EP2867352B1 - Highly concentrated liquid washing or cleaning composition - Google Patents
Highly concentrated liquid washing or cleaning composition Download PDFInfo
- Publication number
- EP2867352B1 EP2867352B1 EP13730592.6A EP13730592A EP2867352B1 EP 2867352 B1 EP2867352 B1 EP 2867352B1 EP 13730592 A EP13730592 A EP 13730592A EP 2867352 B1 EP2867352 B1 EP 2867352B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cleaning agent
- washing
- water
- liquid washing
- anionic surfactant
- 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.)
- Revoked
Links
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
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/043—Liquid or thixotropic (gel) compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
-
- 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
-
- 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
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the invention relates to a packed in a water-soluble wrapper, highly concentrated liquid detergent or cleaning agent with anionic and nonionic surfactants.
- an ultraconcentrated liquid detergent or cleaning composition which comprises (a) from 25 to 60% by weight of nonionic surfactant, (b) from 5 to 30% by weight of anionic surfactant, (c) from 0.5 to 18% by weight of cold water Dispersing aid and (d) contains up to 60% by weight of water.
- liquid detergent packaged in a water-soluble wrapper comprising 5 to 80% by weight of surfactant, 20 to 50% by weight of fatty acid (ie fatty acid and its soap), 1 to 15% by weight of non-aqueous solvent and less than 10% Wt .-% water, wherein the molar ratio of the fatty acid to the fatty acid soap in the range of 5: 1 to 1: 5.
- Detergents or cleaning agents are now available to the consumer in a variety of forms.
- this offer includes, for example, liquids, gels or sachets (tablets or filled bags).
- portion packs containing liquid detergents or cleaning agents are becoming increasingly popular, fulfilling, on the one hand, the consumer's desire for simplified dosing and, on the other hand, more and more consumers prefering liquid detergents or cleaners. Again, it is desirable to use highly concentrated detergents or cleaning agents.
- washing or cleaning agent is packaged in a water-soluble wrapper and the content of water is less than 10 wt .-%, based on the total liquid detergent or cleaning agent.
- phase-stable detergent or cleaning agent can be obtained with good cleaning performance.
- the washing or cleaning agent has a particularly good cleaning performance and good foaming behavior when the sulfonate anionic surfactant is a C 9-13 -alkylbenzenesulfonate.
- the ratio of anionic surfactant of the sulfonate type to nonionic surfactant is from 1.25: 1 to 1: 1.25. It is also preferred that the ratio of sulfonate anionic surfactant to sulfate type anionic surfactant is greater than 2: 1 and / or that the ratio of nonionic surfactant to sulfate type anionic surfactant be greater than 2: 1.
- the washing or cleaning agent is packaged in a water-soluble wrapper.
- liquid detergent or cleaning agent are packaged in the water-soluble wrapper.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
- the liquid washing or cleaning agent contains various surfactants.
- the liquid detergent or cleaning agent contains nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkyl polyglycosides, ethoxylated methyl esters of natural fatty acids and mixtures thereof.
- the alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear.
- EO ethylene oxide
- alcohol ethoxylates having 12 to 18 C atoms for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 12-18 alcohols with 5 EO or 7 EO and mixtures of these.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols containing more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- Alkoxylated fatty alcohols which contain EO and PO groups together in the molecule can also be used according to the invention.
- Oxo alcohols are primary, partially branched higher alcohols, which are obtained in the oxo synthesis.
- oxo-aldehydes or their primary aldokondensations may be converted by catalytic hydrogenation in the corresponding oxo alcohols.
- the alkoxylated, preferably ethoxylated, oxo alcohols have a degree of alkoxylation between 5 and 12.
- the indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
- Preferred oxo-alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- a C 13-15 oxo alcohol with 7 EO, a C 13-15 oxo alcohol with 8 EO or a mixture of these two oxo alcohols in the liquid washing or cleaning agent is preferably used.
- alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably x is 1.2 to 1.4.
- nonionic surfactants are ethoxylated methyl esters of natural fatty acids, such as coconut, palm kernel or olive oil fatty acids, preferably having 8 to 18 EO units.
- liquid detergent or cleaning agent contains only alkoxylated fatty alcohols as nonionic surfactants.
- the liquid washing or cleaning agent contains exclusively alkoxylated oxo alcohols as nonionic surfactants.
- the total amount of nonionic surfactant in the liquid washing or cleaning agent is up to 25% by weight and preferably 16 to 20% by weight, based on the total liquid detergent or cleaning agent.
- the liquid washing or cleaning agent further contains anionic surfactant of the sulfonate type. This is selected from the group consisting of C 9-13 alkyl benzene sulfonates, olefin sulfonates, sulfonated estolides, C 12-18 alkanesulfonates, and mixtures thereof.
- surfactants of the sulfonate type preferably C 9-13 alkylbenzenesulfonates are used.
- Suitable sulfonated estolides which can be used as the sulfonate-type surfactant include compounds of the following formula wherein n is an integer from 1 to 30, one of X or Y is SO 3 -Z and the other is hydrogen, wherein X and Y are present in each repeating unit, A 1 and A 2 are linear or branched, saturated or unsaturated, substituted or unsubstituted C 8 -C 22 alkylene units, a is independently 0, 1, or 2 in each repeat unit, R is a linear or branched, saturated or unsaturated, substituted or unsubstituted C 1 -C 24 alkyl moiety, W is a monovalent or divalent Metal cation, an ammonium cation, a substituted ammonium cation, hydrogen, a
- Z is hydrogen, a monovalent or divalent metal cation, an ammonium cation or a substituted ammonium cation.
- the amount of anionic surfactant of the sulfonate type is 18 to 35 wt .-%, preferably 20 to 30 wt .-%, each based on the total washing or cleaning agent.
- the washing or cleaning agent contains 2 to 15 wt .-%, .-%, preferably 5 to 12 wt .-%, each based on the total washing or cleaning agent, anionic surfactant of the sulfate type selected from the group consisting of Fatty alcohol sulfates, fatty alcohol ether sulfates and mixtures thereof
- fatty alcohol sulfates the salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol are preferred.
- the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- fatty alcohol ether sulfates are, for example, the sulfuric acid monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C 7-21 alcohols such as 2-methyl-branched C 9-11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12th -18 fatty alcohols with 1 to 4 EO used.
- EO ethylene oxide
- the washing or cleaning agent contains a fatty acid and / or a fatty acid soap.
- Suitable are saturated and unsaturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, and soaps or soap mixtures derived from these fatty acids.
- the amount of fatty acid and / or a fatty acid soap in the entire washing or cleaning agent is 0.5 to 20 wt .-% and preferably 2 to 15 wt .-%.
- the anionic surfactants and the fatty acid soaps may be in the form of their sodium, potassium or ammonium salts.
- the anionic surfactants are in the form of their sodium salts or ammonium salts.
- the ammonium salts may be the salts of organic bases.
- the amine used for the neutralization is preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.
- the total amount of nonionic surfactant, sulfonate type anionic surfactant, sulfate type anionic surfactant and fatty acid (soap) in the liquid detergent or cleaner is at least 35 wt .-%, preferably 40 to 75 wt -%, and most preferably 50 to 60 Ges .-%, each based on the total liquid detergent or cleaning agent.
- the liquid washing or cleaning agent may further contain an organic solvent, which preferably comprises 1,2-propanediol, glycerol and / or ethanol.
- the liquid detergent or detergency detergent may contain other ingredients which enhance the performance and / or aesthetics of the laundry or cleaning product Cleaning agent further improved.
- the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils , Anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skincare active ingredients, swelling and anti-slip agents, softening components and UV absorbers.
- the liquid washing or cleaning agent is filled in a water-soluble wrapper and is thus part of a water-soluble packaging.
- the content of water of the liquid washing or cleaning agent is less than 10 wt .-%, based on the total liquid detergent or cleaning agent.
- the water-soluble envelope forms a closed structure, which has in its interior one or more chambers for receiving one or more washing or cleaning agents.
- the water-soluble packaging may be dimensionally stable or deformable.
- the water-soluble packaging may be formed as a dimensionally stable container, for example in the form of a capsule, box, box or container.
- the water-soluble packaging in principle it is also possible and preferred to mold the water-soluble packaging as a non-dimensionally stable container, for example as a bag.
- the shape of such a water-soluble packaging can be largely adapted to the conditions of use.
- various forms such as hoses, pillows, cylinders, bottles or discs in question.
- a water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating.
- the water-soluble coating is preferably formed by a water-soluble film material.
- Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.
- VFFS vertical fill-seal
- the thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.
- the water-soluble coating is preferably formed from a water-soluble film material selected from the group comprising polymers and polymer blends.
