2 ° C.min -1 , the cold cloud point being the temperature at which a slight cloudiness was first detected. After the sample was completely cloudy, the mixture was heated at a heating rate of 0.2 ° C.min -1 . The temperature at which the sample is completely clear for the first time is given as the clear point.
Zur Bestimmung der Auflösezeit wurden 1 ml des Mittels unter Rühren mit 325 Umdrehungen·min-1 in 900 ml 40 °C warmen Leitungswassers gegeben und die Zeit bis zur völligen Auflösung des Spülmittels gemessen.To determine the dissolution time, 1 ml of the agent was added with stirring at 325 revolutions · min -1 in 900 ml of tap water at 40 ° C. and the time until the detergent was completely dissolved.
Die Spülleistung der erfindungsgemäßen Rezepturen wurde größtenteils ebenfalls ermittelt.
Die Bestimmung wurde in einer halbautomatischen Tellertest-Apparatur unter Einsatz von
zwei verschiedenen reinen Fettanschmutzungen (angegeben ist der Mittelwert) und einer fetthaltigen
Mischanschmutzung bestimmt. Dabei wurden bei einer konstanten Temperatur von
40 bzw. 45 °C in 5 I Wasser einer Härte von 16 ° unter konstanten Bedingungen im Vergleich
zu einem hochwertigen klassischen Handgeschirrspülmittel als Laborstandard mit dem Testschmutz
angeschmutzte Teller gespült, bis der - vor Versuchbeginn gebildete - Schaum zerstört
war und die Teller nicht mehr sauber wurden. Die Konzentration des Mittels betrug hierbei
2 ml pro 5 I Wasser bzw. im Falle der Mittel E25 bis E28 4 ml pro 5 I Wasser. Die Anzahl
der gespülten Teller ist in Relation zum Laborstandard mit einer Spülleistung von 100 % gesetzt.
Die verdickende Wirkung der Polymere und der weitere positive Einfluß der Verdicker auf die übrigen Eigenschaften der erfindungsgemäßen Handgeschirrspülmittel sei beispielhaft außerdem an folgenden Rezepturen verdeutlicht (Herstellung und Methoden, soweit nicht anders angegeben, wie Beispiel 1).The thickening effect of the polymers and the further positive influence of the thickeners on the Other properties of the hand dishwashing detergent according to the invention are also exemplary illustrated by the following recipes (production and methods, unless otherwise specified as example 1).
Rezeptur:
Als Polymere wurden Acrylsäure-Polymer, Acrylsäure-Methyacrylsäure-Copolymer und Carboxyvinylpolymer verwendet.The polymers used were acrylic acid polymer, acrylic acid-methacrylic acid copolymer and carboxyvinyl polymer used.
Viskosität (20 °C) 5700 m·Pas; Kältetrübungspunkt +2 °C/+6 °C; Auflösezeit 81 SekundenViscosity (20 ° C) 5700 mPas; Cold cloud point +2 ° C / + 6 ° C; Dissolution time 81 seconds
Eine Veränderung des Sokalan DSC®-Gehaltes bewirkte in Mengen oberhalb 2 Gew.-% eine klare Lösung der Inhaltsstoffe. Ebenfalls kann innerhalb gewisser Grenzen die Viskosität der Mischung durch dieses Mittel beeinflußt werden. Ein weiterer Einfluß des Sokalan DSC® wurde auf die Löslichkeit der Mischung festgestellt.A change in the Sokalan DSC ® content in amounts above 2% by weight resulted in a clear solution of the ingredients. The viscosity of the mixture can also be influenced by this agent within certain limits. Another influence of the Sokalan DSC ® was found on the solubility of the mixture.
Auch die Ethanolmenge hat einen Einfluß auf die Homogenität und die Viskosität. Bei Variation der Menge des Lösungsmittels in obiger Rezeptur zeigt sich eine Inhomogenität unterhalb 4 Gew.-%. Die kann aber von Rezeptur zu Rezeptur verschieden sein. Die Viskosität kann beeinflußt (gesenkt) werden, indem man die Lösungsmittelmenge erhöht.The amount of ethanol also has an influence on the homogeneity and the viscosity. With variation the amount of solvent in the above recipe shows an inhomogeneity below 4% by weight. However, this can differ from recipe to recipe. The viscosity can be influenced (reduced) by increasing the amount of solvent.
Im einem üblichen Geruchstest durch Experten schnitten die verschiedenen Rezepturen differenzierbar, aber insgesamt gut ab. In a usual smell test by experts, the different recipes were cut differentially, but overall good.
In einem Test auf Lichtbeständigkeit (Xenotest 150), in dem die Stabilität einer UV-sensiblen Komponente (Farbstoff) getestet wurde, schnitten die unterschiedlichen Rezepturen differenzierbar gut ab.In a test for light resistance (Xenotest 150), in which the stability of a UV sensitive Component (dye) was tested, the different recipes cut differentiable well off.
