EP3143111B1 - Formulation alcaline aqueuse de détergent liquide de lave-vaisselle à main - Google Patents
Formulation alcaline aqueuse de détergent liquide de lave-vaisselle à main Download PDFInfo
- Publication number
- EP3143111B1 EP3143111B1 EP15717911.0A EP15717911A EP3143111B1 EP 3143111 B1 EP3143111 B1 EP 3143111B1 EP 15717911 A EP15717911 A EP 15717911A EP 3143111 B1 EP3143111 B1 EP 3143111B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formulation
- liquid detergent
- aqueous alkaline
- hand dishwash
- benzene sulfonate
- 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.)
- Active
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
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
Definitions
- This present invention relates to an improved aqueous alkaline hand dishwash liquid detergent formulation
- a surfactant system which includes a linear alkyl benzene sulfonate and an alkyl ether sulfate, and a buffering and thickening system, which provides enhanced cleaning power, particularly against resistant dried-on and burnt-on soil.
- the aqueous alkaline hand dishwash liquid detergent formulation is also isotropic and is an un-built hand dishwash liquid detergent formulation.
- Hand dish-wash liquid detergent formulations suitable for washing dishes are well known. However, it is essential that the formulations are able to deliver excellent grease and soil removal at a competitive price. Unfortunately, changing the components and parameters of hand-dish wash formulations often changes the viscosity of the formulations leading to the requirement of more expensive components to balance the effect. Therefore balancing the components of hand dish wash liquid detergent formulations against cleaning performance poses difficulties for hand dish-wash formulators.
- foaming light-duty detergent compositions may be prepared by formulating an anionic alkyl aryl sulfonate and a non-ionic, surface active polyoxyethylene ether of a multi-branched primary aliphatic alcohol or by formulating an anionic sulfate ester of a polyoxyethylene derivative and an anionic alkyl aryl sulfonate, to create a composition at neutral pH.
- US 3332877 discloses a neutral synergistic ternary detergent composition for light duty dishwashing liquids containing at least 30 weight % surfactant derived from two anionic surfactants and a zwitterionic surfactant but does not include the use of a linear alkyl benzene sulfonate.
- WO 93/14183 discloses stable colourless detergent compositions and is particularly interested in soaps, and shampoos comprising from 9 to 95% anionic or non-ionic surfactant. Whilst this document does also mentions hand dish wash formulations, these formulations are also pH neutral and do not comprise a linear alkyl benzene sulfonate.
- US 6225272 discloses a pourable, storage-stable manual dishwashing detergent which contains various surfactants, an electrolyte, optionally a solvent, and at least 45% percent sodium bicarbonate with a mean particle diameter of at least 150 micrometers and provides good pouring properties and cleaning performance.
- the formulation does not include a linear alkyl benzene sulfonate.
- WO 2010/105816 discloses the use of carbamide or a derivative thereof in various detergent compositions such as for example dishwasher detergents, laundry detergents and cleansers.
- the compositions may contain up to 40% by weight of surfactants and electrolytes.
- a hand dish wash formulation is included which comprises a pH of 5.4.
- WO 2013/064356 and WO 2013/064357 disclose structured detergents or cleaning agent compositions with a flow limit and good dispersing properties.
- the detergent compositions comprise a mixture of anionic and non-ionic surfactants as well as inorganic salts and co-surfactants at a pH slightly above neutral.
- CN 102492574 discloses a tableware detergent comprising by weight percent: N-fatty acyl glutamate (0.1 to 10), sulfonate anionic surfactant (1 to 25), non-ionic surfactant (1 to 25) and optionally, amphoterics, polyol wetting agents, electrolytes, pH regulators, antimicrobial agents, essence and water to produce a detergent with a neutral pH.
- US 5952285 discloses a liquid detergent composition containing water, surfactant in a concentration which would in the absence of electrolyte form a pourable hexagonal, or cubic phase at 20 degrees Celsius; and sufficient dissolved electrolyte to form a substantially Newtonian or optically isotropic liquid.
- the object of the present invention is therefore to deliver control of cleaning performance, rheology, and appearance in a hand dish wash concentrate composition at an acceptable cost.