- the wrapper may be formed of one or two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if present, may be the same or different.
- the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
- Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
- polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
- polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers.
- its degree of hydrolysis is preferably 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acids or mixtures of the above polymers may additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating be.
- a preferred additional polymer is polylactic acids.
- Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
- Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
- polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
- the film material contains further additives.
- the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
- Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
- Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, M8310, C8400 or M8900.
- Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
- the water-soluble packaging has a chamber for receiving the highly concentrated liquid washing or cleaning agent.
- the water-soluble packaging has two chambers.
- the first chamber contains the above-described highly concentrated liquid detergent or cleaning agent and the second chamber may contain a solid or a liquid detergent or cleaning agent.
- the water-soluble packaging in yet another preferred embodiment has three chambers, these chambers can each contain a liquid washing or cleaning agent. But it is also possible that a chamber containing a solid detergent or detergent and two chambers containing a liquid detergent or cleaning agent. It is also possible that a solid detergent or cleaning agent is contained in two chambers and a liquid detergent or cleaning agent in a chamber.
- At least one chamber contains the above-described liquid detergent or cleaning agent according to the invention.
- the liquid detergents or cleaning agents contained in the other chambers of a water-soluble packaging may have the same composition.
- the liquid detergents or cleaners in a water-soluble packaging with at least two chambers preferably have compositions which differ at least in the content of an ingredient.
- the amount of detergent or cleaning agent, which is in total in the water-soluble packaging corresponds to the full dose needed for a wash for 4.5 kg of laundry.
- 20 to 25 g of liquid washing or cleaning agent are packaged in a water-soluble wrapper.
- Liquid detergents or cleaners were prepared by conventional and known methods and procedures. Table 1 below shows the compositions of a washing or cleaning agent E1 according to the invention and a washing or cleaning agent V1 not according to the invention. Table 1: Liquid washing or cleaning agents E1 and V1 [all amounts are given in% by weight of active ingredient, based on the composition] ingredients E1 V1 C 10 -C 13 -alkylbenzenesulfonic acid 20.8 7.2 C 13 -C 15 oxo-alcohol with 8 EO 18 - C 12-18 fatty alcohol with 7 EO - 7 Na lauryl ether sulfate (2 EO) 7.2 12.8 C 12-18 fatty acid 12 5.6 Soil release polymer * 2.8 1.8 glycerin 5.2 1,2-propanediol 5.7 5.7 ethanol 2 2 phosphonate 2 2 Monoethanolamine 10 - NaOH (50%) - 6.9 citric acid 2.2 2.3 boric acid 1 1 Dyes, enzymes (cellulas
- the efficiency of washing or cleaning agents E1 and V1 was determined as the sum of the remission units at different spots (53 fat-containing spots and 18 enzyme-sensitive spots).
- a household washing machine (Miele W 1734) was loaded with 3.5 kg accompanying laundry as well as correspondingly contaminated cloth rags.
- either 39 g of the washing or cleaning agent V1 or 25 g of the washing or cleaning agent E1 were added and it was washed at 40 ° C. After hanging drying and mangling of the cloth rags their remission was determined spectrophotometrically (Minolta CR200-1). The stain removal was evaluated by the Y value.
- a third washing test the graying-inhibiting performance of the washing or cleaning agents E1 and V1 was determined.
- a household washing machine (Miele W 1734) was loaded with 2.5 kg of white accompanying laundry, various test fabrics, five SBL 2004 wipes with standardized dirt load (32 g of dirt ballast).
- either 39 g of the washing or cleaning agent V1, 25 g of the washing or cleaning agent E1 or 20 g of the washing or cleaning agent E1 were added and it was washed at 40 ° C. After hanging Drying and mangling of the cloth rags their whiteness was determined spectrophotometrically (Minolta CR200-1). The stain removal was evaluated by the Y value.
- Table 4 shows these measurements versus the baseline test fabric.
- the cotton fabrics were eight different commercially available cotton fabrics.
- the fabrics made of polyester were five different commercially available polyester fabrics
- the old-day fabrics included four commercial everyday textiles such as kitchen towels, toweling, barley grain towel and white T-shirts.
- Table 4 Whitenesses (average of the respective test fabrics) Washing or cleaning agents cotton polyester everyday life total V1 (39 g) -10.50 -4.05 -13.70 -9.41 E1 (25g) -8.00 -3.65 -13.60 -8.41 E1 (20 g) -8.20 -3.50 -12.90 -8.20
- a fourth washing test the stain removal of detergents E1 and V1 at various spots was determined.
- a household washing machine (Miele W 1734) was loaded with 3.5 kg accompanying laundry as well as correspondingly contaminated cloth rags.
- either 39 g of the washing or cleaning agent V1, 25 g of the washing or cleaning agent E1 or 20 g of the washing or cleaning agent E1 were added and it was washed at 40 ° C. After hanging drying and mangling of the cloth rags their remission was determined spectrophotometrically (Minolta CR200-1). The stain removal was evaluated by the Y value.
- a film of the type M 8630 (ex Monosol) with a thickness of 76 ⁇ m was pulled into a depression by means of a vacuum to form a bulge. Subsequently, the bulge was filled with 25 g of the liquid detergent or cleaning agent E1. After covering the agent filled bulges with a second layer of M 8630 film, the first and second layers were sealed together. The sealing temperature was 150 ° C and the sealing time 1.1 seconds.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Die Erfindung betrifft ein in einer wasserlöslichen Umhüllung verpacktes, hochkonzentriertes flüssiges Wasch- oder Reinigungsmittel mit anionischen und nichtionischen Tensiden.The invention relates to a packed in a water-soluble wrapper, highly concentrated liquid detergent or cleaning agent with anionic and nonionic surfactants.
Im Zuge des steigenden Umweltbewusstseins bei Industrie und Verbrauchern ist es wünschenswert, möglichst hochkonzentrierte Wasch- oder Reinigungsmittel zu formulieren, die in kleineren Verpackungen angeboten werden können und so nach ihrer Verwendung weniger Abfall hinterlassen.In the context of increasing environmental awareness among industry and consumers, it is desirable to formulate highly concentrated detergents or cleaning agents that can be offered in smaller packages and thus leave less waste after their use.
Aus der
Aus der Druckschrift
Wasch- oder Reinigungsmittel sind heute für den Verbraucher in vielfältigen Angebotsformen erhältlich, Neben Pulvern und Granulaten umfasst dieses Angebot beispielsweise auch Flüssigkeiten, Gele oder Portionspackungen (Tabletten oder gefüllte Beutel). Insbesondere Portionspackungen mit flüssigen Wasch- oder Reinigungsmitteln werden immer beliebter, erfüllen sie einerseits den Wunsch des Verbrauchers nach vereinfachter Dosierung und andererseits bevorzugen immer mehr Verbraucher flüssige Wasch- oder Reinigungsmittel. Auch hier ist es wünschenswert, möglichst hochkonzentrierte Wasch- oder Reinigungsmittel zu verwenden.Detergents or cleaning agents are now available to the consumer in a variety of forms. In addition to powders and granules, this offer includes, for example, liquids, gels or sachets (tablets or filled bags). In particular, portion packs containing liquid detergents or cleaning agents are becoming increasingly popular, fulfilling, on the one hand, the consumer's desire for simplified dosing and, on the other hand, more and more consumers prefering liquid detergents or cleaners. Again, it is desirable to use highly concentrated detergents or cleaning agents.
Bei der Formulierung von flüssigen Wasch- oder Reinigungsmitteln zur Verpackung in wasserlöslichen Beuteln muss insbesondere darauf geachtet werden, dass die Inhaltsstoffe des Wasch- oder Reinigungsmittels die wasserlösliche Umhüllung des Beutels nicht schon vor ihrem Einsatz auf- oder anlösen und so zu unerwünschten Leckagen führen.When formulating liquid detergents or cleaners for packaging in water-soluble bags, particular care must be taken to ensure that the ingredients of the washing or cleaning agent do not dissolve or dissolve the water-soluble envelope of the bag before they are used and thus lead to undesirable leaks.
Auch kann es bei hochkonzentrierten Wasch- oder Reinigungsmittel Probleme mit der Stabilität, insbesondere mit der Stabilität des Tensidsystems, geben. Hochkonzentrierte Wasch- oder Reinigungsmittel (> 35 Gew.-% Tensid) mit einem auf Stabilität optimierten Tensidsystem mit hohen Mengen weisen gelegentlich Defizite in der Reinigungsleistung auf.Also, with highly concentrated detergents or cleaning agents, there may be problems with the stability, in particular with the stability of the surfactant system. Highly concentrated detergents or cleaning agents (> 35% by weight of surfactant) with a stability-optimized surfactant system with high amounts occasionally have deficits in the cleaning performance.