In einem Test einer erfindungsgemäßen Mischung auf Spüleigenschaften wurde eine Zusammensetzung analog Rezeptur aber mit 0.7 Gew.-% Carbopol® EX 473 (Acrylsäure-Polymer) durchgeführt.In a test of a mixture according to the invention for rinsing properties, a composition was carried out analogously to the recipe but with 0.7% by weight Carbopol® EX 473 (acrylic acid polymer).
Die Viskosität betrug 3500 bis 4000 m·Pas, die Auflösezeit zwischen 45 bis 70 Sekunden.The viscosity was 3500 to 4000 m · Pas, the dissolution time between 45 to 70 seconds.
Die Reinigungsleistung an Schmutz war sehr gut, die Reinigungsleistung an Fett war überdurchschnittlich gut, das Schaumvermögen mit und ohne Ölzusatz war gut, ebenso das Emulgiervermögen.The cleaning performance of dirt was very good, the cleaning performance of grease was above average good, the foaming power with and without oil was good, as was the emulsifying power.
Das verdickte Produkt wirkt also stärker als vergleichbare Handgeschirrspülmittel.The thickened product therefore has a stronger effect than comparable hand dishwashing detergents.
Claims (13)
- Pourable storage-stable hand dishwashing composition comprising a surfactant mixture of anionic surfactants and/or nonionic surfactants and/or betaine surfactants, characterized in that it comprises between 0.01 and 5% by weight of polymers and, at 20°C and a shear rate of 10 s-1, has a viscosity between 1000 and 10 000 mPa·s and, at 20°C and a shear rate of 30 s-1, has a viscosity between 500 and 8000 mPa·s.
- Composition according to Claim 1, characterized in that, at 20°C and a shear rate of 10 s-1, it has a viscosity between 1300 and 9000 mPa·s, particularly preferably between 1500 and 7000 mPa·s and, at 20°C and a shear rate of 30 s-1, has a viscosity between 900 and 7000 mPa·s, particularly preferably between 1100 and 6000 mPa·s.
- Composition according to Claim 1 or 2, characterized in that the surfactant mixture comprises anionic and nonionic surfactants.
- Composition according to one of Claims 1 to 3, characterized in that the surfactant mixture comprises betaine surfactants.
- Composition according to one of Claims 1 to 4, characterized in that it comprises alkyl polyglycosides, preferably alkylpolyglucosides, as a nonionic surfactant.
- Composition according to one of Claims 1 to 5, characterized in that it comprises between 0.05 and 3% by weight, preferably 0.1 to 1.5% by weight and particularly preferably between 0.2 and 0.9% by weight, of polymers.
- Composition according to one of Claims 1 to 6, characterized in that the polymers are chosen from the group of acrylic acid polymers, of acrylic acid-methacrylic acid copolymers and of carboxyvinyl polymers.
- Composition according to one of Claims 1 to 7, characterized in that it comprises 0.2 to 60% by weight, preferably 1 to 55% by weight, particularly preferably 3 to 50% by weight, most preferably 5 to 45% by weight, of surfactant mixture.
- Composition according to one of Claims 1 to 8, characterized in that it comprises(a) 0.2 to 49.8% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight, of anionic surfactants, in particular fatty alcohol ether sulphates,(b) 0.1 to 14.9% by weight, preferably 1 to 8% by weight, of nonionic surfactants, in particular alkyl polyglucosides, and(c) 0.1 to 14.9% by weight, preferably 0.5 to 10% by weight, of betaine surfactants, in particular alkylamidobetaines.
- Composition according to one of Claims 1 to 9, characterized in that between 0.5 and 15% by weight of fatty alcohol sulphates are additionally present.
- Composition according to one of Claims 1 to 10, characterized in that, as a further ingredient, one or more dicarboxylic acids and/or salts thereof or sodium formate, sodium acetate, sodium tartrate, sodium chloride or magnesium chloride or salts of the abovementioned anions with other alkali metal or alkaline earth metals, on their own or in a mixture, preferably in amounts of from 0.1 to 8% by weight, particularly preferably between 0.5 and 7% by weight, are present.
- Composition according to one of Claims 1 to 11, characterized in that a solvent, for example one or more lower molecular weight alcohols, e.g. ethanol, is present in amounts preferably between 3 and 12% by weight, in particular between 4 and 10% by weight.