- an alkaline formulation with a specified range of anionic surfactants in combination with a pH adjustment, buffering and thickening system is able to meet the demanding performance requirements of hand dish wash formulations if provided with a sufficient buffering capacity to maintain the alkaline pH during the cleaning process.
- buffering and thickening system is meant a material which is able to maintain the pH of a formulation and generate the required viscosity.
- a particular example is sodium carbonate.
- a builder is able to sequester calcium and magnesium ions.
- a buffer may not necessarily be a builder. This depends on whether or not the functional group is able to sequester calcium and/or magnesium ions.
- carboxylic acid or phosphonate based buffers are also builders whereas amine based buffers are not builders.
- an aqueous alkaline hand dishwash liquid detergent formulation comprising:
- the linear alkyl benzene sulfonate has between 6 to 20 carbon atoms in its alkyl group. It is also preferred that the linear alkyl benzene sulfonate is sodium linear alkyl benzene sulfonate.
- the alkyl ether sulfate has between 8 and 22 carbon atoms in its alkyl group. More preferably the alkyl ether sulfate is sodium alkyl ether sulfate. Even more preferably the sodium alkyl ether sulfate is sodium alkyl ether sulfate (SLES) 1EO.
- the pH of the formulation is preferably in the range 9.2 to 10.8. More preferably the pH of the formulation is in the range 9.2 to 10.5. Even more preferably, the pH of the formulation is in the range 9.2 to 9.8.
- the pH adjustment, buffering and thickening system comprises one or more of the components selected from the group consisting of: sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate. Most preferably, the pH adjustment, buffering and thickening system comprises a mixture of sodium carbonate and sodium hydrogen carbonate.
- the pH adjustment, buffering and thickening system comprises a maximum of 10 wt% of the total formulation. More preferably, however, the buffering and thickening system comprises between 5 and 7 wt% of the total formulation.
- the formulation preferably comprises at least 65 wt% water. More preferably, the formulation comprises at least 68 wt% water.
- the formulation preferably comprises a ratio of linear alkyl benzene sulfonate to alkyl ether sulfate in the range of 1 : 2.2 to 1 : 5.5 by weight. More preferably, the formulation comprises a ratio of linear alkyl benzene sulfonate to alkyl ether sulfate in the range of 1 : 2.2 to 1 : 5.0 by weight. Even more preferably the formulation comprises a ratio of linear alkyl benzene sulfonate to alkyl ether sulfate in the range of 1 : 22 to 1: 1.40 by weight.
- the formulation comprises a ratio of linear alkyl benzene sulfonate to alkyl ether sulfate in the range of 1 : 2.2 to 1 : 3.5 by weight or even 1 : 2.2 to 1 : 3.0 by weight.
- the term 'dish' means a hard surface, as is intended to be cleaned using a hand dish-wash formulation and includes: dishes, glasses, pots, pans, baking dishes and flatware made from any material or a combination of hard surface materials commonly used in the making of articles used for eating and/or cooking.
- the surfactant system is comprised of a mixture of a linear alkyl benzene sulfonate and alkyl ether sulfate with less than 1 wt% of the surfactant system comprising non-ionic surfactant.
- the linear alkyl benzene sulfonate is preferably present in the hand dish wash formulation is an amount of 2 to 5.0 wt%. More preferably the linear alkyl benzene sulfonate is preferably present in the hand dish wash formulation in an amount of from 3 to 5 wt%. More preferably, the linear alkyl benzene sulfonate is preferably present in the hand dish wash formulation is an amount of from 3.25 to 4.95 wt%.
- the linear alkyl benzene sulfonate present in the hand dish wash formulation is in the form of a sodium salt.
- other counter-ions to the linear alkyl benzene sulfonate may be present, such as for example, potassium.
- the preferred length of the alkyl group is C8 to C18.
- the alkyl ether sulfate is preferably present in the hand dish wash formulation in an amount of from 6 to 17 wt%. More preferably, the alkyl ether sulfate is present in the hand dish wash formulation in an amount of from 9 to 15 wt%.
- the alkyl ether sulfate present in the hand dish wash formulation is in the form of a sodium salt.
- other counter-ions to the alkyl ether sulfate may be present, such as for example, potassium.