Entsprechend war es eine Aufgabe der vorliegenden Erfindung, ein stabiles, hochkonzentriertes flüssiges Wasch- oder Reinigungsmittel mit guter Reinigungsleistung bereit zu stellen, welches auch zur Verpackung in einer wasserlöslichen Umhüllung geeignet ist.Accordingly, it was an object of the present invention to provide a stable, highly concentrated liquid washing or cleaning agent with good cleaning performance, which is also suitable for packaging in a water-soluble casing.
Diese Aufgabe wird gelöst durch ein flüssiges Wasch- oder Reinigungsmittel enthaltend:
- a) 18 bis 35 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, anionisches Tensid vom Sulfonat-Typ ausgewählt aus der Gruppe bestehend aus C9-13-Alkylbenzolsulfonaten, Olefinsulfonaten, sulfonierten Estoliden, C12-18-Alkansulfonaten und Mischungen daraus,
- b) 15 bis 25 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen, alkoxylierten Oxo-Alkoholen, Alkylpolyglycosiden und Mischungen daraus,
- c) 2 bis 15 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, anionisches Tensid vom Sulfat-Typ ausgewählt aus der Gruppe bestehend aus Fettalkoholsulfaten, Fettalkoholethersulfaten und Mischungen daraus und
- d) 0,5 bis 20 Gew.-%, bezogen auf das gesamte Wasch- oder Reinigungsmittel, Fettsäure und/oder Fettsäureseife.
- a) 18 to 35 wt .-%, based on the total washing or cleaning agent, anionic surfactant sulfonate type selected from the group consisting of C 9-13 alkyl benzene sulfonates, olefin sulfonates, sulfonated estolides, C 12-18 alkanesulfonates and Mixtures thereof,
- b) from 15 to 25% by weight, based on the total washing or cleaning agent, of nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkylpolyglycosides and mixtures thereof,
- c) 2 to 15 wt .-%, based on the total washing or cleaning agent, anionic surfactant of the sulfate type selected from the group consisting of fatty alcohol sulfates, fatty alcohol ether sulfates and mixtures thereof and
- d) 0.5 to 20 wt .-%, based on the total washing or cleaning agent, fatty acid and / or fatty acid soap.
das dadurch gekennzeichnet ist, dass das Wasch- oder Reinigungsmittel in einer wasserlöslichen Umhüllung verpackt vorliegt und der Gehalt an Wasser weniger als 10 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel, beträgt.which is characterized in that the washing or cleaning agent is packaged in a water-soluble wrapper and the content of water is less than 10 wt .-%, based on the total liquid detergent or cleaning agent.
Es hat sich überraschenderweise gezeigt, dass mit Hilfe des ausgewählten hochkonzentrierten Tensidsystems ein phasenstabiles Wasch- oder Reinigungsmittel mit guter Reinigungsleistung erhalten werden kann.It has surprisingly been found that with the help of the selected highly concentrated surfactant system, a phase-stable detergent or cleaning agent can be obtained with good cleaning performance.
Das Wasch- oder Reinigungsmittel weist eine besonders gute Reinigungsleistung und gutes Schaumverhalten auf, wenn das anionische Tensid vom Sulfonat-Typ ein C9-13-Alkylbenzolsulfonat ist.The washing or cleaning agent has a particularly good cleaning performance and good foaming behavior when the sulfonate anionic surfactant is a C 9-13 -alkylbenzenesulfonate.
Es ist bevorzugt, dass das Verhältnis anionisches Tensid vom Sulfonat-Typ zu nichtionischem Tensid von 1,25 : 1 bis 1 : 1,25 beträgt. Ebenso ist es bevorzugt, dass das Verhältnis anionisches Tensid vom Sulfonat-Typ zu anionischem Tensid vom Sulfat-Typ größer 2 : 1 ist und/oder dass das Verhältnis nichtionisches Tensid zu anionischem Tensid vom Sulfat-Typ größer 2: 1 ist.It is preferred that the ratio of anionic surfactant of the sulfonate type to nonionic surfactant is from 1.25: 1 to 1: 1.25. It is also preferred that the ratio of sulfonate anionic surfactant to sulfate type anionic surfactant is greater than 2: 1 and / or that the ratio of nonionic surfactant to sulfate type anionic surfactant be greater than 2: 1.
Das Wasch- oder Reinigungsmittel ist in einer wasserlöslichen Umhüllung verpackt.The washing or cleaning agent is packaged in a water-soluble wrapper.
In dieser Ausführungsform kann es bevorzugt sein, dass 20 bis 25 g flüssiges Wasch- oder Reinigungsmittel in der wasserlöslichen Umhüllung verpackt sind.In this embodiment, it may be preferred that 20 to 25 g of liquid detergent or cleaning agent are packaged in the water-soluble wrapper.
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.It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
Im Folgenden soll die Erfindung, unter anderem anhand von Beispielen, eingehender erläutert werden.In the following, the invention will be explained in more detail, inter alia, by way of examples.
Das flüssige Wasch- oder Reinigungsmittel enthält verschiedene Tenside.The liquid washing or cleaning agent contains various surfactants.
Das flüssige Wasch- oder Reinigungsmittel enthält nichtionisches Tensid ausgewählt aus der Gruppe bestehend aus alkoxylierten Fettalkoholen, alkoxylierte Oxo-Alkohole, Alkylpolyglycosiden, ethoxylierten Methylestern von natürlichen Fettsäuren und Mischungen daraus.The liquid detergent or cleaning agent contains nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkyl polyglycosides, ethoxylated methyl esters of natural fatty acids and mixtures thereof.
Als alkoxylierte Fettalkohole werden vorzugsweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 4 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear ist. Insbesondere sind Alkoholethoxylate mit 12 bis 18 C-Atomen, zum Beispiel aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 5 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 4 EO oder 7 EO, C9-11-Alkohol mit 7 EO, C12-18-Alkohole mit 5 EO oder 7 EO und Mischungen aus diesen. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen alkoxylierte Fettalkoholen oder alternativ können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Auch alkoxylierte Fettalkohole, die EO- und PO-Gruppen zusammen im Molekül enthalten, sind erfindungsgemäß einsetzbar.The alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear. In particular, alcohol ethoxylates having 12 to 18 C atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 12-18 alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these alkoxylated fatty alcohols, or alternatively, fatty alcohols containing more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Alkoxylated fatty alcohols which contain EO and PO groups together in the molecule can also be used according to the invention.
Oxo-Alkohole sind primäre, teilweise verzweigte höhere Alkohole, die bei der Oxo-Synthese gewonnen werden. Dabei werden Oxo-Aldehyde oder deren primäre Aldokondensationsprodukte durch katalytische Hydrierung in die entsprechenden Oxo-Alkohole überführt.Oxo alcohols are primary, partially branched higher alcohols, which are obtained in the oxo synthesis. In this case, oxo-aldehydes or their primary aldokondensationsprodukte be converted by catalytic hydrogenation in the corresponding oxo alcohols.
Die alkoxylierten, vorzugsweise ethoxylierten, Oxo-Alkohole weisen einen Alkoxylierungsgrad zwischen 5 und 12 auf. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Oxo-Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).The alkoxylated, preferably ethoxylated, oxo alcohols have a degree of alkoxylation between 5 and 12. The indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred oxo-alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
Bevorzugt wird ein C13-15-Oxo-Alkohol mit 7 EO, ein C13-15-Oxo-Alkohol mit 8 EO oder eine Mischung aus diesen beiden Oxo-Alkoholen in dem flüssigen Wasch- oder Reinigungsmittel eingesetzt.A C 13-15 oxo alcohol with 7 EO, a C 13-15 oxo alcohol with 8 EO or a mixture of these two oxo alcohols in the liquid washing or cleaning agent is preferably used.
Außerdem können als nichtionische Tenside Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10, vorzugsweise liegt x bei 1,2 bis 1,4.In addition, as nonionic surfactants alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably x is 1.2 to 1.4.
Weitere geeignete nichtionische Tenside sind ethoxylierte Methylester von natürlichen Fettsäuren, wie beispielsweise Kokos-, Palmkern- oder Olivenölfettsäuren, mit vorzugsweise 8 bis 18 EO-Einheiten.Further suitable nonionic surfactants are ethoxylated methyl esters of natural fatty acids, such as coconut, palm kernel or olive oil fatty acids, preferably having 8 to 18 EO units.
Es kann bevorzugt sein, dass das flüssige Wasch- oder Reinigungsmittel ausschließlich alkoxylierte Fettalkohole als nichtionische Tenside enthält.It may be preferred that the liquid detergent or cleaning agent contains only alkoxylated fatty alcohols as nonionic surfactants.