- Composition according to one of Claims 1 to 12, characterized in that it comprises further ingredients customary in hand dishwashing compositions, such as UV stabilizers, antifoams, solvents, structuring agents, perfume substances, dyes, corrosion inhibitors, preservatives and the like.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1997152454 DE19752454B4 (en) | 1997-11-26 | 1997-11-26 | Dishwashing detergent with specific viscosity profile |
DE19752454 | 1997-11-26 | ||
DE19817833A DE19817833A1 (en) | 1997-11-26 | 1998-04-22 | Dishwashing liquid with a specific viscosity profile |
DE19817833 | 1998-04-22 | ||
PCT/EP1998/007346 WO1999027062A1 (en) | 1997-11-26 | 1998-11-17 | Dish washing detergent with a specific viscosity profile |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1036157A1 EP1036157A1 (en) | 2000-09-20 |
EP1036157B1 true EP1036157B1 (en) | 2004-09-01 |
Family
ID=26041932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98963466A Expired - Lifetime EP1036157B1 (en) | 1997-11-26 | 1998-11-17 | Dish washing detergent with a specific viscosity profile |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1036157B1 (en) |
JP (1) | JP4365024B2 (en) |
AT (1) | ATE275188T1 (en) |
DE (2) | DE19817833A1 (en) |
WO (1) | WO1999027062A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19950925A1 (en) * | 1999-10-21 | 2001-04-26 | Henkel Kgaa | Portion of detergent containing little water, used for cleaning hard surface, preferably for washing dishes by hand, comprises detergent formulation in water-soluble polymer envelope |
FR2826017B1 (en) * | 2001-06-15 | 2004-06-11 | Cognis France Sa | SURFACTANT MIXTURES |
US20080032909A1 (en) * | 2006-05-05 | 2008-02-07 | De Buzzaccarini Francesco | Compact fluid laundry detergent composition |
JP5422110B2 (en) * | 2007-11-02 | 2014-02-19 | 花王株式会社 | Surfactant composition |
JP2016145306A (en) * | 2015-02-09 | 2016-08-12 | 花王株式会社 | Liquid tableware detergent composition |
PL3686118T3 (en) | 2019-01-24 | 2022-01-03 | The Procter & Gamble Company | Non-drip upside down bottles |
EP3910049A1 (en) * | 2020-05-11 | 2021-11-17 | Henkel AG & Co. KGaA | Method for producing a surfactant-containing liquid |
PL4098727T3 (en) * | 2021-06-02 | 2024-04-29 | Henkel Ag & Co. Kgaa | Viscosity-modified washing up liquid |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1206391A (en) * | 1982-04-15 | 1986-06-24 | American Home Products Corporation | Pourable gel dishwasher compositions |
JPH04120012A (en) * | 1990-09-10 | 1992-04-21 | Sakamoto Yakuhin Kogyo Kk | Transparent gelatinous cleaning agent |
DE4122470A1 (en) * | 1991-07-06 | 1993-01-07 | Bitterfeld Wolfen Chemie | Aq. cleaning paste for hands, hard surfaces and glass - contains surfactants, copolymer, phosphate, white spirit and reducing or oxidising agent |
DE4209922A1 (en) * | 1992-03-27 | 1993-09-30 | Henkel Kgaa | Liquid detergent |
DE19521351A1 (en) * | 1995-06-12 | 1996-12-19 | Henkel Kgaa | Dilute aqueous surfactant solutions with increased viscosity |
DE19523119A1 (en) * | 1995-06-26 | 1997-01-02 | Henkel Kgaa | Aq. compsn. with raised viscosity for cleaning of hard surfaces |
US5700331A (en) * | 1996-06-14 | 1997-12-23 | Colgate-Palmolive Co. | Thickened cleaning composition |
JP2002507239A (en) * | 1997-06-30 | 2002-03-05 | ザ、プロクター、エンド、ギャンブル、カンパニー | Liquid or gel light dishwashing detergent composition with a controlled pH having desirable food stain removal, rheological and foaming properties |
-
1998
- 1998-04-22 DE DE19817833A patent/DE19817833A1/en not_active Withdrawn
- 1998-11-17 JP JP2000522205A patent/JP4365024B2/en not_active Expired - Fee Related
- 1998-11-17 WO PCT/EP1998/007346 patent/WO1999027062A1/en active IP Right Grant
- 1998-11-17 EP EP98963466A patent/EP1036157B1/en not_active Expired - Lifetime
- 1998-11-17 AT AT98963466T patent/ATE275188T1/en not_active IP Right Cessation
- 1998-11-17 DE DE59811905T patent/DE59811905D1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP4365024B2 (en) | 2009-11-18 |
JP2001524589A (en) | 2001-12-04 |
WO1999027062A1 (en) | 1999-06-03 |
DE19817833A1 (en) | 1999-10-28 |
DE59811905D1 (en) | 2004-10-07 |
ATE275188T1 (en) | 2004-09-15 |
EP1036157A1 (en) | 2000-09-20 |
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