- the preferred length of the alkyl ether group is C8 to C18 alkyl with 1 to 3 ethoxylate (EO) groups. Most preferably the length of the alkyl ether group is C8 to C18 alkyl with 1 or 2 ethoxylate groups (EO).
- EO ethoxylate
- additional surfactant may be present in the formulation.
- Additional surfactants may be chosen from, for example, other anionic and/or nonionic detergent actives.
- the cleaning formulation may further, or alternatively, comprise cationic, amphoteric and zwitterionic surfactants.
- the surfactant system comprises less than 1 wt% non-ionic surfactant.
- the surfactant system preferably comprises less than 1 wt% cationic surfactants, less than 1 wt% amphoteric surfactants and less than 1 wt% zwitterionic surfactants.
- Suitable synthetic (non-soap) anionic surfactants are water-soluble salts of organic sulphuric acid mono-esters and sulfonic acids which have in the molecular structure a branched or straight chain alkyl group containing from 6 to 22 carbon atoms in the alkyl part.
- anionic surfactants are (primary) long chain (e.g. 6-22 C-atoms) alcohol sulfates (hereinafter referred to as PAS), especially those obtained by sulphating the fatty alcohols produced by reducing the glycerides of tallow or coconut oil; secondary alkanesulfonates; and mixtures thereof.
- PAS primary alcohol sulfates
- alkylglyceryl ether sulfates especially the ethers of fatty alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulfates; sulfates of ethoxylated aliphatic alcohols containing 1-12 ethyleneoxy groups; alkylphenol ethyleneoxy-ether sulfates with from 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralised with alkali, and mixtures thereof.
- Nonionic surfactants tend to reduce the foam produced on use of the composition. Consumers frequently associate high foam with powerful cleaning so it is desirable to either avoid the use of nonionic surfactant altogether, or to use less than 1 wt%.
- suitable nonionic surfactants may be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom.
- the length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group may be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right 'HLB' value to be selected.
- the HLB value is a measure of the hydrophilic/lipophilic balance of such a surfactant.
- nonionic surfactants include: the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut alcohol/ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols having C 6 -C 15 alkyl groups with 5 to 25 moles of ethylene oxide per mole of alkylphenol; and condensates of the reaction product of ethylene-diamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80 wt% of ethyleneoxy groups and having a molecular weight of from 5,000 to 11,000.
- nonionic surfactants include for example: tertiary amine oxides of structure R 1 R 2 R 3 N-O, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, e.g.
- R 1 R 2 R 3 P-O tertiary phosphine oxides of structure R 1 R 2 R 3 P-O, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide
- dialkyl sulphoxides of structure R 1 R 2 S O, where R 1 is an alkyl group of from 10 to 18 carbon atoms and R 2 is methyl or ethyl, for instance methyl-tetradecyl sulphoxide
- fatty acid alkylolamides such as the ethanol amides
- alkyl mercaptans alkyl mercaptans
- the amount present in the cleaning compositions of the invention will generally be at least 0.1 wt%.
- the amount of nonionic surfactant will be in the region of 0.5 wt%.
- Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane-sulfonate and sodium N-2-hydroxy-dodecyl-N-methyltau rate.
- Suitable cationic surfactants may be selected from quaternary ammonium salts having one or two alkyl or aralkyl groups of from 8 to 20 carbon atoms and two or three small aliphatic (for example, methyl) groups, for instance cetyltrimethylammonium chloride.
- a specific group of surfactants are the tertiary amines obtained by condensation of ethylene and/or propylene oxide with long chain aliphatic amines.
- the compounds behave like nonionic surfactants in alkaline medium and like cationic surfactants in acid medium.
- Suitable zwitterionic surfactants may be selected from derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance betaine and betaine derivatives such as alkyl betaine, in particular C 12 -C 16 alkyl betaine, 3-(N,N-dimethyl-N-hexadecylammonium)-propane 1-sulfonate betaine, 3-(dodecylmethyl-sulfonium)-propane 1-sulfonate betaine, 3-(cetylmethyl-phosphonium)-propane-1-sulfonate betaine and N,N-dimethyl-N-dodecyl-glycine.