In einer ganz besonders bevorzugten Ausführungsform enthält das flüssige Wasch- oder Reinigungsmittel ausschließlich alkoxylierte Oxo-Alkohole als nichtionische Tenside.In a very particularly preferred embodiment, the liquid washing or cleaning agent contains exclusively alkoxylated oxo alcohols as nonionic surfactants.
Die Gesamtmenge an nichtionischem Tensid in dem flüssigen Wasch- oder Reinigungsmittel beträgt bis zu 25 Gew.-% und vorzugsweise 16 bis 20 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The total amount of nonionic surfactant in the liquid washing or cleaning agent is up to 25% by weight and preferably 16 to 20% by weight, based on the total liquid detergent or cleaning agent.
Das flüssige Wasch- oder Reinigungsmittel enthält ferner anionisches Tensid vom Sulfonat-Typ. Dieses ausgewählt aus der Gruppe bestehend aus C9-13-Alkylbenzolsulfonaten, Olefinsulfonaten, sulfonierten Estoliden, C12-18-Alkansulfonaten und Mischungen daraus.The liquid washing or cleaning agent further contains anionic surfactant of the sulfonate type. This is selected from the group consisting of C 9-13 alkyl benzene sulfonates, olefin sulfonates, sulfonated estolides, C 12-18 alkanesulfonates, and mixtures thereof.
Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate zum Einsatz.As surfactants of the sulfonate type preferably C 9-13 alkylbenzenesulfonates are used.
Geeignete sulfonierte Estolide, die als Tensid vom Sulfonat-Typ eingesetzt werden können, umfassen Verbindungen der folgenden Formel
Alkylgruppe oder eine substituierte Alkylgruppe ist und Z Wasserstoff, ein einwertiges oder zweiwertiges Metallkation, ein Ammoniumkation oder substituiertes Ammoniumkation ist.And Z is hydrogen, a monovalent or divalent metal cation, an ammonium cation or a substituted ammonium cation.
Die Menge an anionischem Tensid vom Sulfonat-Typ beträgt 18 bis 35 Gew.-%, vorzugsweise 20 bis 30 Gew.-%, jeweils bezogen auf das gesamte Wasch- oder Reinigungsmittel.The amount of anionic surfactant of the sulfonate type is 18 to 35 wt .-%, preferably 20 to 30 wt .-%, each based on the total washing or cleaning agent.
Ferner enthält das Wasch- oder Reinigungsmittel 2 bis 15 Gew.-%, .-%, vorzugsweise 5 bis 12 Gew.-%, jeweils bezogen auf das gesamte Wasch- oder Reinigungsmittel, anionisches Tensid vom Sulfat-Typ ausgewählt aus der Gruppe bestehend aus Fettalkoholsulfaten, Fettalkoholethersulfaten und Mischungen darausFurthermore, the washing or cleaning agent contains 2 to 15 wt .-%, .-%, preferably 5 to 12 wt .-%, each based on the total washing or cleaning agent, anionic surfactant of the sulfate type selected from the group consisting of Fatty alcohol sulfates, fatty alcohol ether sulfates and mixtures thereof
Als Fettalkoholsulfate werden die Salze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol bevorzugt. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt.As fatty alcohol sulfates, the salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol are preferred. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
Als Fettalkoholethersulfate werden beispielsweise die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, eingesetzt.As fatty alcohol ether sulfates are, for example, the sulfuric acid monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C 7-21 alcohols such as 2-methyl-branched C 9-11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12th -18 fatty alcohols with 1 to 4 EO used.
Außerdem enthält das Wasch- oder Reinigungsmittel eine Fettsäure und/oder eine Fettsäureseife. Geeignet sind gesättigte und ungesättigte Fettsäuren, wie Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Talgfettsäuren, sowie von diesen Fettsäuren abgeleitete Seifen oder Seifengemische. Die Menge an Fettsäure und/oder eine Fettsäureseife in dem gesamten Wasch- oder Reinigungsmittel beträgt 0,5 bis 20 Gew.-% und bevorzugt 2 bis 15 Gew.-%.In addition, the washing or cleaning agent contains a fatty acid and / or a fatty acid soap. Suitable are saturated and unsaturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, and soaps or soap mixtures derived from these fatty acids. The amount of fatty acid and / or a fatty acid soap in the entire washing or cleaning agent is 0.5 to 20 wt .-% and preferably 2 to 15 wt .-%.
Die anionischen Tenside sowie die Fettsäureseifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natriumsalze oder Ammoniumsalze vor. Die Ammoniumsalze können die Salze organischer Basen sein. Das zur Neutralisation eingesetzte Amin ist vorzugsweise Cholin, Triethylamin, Monoethanolamin, Diethanolamin, Triethanolamin, Methylethylamin oder eine Mischung daraus, wobei Monoethanolamin bevorzugt ist.The anionic surfactants and the fatty acid soaps may be in the form of their sodium, potassium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts or ammonium salts. The ammonium salts may be the salts of organic bases. The amine used for the neutralization is preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.
Die Gesamtmenge an nichtionischem Tensid, anionischem Tensid vom Sulfonat-Typ, anionischem Tensid vom Sulfat-Typ und Fettsäure(seife) in dem flüssigen Wasch- oder Reinigungsmittel beträgt mindestens 35 Gew.-%, vorzugsweise 40 bis 75 Gew,-%, und ganz besonders bevorzugt 50 bis 60 Ges.-%, jeweils bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The total amount of nonionic surfactant, sulfonate type anionic surfactant, sulfate type anionic surfactant and fatty acid (soap) in the liquid detergent or cleaner is at least 35 wt .-%, preferably 40 to 75 wt -%, and most preferably 50 to 60 Ges .-%, each based on the total liquid detergent or cleaning agent.
Das flüssige Wasch- oder Reinigungsmittel kann ferner ein organisches Lösungsmittel enthalten, welches vorzugsweise 1,2-Propandiol, Glycerin und/oder Ethanol umfasst.The liquid washing or cleaning agent may further contain an organic solvent, which preferably comprises 1,2-propanediol, glycerol and / or ethanol.
Zusätzlich zu dem nichtionischen Tensid, dem anionischen Tensid vom Sulfonat-Typ, dem anionischem Tensid vom Sulfat-Typ und der Fettsäure(seife) kann das flussige Wasch- oder Reinigungsmittel weitere Inhaltsstoffe enthalten, die die anwendungstechnischen und/oder ästhetischen Eigenschaften des Wasch- oder Reinigungsmittels weiter verbessem. Im Rahmen der vorliegenden Erfindung enthält das Wasch- oder Reinigungsmittel vorzugsweise zusätzlich einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichkatalysatoren, Bleichaktivatoren, Enzyme, Elektrolyte, pH-Stellmittel, Parfüme, Parfümträger, Fluoreszenzmittel, Farbstoffe, Hydrotope, Schauminhibitoren, Silikonöle, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Hautpflegende Wirkstoffe, Quell- und Schiebefestmittel, weichmachenden Komponenten sowie UV-Absorber.In addition to the nonionic surfactant, the sulfonate type anionic surfactant, the sulfate type anionic surfactant and the fatty acid (soap), the liquid detergent or detergency detergent may contain other ingredients which enhance the performance and / or aesthetics of the laundry or cleaning product Cleaning agent further improved. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils , Anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skincare active ingredients, swelling and anti-slip agents, softening components and UV absorbers.
Das flüssige Wasch- oder Reinigungsmittel wird in eine wasserlösliche Umhüllung gefüllt und ist somit Bestandteil einer wasserlöslichen Verpackung. Der Gehalt an Wasser des flüssigen Wasch- oder Reinigungsmittels beträgt weniger als 10 Gew.-%, bezogen auf das gesamte flüssige Wasch- oder Reinigungsmittel.The liquid washing or cleaning agent is filled in a water-soluble wrapper and is thus part of a water-soluble packaging. The content of water of the liquid washing or cleaning agent is less than 10 wt .-%, based on the total liquid detergent or cleaning agent.
Die wasserlösliche Umhüllung bildet eine geschlossene Struktur aus, die in ihrem Inneren eine oder mehrere Kammern zur Aufnahme eines oder mehrerer Wasch- oder Reinigungsmittel aufweist Die wasserlösliche Verpackung kann formstabil oder verformbar ausgebildet sein,The water-soluble envelope forms a closed structure, which has in its interior one or more chambers for receiving one or more washing or cleaning agents. The water-soluble packaging may be dimensionally stable or deformable.
Die wasserlösliche Verpackung kann als formstabiler Behälter, beispielsweise in Form einer Kapsel, Box, Dose oder eines Containers ausgebildet sein.The water-soluble packaging may be formed as a dimensionally stable container, for example in the form of a capsule, box, box or container.
Es ist grundsätzlich jedoch auch möglich und bevorzugt, die wasserlösliche Verpackung als einen nicht formstabilen Behälter, beispielsweise als Beutel auszuformen. Die Form einer derartigen wasserlöslichen Verpackung kann den Gebrauchsgegebenheiten weitgehend angepasst werden. Es kommen beispielsweise verschiedenste Formen wie beispielsweise Schläuche, Kissen, Zylinder, Flaschen oder Scheiben in Frage.However, in principle it is also possible and preferred to mold the water-soluble packaging as a non-dimensionally stable container, for example as a bag. The shape of such a water-soluble packaging can be largely adapted to the conditions of use. There are, for example, various forms such as hoses, pillows, cylinders, bottles or discs in question.
Eine wasserlösliche Verpackung enthält neben dem flüssigen Wasch- oder Reinigungsmittel eine wasserlösliche Umhüllung. Die wasserlösliche Umhüllung wird vorzugsweise durch ein wasserlösliches Folienmaterial gebildet.A water-soluble packaging contains, in addition to the liquid washing or cleaning agent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.
Solche wasserlöslichen Verpackungen können entweder durch Verfahren des vertikalen Formfüllversiegelns (VFFS) oder Warmformverfahren hergestellt werden.Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.
Das Warmformverfahren schließt im Allgemeinen das Formen einer ersten Lage aus einem wasserlöslichen Folienmaterial zum Bilden von Ausbuchtungen zum Aufnehmen einer Zusammensetzung darin, Einfüllen der Zusammensetzung in die Ausbuchtungen, Bedecken der mit der Zusammensetzung gefüllten Ausbuchtungen mit einer zweiten Lage aus einem wasserlöslichen Folienmaterial und Versiegeln der ersten und zweiten Lagen miteinander zumindest um die Ausbuchtungen herum ein.The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.
Die wasserlösliche Umhüllung wird vorzugsweise aus einem wasserlöslichen Folienmaterial ausgewählt aus der Gruppe umfassend Polymeren und Polymergemischen gebildet. Die Umhüllung kann aus einer oder aus zwei oder mehr Lagen aus dem wasserlöslichen Folienmaterial gebildet werden. Das wasserlösliche Folienmaterial der ersten Lage und der weiteren Lagen, falls vorhanden, kann gleich oder unterschiedlich sein.The water-soluble coating is preferably formed from a water-soluble film material selected from the group comprising polymers and polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.
Es ist bevorzugt, dass die wasserlösliche Umhüllung Polyvinylalkohol oder ein Polyvinylalkoholcopolymer enthält.It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
Geeignete wasserlösliche Folien zur Herstellung der wasserlöslichen Umhüllung basieren bevorzugt auf einem Polyvinylalkohol oder einem Polyvinylalkoholcopolymer, dessen Molekulargewicht im Bereich von 10.000 bis 1.000.000 gmol-1, vorzugsweise von 20.000 bis 500.000 gmol-1, besonders bevorzugt von 30.000 bis 100.000 gmol-1 und insbesondere von 40.000 bis 80.000 gmol-1 liegt.Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
Die Herstellung von Polyvinylalkohol geschieht üblicherweise durch Hydrolyse von Polyvinylacetat, da der direkte Syntheseweg nicht möglich ist. Ähnliches gilt für Polyvinylalkoholcopolymere, die aus entsprechend aus Polyvinylacetatcopolymeren hergestellt werden. Bevorzugt ist, wenn wenigstens eine Lage der wasserlöslichen Umhüllung einen Polyvinylalkohol umfasst, dessen Hydrolysegrad 70 bis 100 Mol-%, vorzugsweise 80 bis 90 Mol-%, besonders bevorzugt 81 bis 89 Mol-% und insbesondere 82 bis 88 Mol-% ausmacht.The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. When at least one layer of the water-soluble casing comprises a polyvinyl alcohol, its degree of hydrolysis is preferably 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
Einem zur Herstellung der wasserlöslichen Umhüllung geeignetem Polyvinylalkohol-enthaltendem Folienmaterial kann zusätzlich ein Polymer ausgewählt aus der Gruppe umfassend (Meth)Acrylsäurehaltige (Co)Polymere, Polyacrylamide, Oxazolin-Polymere, Polystyrolsulfonate, Polyurethane, Polyester, Polyether, Polymilchsäuren oder Mischungen der vorstehenden Polymere zugesetzt sein. Ein bevorzugtes zusätzliches Polymer sind Polymilchsäuren.A polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acids or mixtures of the above polymers may additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating be. A preferred additional polymer is polylactic acids.
Bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol Dicarbonsäuren als weitere Monomere. Geeignete Dicarbonsäure sind Itaconsäure, Malonsäure, Bernsteinsäure und Mischungen daraus, wobei Itaconsäure bevorzugt ist.Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
Ebenfalls bevorzugte Polyvinylalkoholcopolymere umfassen neben Vinylalkohol eine ethylenisch ungesättige Carbonsäure, deren Salz oder deren Ester. Besonders bevorzugt enthalten solche Polyvinylalkoholcopolymere neben Vinylalkohol Acrylsäure, Methacrylsäure, Acrylsäureester, Methacrylsäureester oder Mischungen daraus.Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
Es kann bevorzugt sein, dass das Folienmaterial weitere Zusatzstoffe enthält. Das Folienmaterial kann beispielsweise Weichmacher wie Dipropylenglycol, Ethylenglycol, Diethylenglycol, Propylenglycol, Glycerin, Sorbitol, Mannitol oder Mischungen daraus enthalten. Weitere Zusatzstoffe umfassen beispielsweise Freisetzungshilfen, Füllmittel, Vernetzungsmittel, Tenside, Antioxidationsmittel, UV-Absorber, Antiblockmittel, Antiklebemittel oder Mischungen daraus.It may be preferred that the film material contains further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
Geeignete wasserlösliche Folien zum Einsatz in den wasserlöslichen Umhüllungen der wasserlöslichen Verpackungen gemäß der Erfindung sind Folien, die von der Firma MonoSol LLC beispielsweise unter der Bezeichnung M8630, M8310, C8400 oder M8900 vertrieben werden. Andere geeignete Folien umfassen Folien mit der Bezeichnung Solublon® PT, Solublon® GA, Solublon® KC oder Solublon® KL von der Aicello Chemical Europe GmbH oder die Folien VF-HP von Kuraray.Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, M8310, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
In einer bevorzugten Ausführungsform weist die wasserlösliche Verpackung eine Kammer zur Aufnahme des hochkonzentrierten flüssigen Wasch- oder Reinigungsmittels auf.In a preferred embodiment, the water-soluble packaging has a chamber for receiving the highly concentrated liquid washing or cleaning agent.
In einer weiteren, ebenfalls bevorzugten Ausführungsform weist die wasserlösliche Verpackung zwei Kammern auf. In dieser Ausführungsform enthält die erste Kammer das oben beschriebene hochkonzentrierte flüssige Wasch- oder Reinigungsmittel und die zweite Kammer kann ein festes oder ein flüssiges Wasch- oder Reinigungsmittel enthalten.In a further, likewise preferred embodiment, the water-soluble packaging has two chambers. In this embodiment, the first chamber contains the above-described highly concentrated liquid detergent or cleaning agent and the second chamber may contain a solid or a liquid detergent or cleaning agent.
Weist die wasserlösliche Verpackung in noch einer weiteren bevorzugten Ausführungsform drei Kammern auf, können diese Kammern alle jeweils ein flüssiges Wasch- oder Reinigungsmittel enthalten. Möglich ist aber auch, dass eine Kammer ein festes Wasch- oder Reinigungsmittel und zwei Kammern ein flüssiges Wasch- oder Reinigungsmittel enthalten. Außerdem ist es möglich, dass in zwei Kammern ein festes Wasch- oder Reinigungsmittel und in einer Kammer ein flüssiges Wasch- oder Reinigungsmittel enthalten ist.If the water-soluble packaging in yet another preferred embodiment has three chambers, these chambers can each contain a liquid washing or cleaning agent. But it is also possible that a chamber containing a solid detergent or detergent and two chambers containing a liquid detergent or cleaning agent. It is also possible that a solid detergent or cleaning agent is contained in two chambers and a liquid detergent or cleaning agent in a chamber.
Bei wasserlöslichen Verpackungen mit vier oder mehr Kammern bestehen entsprechend noch mehr Kombinationsmöglichkeiten im Hinblick auf die Zahl der Kammern mit einem festen oder einem flüssigen Wasch- oder Reinigungsmittel.In the case of water-soluble packaging with four or more chambers, there are correspondingly even more possible combinations with regard to the number of chambers with a solid or a liquid washing or cleaning agent.
Bei wasserlöslichen Verpackungen mit zwei oder mehr Kammern enthält mindestens eine Kammer das oben beschriebene, erfindungsgemäße flüssige Wasch- oder Reinigungsmittel. Die flüssigen Wasch- oder Reinigungsmittel, die in den anderen Kammern einer wasserlöslichen Verpackung enthalten sind, können dieselbe Zusammensetzung aufweisen. Vorzugsweise weisen die flüssigen Wasch- oder Reinigungsmittels in einer wasserlöslichen Verpackung mit mindestens zwei Kammern Zusammensetzungen auf, die sich mindestens im Gehalt eines Inhaltsstoffs unterscheiden.In the case of water-soluble packaging with two or more chambers, at least one chamber contains the above-described liquid detergent or cleaning agent according to the invention. The liquid detergents or cleaning agents contained in the other chambers of a water-soluble packaging may have the same composition. The liquid detergents or cleaners in a water-soluble packaging with at least two chambers preferably have compositions which differ at least in the content of an ingredient.
Die Menge an Wasch- oder Reinigungsmittel, welche sich insgesamt in der wasserlöslichen Verpackung befindet, entspricht der vollen Dosis, die für einen Waschgang für 4,5 kg Wäsche benötigt wird. In einer bevorzugten Ausführungsform der Erfindung sind 20 bis 25 g flüssiges Wasch- oder Reinigungsmittel in einer wasserlöslichen Umhüllung verpackt.The amount of detergent or cleaning agent, which is in total in the water-soluble packaging corresponds to the full dose needed for a wash for 4.5 kg of laundry. In a preferred embodiment of the invention, 20 to 25 g of liquid washing or cleaning agent are packaged in a water-soluble wrapper.
Es wurden flüssige Wasch- oder Reinigungsmittel mittels üblicher und bekannter Methoden und Verfahren hergestellt. In der folgenden Tabelle 1 sind die Zusammensetzungen von einem erfindungsgemäßen Wasch- oder Reinigungsmitteln E1 sowie einem nicht erfindungsgemäßen Wasch- oder Reinigungsmitteln V1 gezeigt.
In einem ersten Waschversuch wurde der Effizienzgrad der Wasch- oder Reinigungsmittel E1 und V1 als die Summe der Remissionseinheiten an verschiedenen Flecken (53 Fett-haltige Flecken und 18 Enzym-sensitive Flecken) bestimmt. Dazu wurde jeweils eine Haushaltswaschmaschine (Miele W 1734) mit 3,5 kg Begleitwäsche sowie entsprechend verschmutzten Stofflappen beladen. Zusätzlich wurden entweder 39 g des Wasch- oder Reinigungsmittels V1 oder 25 g des Wasch- oder Reinigungsmittels E1 zudosiert und es wurde bei 40 °C gewaschen. Nach hängender Trocknung und Mangeln der Stofflappen wurde deren Remission spektralphotometrisch (Minolta CR200-1) bestimmt. Die Bewertung der Fleckentfernung erfolgte über den Y-Wert.In a first washing test, the efficiency of washing or cleaning agents E1 and V1 was determined as the sum of the remission units at different spots (53 fat-containing spots and 18 enzyme-sensitive spots). For this purpose, a household washing machine (Miele W 1734) was loaded with 3.5 kg accompanying laundry as well as correspondingly contaminated cloth rags. In addition, either 39 g of the washing or cleaning agent V1 or 25 g of the washing or cleaning agent E1 were added and it was washed at 40 ° C. After hanging drying and mangling of the cloth rags their remission was determined spectrophotometrically (Minolta CR200-1). The stain removal was evaluated by the Y value.
Es zeigte sich, dass die erhaltenen Werte im Fall von Enzym-sensitiven Flecken nahezu identisch waren, während das Wasch- oder Reinigungsmittel E1 an Fett-haltigen Flecken einen besseren Effizienzgrad als das nicht erfindungsgemäße Wasch- oder Reinigungsmittel V1 zeigte.
In einem zweiten Waschversuch wurde der Effizienzgrad der Wasch- oder Reinigungsmittel E1 und V1 an 53 Fett-haltige Flecken bei unterschiedlichen Waschtemperaturen bestimmt. Dazu wurde jeweils eine Haushaltswaschmaschine (Miele W 1734) mit 3,5 kg Begleitwäsche sowie entsprechend verschmutzten Stofflappen beladen. Zusätzlich wurden entweder 39 g des Wasch- oder Reinigungsmittels V1 oder 20 g des Wasch- oder Reinigungsmittels E1 zudosiert und es wurde bei 20°C, 40 °C oder 60 °C gewaschen. Nach hängender Trocknung und Mangeln der Stofflappen wurde deren Remission spektralphotometrisch (Minolta CR200-1) bestimmt. Die Bewertung der Fleckentfernung erfolgte über den Y-Wert.In a second washing test, the efficiency of washing or cleaning agents E1 and V1 was determined on 53 fat-containing stains at different washing temperatures. For this purpose, a household washing machine (Miele W 1734) was loaded with 3.5 kg accompanying laundry as well as correspondingly contaminated cloth rags. In addition, either 39 g of the washing or cleaning agent V1 or 20 g of the washing or cleaning agent E1 were added and it was washed at 20 ° C, 40 ° C or 60 ° C. After hanging drying and mangling of the cloth rags their remission was determined spectrophotometrically (Minolta CR200-1). The stain removal was evaluated by the Y value.
Es zeigte sich, dass bei allen drei Waschtemperaturen das Wasch- oder Reinigungsmittel E1 einen besseren Effizienzgrad als das nicht erfindungsgemäße Wasch- oder Reinigungsmittel V1 aufwies.
In einem dritten Waschversuch wurde die vergrauungsinhibierende Leistung der Wasch- oder Reinigungsmittel E1 und V1 bestimmt. Dazu wurde jeweils eine Haushaltswaschmaschine (Miele W 1734) mit 2,5 kg weißer Begleitwäsche, verschiedenen Testgeweben, fünf SBL 2004 Tüchern mit standardisierter Schmutzbeladung (32 g Schmutzballast), beladen. Zusätzlich wurden entweder 39 g des Wasch- oder Reinigungsmittels V1, 25 g des Wasch- oder Reinigungsmittels E1 oder 20 g des Wasch- oder Reinigungsmittels E1 zudosiert und es wurde bei 40 °C gewaschen. Nach hängender Trocknung und Mangeln der Stofflappen wurde deren Weißgrad spektralphotometrisch (Minolta CR200-1) bestimmt. Die Bewertung der Fleckentfernung erfolgte über den Y-Wert.In a third washing test, the graying-inhibiting performance of the washing or cleaning agents E1 and V1 was determined. For this purpose, a household washing machine (Miele W 1734) was loaded with 2.5 kg of white accompanying laundry, various test fabrics, five SBL 2004 wipes with standardized dirt load (32 g of dirt ballast). In addition, either 39 g of the washing or cleaning agent V1, 25 g of the washing or cleaning agent E1 or 20 g of the washing or cleaning agent E1 were added and it was washed at 40 ° C. After hanging Drying and mangling of the cloth rags their whiteness was determined spectrophotometrically (Minolta CR200-1). The stain removal was evaluated by the Y value.
In Tabelle 4 sind diese Messwerte im Vergleich zum jeweiligen Ausgangswert der Testgewebe angegeben.Table 4 shows these measurements versus the baseline test fabric.
Bei den Geweben aus Baumwolle handelte es sich um acht verschiedene kommerziell erhältliche Baumwollgewebe. Bei den Geweben aus Polyester handelte es sich um fünf verschiedene kommerziell erhältliche Polyestergewebe Die Alttagsgewebe umfassten vier handelsübliche Alltagstextilien wie zum Beispiel Küchen-, Frottier-, Gerstenkornhandtuch und weiße T-Shirts.
Die Ergebnisse zeigen, dass die vergrauungsinhibierende Leistung des Wasch- oder Reinigungsmittels E1 höher ist, als bei dem nicht erfindungsgemäßen Wasch- oder Reinigungsmittel V1.The results show that the graying-inhibiting performance of the washing or cleaning agent E1 is higher than that of the washing or cleaning agent V1 not according to the invention.
In einem vierten Waschversuch wurde die Fleckentfernung der Wasch- oder Reinigungsmittel E1 und V1 an verschiedenen Flecken bestimmt. Dazu wurde jeweils eine Haushaltswaschmaschine (Miele W 1734) mit 3,5 kg Begleitwäsche sowie entsprechend verschmutzten Stofflappen beladen. Zusätzlich wurden entweder 39 g des Wasch- oder Reinigungsmittels V1, 25 g des Wasch- oder Reinigungsmittels E1 oder 20 g des Wasch- oder Reinigungsmittels E1 zudosiert und es wurde bei 40 °C gewaschen. Nach hängender Trocknung und Mangeln der Stofflappen wurde deren Remission spektralphotometrisch (Minolta CR200-1) bestimmt. Die Bewertung der Fleckentfernung erfolgte über den Y-Wert.
PES = Polyester
CO/PES = Baumwolle-Polyester-Mischgewebe
PES = polyester
CO / PES = cotton-polyester blend
Zur Herstellung von wasserlöslichen Verpackungen mit dem Wasch- oder Reinigungsmittel E1 wurde eine Folie vom Typ M 8630 (ex Monosol) mit einer Dicke von 76 µm zum Ausbilden einer Ausbuchtung mittels Vakuum in eine Mulde gezogen. Anschließend wurde die Ausbuchtung mit 25 g des flüssigen Wasch- oder Reinigungsmittel E1 befüllt. Nach Bedecken der mit dem Mittel befüllten Ausbuchtungen mit einer zweiten Lage einer Folie vom Typ M 8630 wurden die erste und zweite Lage miteinander versiegelt. Die Siegelungstemperatur betrug 150 °C und die Siegelungsdauer 1,1 Sekunden.To produce water-soluble packaging with the detergent or cleaning agent E1, a film of the type M 8630 (ex Monosol) with a thickness of 76 μm was pulled into a depression by means of a vacuum to form a bulge. Subsequently, the bulge was filled with 25 g of the liquid detergent or cleaning agent E1. After covering the agent filled bulges with a second layer of M 8630 film, the first and second layers were sealed together. The sealing temperature was 150 ° C and the sealing time 1.1 seconds.
Nach 4, 8 und 12 Wochen Lagerzeit der wasserlöslichen Verpackungen mit dem Wasch- oder Reinigungsmittel E1 unter verschiedenen klimatischen Bedingungen konnte keinerlei An- oder Auflösung der wasserlöslichen Umhüllung beobachtet werden. Zudem konnten keine Poren oder Löcher, die ebenfalls zum Produktaustritt oder Leckagen führen würden, festgestellt werden.After 4, 8 and 12 weeks storage time of the water-soluble packaging with the detergent or cleaning agent E1 under various climatic conditions no arrival or dissolution of the water-soluble coating could be observed. In addition, no pores or holes, which would also lead to product leakage or leaks, were found.
Wasserlösliche Verpackungen mit dem flüssigen Wasch- oder Reinigungsmittel E1 lösten sich in Waschgängen bei Temperaturen, die im Bereich von 20 bis 95 °C lagen, rückstandslos auf.Water-soluble packaging with the liquid detergent or cleaning agent E1 dissolved in washes at temperatures ranging from 20 to 95 ° C, leaving no residue.
Claims (7)
- A liquid washing or cleaning agent containing:a) 18 to 35 wt.%, based on the entire washing or cleaning agent, of an anionic surfactant of the sulfonate type, selected from the group consisting of C9-13 alkylbenzene sulfonates, olefin sulfonates, sulfonated estolides, C12-18 alkane sulfonates and mixtures thereof,b) 15 to 25 wt.%, based on the entire washing or cleaning agent, of a nonionic surfactant selected from the group consisting of alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkyl polyglycosides and mixtures thereof,c) 2 to 15 wt.%, based on the entire washing or cleaning agent, of an anionic surfactant of the sulfate type, selected from the group consisting of fatty alcohol sulfates, fatty alcohol ether sulfates and mixtures thereof, andd) 0.5 to 20 wt.%, based on the entire washing or cleaning agent, of a fatty acid and/or fatty acid soap,characterized in that the washing or cleaning agent is packaged in a water-soluble wrapping and the water content is less than 10 wt.%, based on the entire liquid washing or cleaning agent.
- The liquid washing or cleaning agent according to claim 1, characterized in that the anionic surfactant of the sulfonate type is a C9-13 alkylbenzene sulfonate.
- The liquid washing or cleaning agent according to claim 1 or claim 2, characterized in that the ratio of the anionic surfactant of the sulfonate type to the nonionic surfactant is from 1.25:1 to 1:1.25.
- The liquid washing or cleaning agent according to one of claims 1 to 3, characterized in that the ratio of the anionic surfactant of the sulfonate type to the anionic surfactant of the sulfate type is greater than 2:1.
- The liquid washing or cleaning agent according to one of claims 1 to 4, characterized in that the ratio of the nonionic surfactant to the anionic surfactant of the sulfate type is greater than 2:1.
- The liquid washing or cleaning agent according to one of claims 1 to 5, characterized in that 20 to 25 g of liquid washing or cleaning agent is packaged in the water-soluble wrapping.
- The liquid washing or cleaning agent according to one of claims 1 to 6, characterized in that the water-soluble wrapping contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL13730592T PL2867352T3 (en) | 2012-06-27 | 2013-06-24 | Highly concentrated liquid washing or cleaning composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE201210211028 DE102012211028A1 (en) | 2012-06-27 | 2012-06-27 | Highly concentrated liquid washing or cleaning agent |
PCT/EP2013/063146 WO2014001260A1 (en) | 2012-06-27 | 2013-06-24 | Highly concentrated liquid washing or cleaning composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2867352A1 EP2867352A1 (en) | 2015-05-06 |
EP2867352B1 true EP2867352B1 (en) | 2017-11-01 |
Family
ID=48670581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13730592.6A Revoked EP2867352B1 (en) | 2012-06-27 | 2013-06-24 | Highly concentrated liquid washing or cleaning composition |
Country Status (7)
Country | Link |
---|---|
US (1) | US9150821B2 (en) |
EP (1) | EP2867352B1 (en) |
DE (1) | DE102012211028A1 (en) |
ES (1) | ES2655025T3 (en) |
HU (1) | HUE035741T2 (en) |
PL (1) | PL2867352T3 (en) |
WO (1) | WO2014001260A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3101102B2 (en) | 2015-06-05 | 2023-12-13 | The Procter & Gamble Company | Compacted liquid laundry detergent composition |
EP3101107B1 (en) | 2015-06-05 | 2019-04-24 | The Procter and Gamble Company | Compacted liquid laundry detergent composition |
EP3101106B1 (en) * | 2015-06-05 | 2019-04-24 | The Procter and Gamble Company | Compacted liquid laundry detergent composition |
EP3101100B1 (en) | 2015-06-05 | 2018-02-07 | The Procter and Gamble Company | Compacted liquid laundry detergent composition |
HUE039814T2 (en) * | 2015-07-30 | 2019-02-28 | Procter & Gamble | Water-soluble unit dose article |
WO2019038049A1 (en) * | 2017-08-25 | 2019-02-28 | Unilever N.V. | An antimicrobial composition |
DE102017215016A1 (en) * | 2017-08-28 | 2019-02-28 | Henkel Ag & Co. Kgaa | Structured washing or cleaning agent with yield point |
EP3623458A1 (en) * | 2018-09-11 | 2020-03-18 | The Procter & Gamble Company | Water-soluble unit dose article |
EP3892707A1 (en) | 2020-04-06 | 2021-10-13 | Dalli-Werke GmbH & Co. KG | Liquid detergent composition, kit and dosing system |
DE102020212100A1 (en) * | 2020-09-25 | 2022-03-31 | Henkel Ag & Co. Kgaa | Concentrated flowable detergent preparation with improved properties |
US20220298453A1 (en) * | 2021-03-18 | 2022-09-22 | Henkel IP & Holding GmbH | Liquid Laundry Detergent Compositions Containing Soil Release Polymers |
CN114653213A (en) * | 2021-12-25 | 2022-06-24 | 华能酒泉发电有限公司 | Preparation method and application of cleaning agent for removing ultrafiltration membrane grease and organic matters |
CN115386435A (en) * | 2022-09-06 | 2022-11-25 | 湖北雅绿镓新材料科技有限公司 | Colorful deep sea crystal salt bacteriostatic decontamination fragrance-retaining washing gel bead and preparation method thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0985017A1 (en) | 1997-04-10 | 2000-03-15 | Henkel Corporation | Cleaning compositions having enhanced enzyme activity |
WO2002094974A1 (en) * | 2001-05-22 | 2002-11-28 | The Procter & Gamble Company | Pouched compositions |
WO2009061990A1 (en) | 2007-11-09 | 2009-05-14 | The Procter & Gamble Company | Cleaning compositions with amphiphilic water-soluble polyalkylenimines having an inner polyethylene oxide block and an outer polypropylene oxide block |
WO2011005943A1 (en) | 2009-07-10 | 2011-01-13 | The Procter & Gamble Company | Compositions containing benefit agent delivery particles |
US20110119841A1 (en) | 2008-06-16 | 2011-05-26 | Julie Bennett | Fabric cleaning |
WO2011075556A1 (en) | 2009-12-18 | 2011-06-23 | The Procter & Gamble Company | Composition comprising encapsulates, and process for making them |
US20110186468A1 (en) | 2010-01-29 | 2011-08-04 | Denome Frank William | Water-soluble film having improved dissolution and stress properties, and packets made therefrom |
US20110268778A1 (en) | 2010-04-28 | 2011-11-03 | Jiten Odhavji Dihora | Delivery particles |
US20110268802A1 (en) | 2010-04-28 | 2011-11-03 | Jiten Odhavji Dihora | Delivery particle |
US20120017947A1 (en) | 2010-07-20 | 2012-01-26 | Susana Fernandez Prieto | Delivery particle |
US20120028874A1 (en) | 2010-07-20 | 2012-02-02 | Susana Fernandez Prieto | Particles |
WO2013139726A1 (en) * | 2012-03-19 | 2013-09-26 | Henkel Ag & Co. Kgaa | Liquid detergent with increased cleaning performance |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK131638A (en) | 1969-06-07 | |||
DE3063434D1 (en) * | 1979-05-16 | 1983-07-07 | Procter & Gamble Europ | Highly concentrated fatty acid containing liquid detergent compositions |
DE4028850A1 (en) * | 1990-09-11 | 1992-03-12 | Johannes Kiehl Kg | Low viscosity liq. washing compsn. concentrate - contains anionic and nonionic surfactants, copolymer of acrolein, acrylic¨ acid and/or maleic acid, etc. and fatty acid soap |
DE60307105T2 (en) * | 2003-09-22 | 2007-02-15 | The Procter & Gamble Company, Cincinnati | Liquid single serving washing or cleaning agent |
WO2010019841A2 (en) | 2008-08-14 | 2010-02-18 | Melaleuca, Inc. | Ultra concentrated liquid laundry detergent |
-
2012
- 2012-06-27 DE DE201210211028 patent/DE102012211028A1/en not_active Withdrawn
-
2013
- 2013-06-24 HU HUE13730592A patent/HUE035741T2/en unknown
- 2013-06-24 PL PL13730592T patent/PL2867352T3/en unknown
- 2013-06-24 WO PCT/EP2013/063146 patent/WO2014001260A1/en active Application Filing
- 2013-06-24 EP EP13730592.6A patent/EP2867352B1/en not_active Revoked
- 2013-06-24 ES ES13730592.6T patent/ES2655025T3/en active Active
-
2014
- 2014-12-18 US US14/574,585 patent/US9150821B2/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0985017A1 (en) | 1997-04-10 | 2000-03-15 | Henkel Corporation | Cleaning compositions having enhanced enzyme activity |
WO2002094974A1 (en) * | 2001-05-22 | 2002-11-28 | The Procter & Gamble Company | Pouched compositions |
WO2009061990A1 (en) | 2007-11-09 | 2009-05-14 | The Procter & Gamble Company | Cleaning compositions with amphiphilic water-soluble polyalkylenimines having an inner polyethylene oxide block and an outer polypropylene oxide block |
US20110119841A1 (en) | 2008-06-16 | 2011-05-26 | Julie Bennett | Fabric cleaning |
WO2011005943A1 (en) | 2009-07-10 | 2011-01-13 | The Procter & Gamble Company | Compositions containing benefit agent delivery particles |
WO2011075556A1 (en) | 2009-12-18 | 2011-06-23 | The Procter & Gamble Company | Composition comprising encapsulates, and process for making them |
US20110186468A1 (en) | 2010-01-29 | 2011-08-04 | Denome Frank William | Water-soluble film having improved dissolution and stress properties, and packets made therefrom |
US20110268778A1 (en) | 2010-04-28 | 2011-11-03 | Jiten Odhavji Dihora | Delivery particles |
US20110268802A1 (en) | 2010-04-28 | 2011-11-03 | Jiten Odhavji Dihora | Delivery particle |
US20120017947A1 (en) | 2010-07-20 | 2012-01-26 | Susana Fernandez Prieto | Delivery particle |
US20120028874A1 (en) | 2010-07-20 | 2012-02-02 | Susana Fernandez Prieto | Particles |
WO2013139726A1 (en) * | 2012-03-19 | 2013-09-26 | Henkel Ag & Co. Kgaa | Liquid detergent with increased cleaning performance |
Non-Patent Citations (1)
Title |
---|
RÖMPP: "Alkylarensulfonate", BIOTECHNOLOGIE LEXIKON, vol. 7, 1991, pages 116, XP055506268 |
Also Published As
Publication number | Publication date |
---|---|
DE102012211028A1 (en) | 2014-01-02 |
EP2867352A1 (en) | 2015-05-06 |
US9150821B2 (en) | 2015-10-06 |
PL2867352T3 (en) | 2018-04-30 |
ES2655025T3 (en) | 2018-02-16 |
HUE035741T2 (en) | 2018-05-28 |
US20150105313A1 (en) | 2015-04-16 |
WO2014001260A1 (en) | 2014-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2867352B1 (en) | Highly concentrated liquid washing or cleaning composition | |
EP3024917B1 (en) | Detergent containing amine oxide | |
EP2850169B1 (en) | Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials | |
EP2828368B1 (en) | Liquid detergent composition with increased cleaning performance | |
DE102013218614A1 (en) | Detergent containing ether carboxylates | |
EP2809759B1 (en) | Low-water, liquid detergent having increased fat-dissolving power | |
WO2015091110A2 (en) | Detergent containing methyl ester sulfonates (mes) and methyl ester ethoxylates (mee) | |
EP2875107B1 (en) | Stable, liquid detergent with anti-redeposition action | |
EP3250668B1 (en) | Acid liquid compact washing agent containing hydroxycarboxylic acid, non-ionic surfactant and -amylase | |
DE102011085639A1 (en) | Liquid detergent or cleaning agent useful e.g. for washing textile sheet material or hard surface, comprises anionic surfactant including sulfonate- or sulfate surfactants, nonionic surfactant including e.g. amine oxides and inorganic salt | |
DE102014205928A1 (en) | Detergents or cleaning agents with anionic surfactant, fatty alcohol alkoxylate, fatty acid esters and alkylene glycol monoether | |
WO2015091108A1 (en) | Washing composition comprising alkyl carboxylates | |
EP2875106B1 (en) | Stable liquid detergent composition showing anti redepositon effect | |
EP4077623B1 (en) | Textile treatment composition | |
DE102016206647A1 (en) | liquid detergent | |
DE102015214056A1 (en) | Detergency enhancing hydroxyamine oxides | |
DE102014204826A1 (en) | Detergent containing esterquats | |
DE102013211954A1 (en) | Detergent or cleaning agent containing sucrose alkyl esters |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20140306 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAX | Request for extension of the european patent (deleted) | ||
TPAC | Observations filed by third parties |
Free format text: ORIGINAL CODE: EPIDOSNTIPA |
|
17Q | First examination report despatched |
Effective date: 20160211 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20170621 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 942031 Country of ref document: AT Kind code of ref document: T Effective date: 20171115 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502013008720 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2655025 Country of ref document: ES Kind code of ref document: T3 Effective date: 20180216 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20171101 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180201 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E035741 Country of ref document: HU |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180301 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180202 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180201 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 502013008720 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
26 | Opposition filed |
Opponent name: DALLI-WERKE GMBH CO. KG Effective date: 20180727 Opponent name: THE PROCTER GAMBLE COMPANY Effective date: 20180801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180630 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180624 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180624 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 942031 Country of ref document: AT Kind code of ref document: T Effective date: 20180624 |
|
R26 | Opposition filed (corrected) |
Opponent name: THE PROCTER & GAMBLE COMPANY Effective date: 20180801 |
|
RDAF | Communication despatched that patent is revoked |
Free format text: ORIGINAL CODE: EPIDOSNREV1 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBM | Appeal reference recorded |
Free format text: ORIGINAL CODE: EPIDOSNREFNO |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180624 |
|
APBQ | Date of receipt of statement of grounds of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA3O |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20171101 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20210622 Year of fee payment: 9 Ref country code: DE Payment date: 20210618 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20210826 Year of fee payment: 9 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: THE PROCTER & GAMBLE COMPANY Effective date: 20180801 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R103 Ref document number: 502013008720 Country of ref document: DE Ref country code: DE Ref legal event code: R064 Ref document number: 502013008720 Country of ref document: DE |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: FI Ref legal event code: MGE |
|
27W | Patent revoked |
Effective date: 20220609 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Effective date: 20220609 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20220627 Year of fee payment: 10 Ref country code: HU Payment date: 20220617 Year of fee payment: 10 Ref country code: GB Payment date: 20220627 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20220620 Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MA03 Ref document number: 942031 Country of ref document: AT Kind code of ref document: T Effective date: 20220609 |