- betaines are the alkylamidopropyl betaines for example, those wherein the alkylamido group is a
- surfactants are compounds commonly used as surface-active agents given in the well-known textbooks: 'Surface Active Agents' Vol.1, by Schwartz & Perry, Interscience 1949 ; 'Surface Active Agents' Vol.2 by Schwartz, Perry & Berch, Interscience 1958 ; and 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company ; 'Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
- the formulation comprises at least 5 wt% of a pH adjustment, buffering and thickening system.
- the pH adjustment, buffering and thickening system preferably comprises no more than 10 wt% of the total formulation.
- Most preferably the amount of pH adjustment, buffering and thickening system comprises 5 to 7 wt% of the total formulation.
- the components of the pH adjustment, buffering and thickening system are selected from the group consisting of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate.
- the pH adjustment, buffering and thickening system comprises a mixture of sodium carbonate and sodium hydrogen carbonate.
- the pH adjustment, buffering and thickening system provides a formulation with a viscosity level of between 1.8 and 6.0 Pa.s over the preferred pH range of 9.2 to 11. More preferably, the pH adjustment, buffering and thickening system provides a formulation with the required viscosity level of between 1.85 and 6.0 Pa.s over the preferred pH range of 9.2 to 10.8. Even more preferably, the pH adjustment, buffering and thickening system provides a formulation with the required viscosity level of between 1.85 and 6.0 Pa.s over the preferred pH range of 9.2 to 10.5.
- the formulation comprises a perfume.
- the perfume is preferably present in the range from 0.001 to 3 wt%, most preferably 0.1 to 1 wt%.
- Suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
- the formulation may include optional ingredients, such as, abrasive particles and additional ingredients which aid formulation properties, stability and cleaning performance as well as one or more optional ingredients conventionally included in liquid hand dish wash formulations such as, for example: perfume carriers, fluorescers, colourants, hydrotropes, anti-redeposition agents, polyelectrolytes, enzymes, pearlescers, anti-spotting agents, germicides, fungicides, anti-corrosion agents, anti-static agents, crystal growth inhibitors, anti-oxidants, anti-reducing agents, dyes, and water activity modifiers such as sugars, salts, proteins and water soluble homo- and co-polymers.
- optional ingredients such as, abrasive particles and additional ingredients which aid formulation properties, stability and cleaning performance as well as one or more optional ingredients conventionally included in liquid hand dish wash formulations such as, for example: perfume carriers, fluorescers, colourants, hydrotropes, anti-redeposition agents, polyelectrolytes, enzymes, pearlescers, anti-spotting agents, germicide
- preservative is also desirable in the formulation of the present invention, for example a mixture of biocides CIT and MIT (5-Chloro-2-methyl-4-isothiazolinon-3-one / 2-Methyl-4-isothiazolin-3-one).
- BIT (1,2-Benzisothiazol-3(2H)-one) may also be used.
- the level of preservative will vary according to the expected storage temperature and the quality of raw materials. A value of from 0.0001 to 0.1 wt % is typical.
- Sodium EDTA chelant may also be advantageously included in the formulation at a level of 0.01 to 0.5 wt%.
- DMDMH glycol dimethoxylate
- DMDMH glycol dimethoxylate
- the formulation may comprise detergent builders in an amount of from 0.1 to 25 wt%. Suitable inorganic and organic builders are well known to those skilled in the art. For example, citric acid is a preferred buffer/builder and may suitably be included at a level of from 0.01 to 0.5 wt%.
- the formulation may also comprise ingredients such as but not limited to: colorants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, hydrotropes, polymers and perfumes.
- ingredients such as but not limited to: colorants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, hydrotropes, polymers and perfumes.
- optional enzymes include amylase, lipase, cellulase, protease, mannanase, and pectate lyase.
- the alkaline hand dishwash aqueous liquid formulation has a viscosity in the range of from 1.5 to 6.0 Pa.s when measured at a shear rate of 21 s -1 at 25 °C. More preferably the formulation has a viscosity in the range of from 1.75 to 5.5 Pa.s when measured at a shear rate of 21 s -1 at 25 °C. Even more preferably the formulation has a viscosity in the range of from 2.0 to 5.5 Pa.s when measured at a shear rate of 21 s -1 at 25 °C. Still even more preferably the formulation has a viscosity in the range of from 2.5 to 4.5 Pa.s, when measured at a shear rate of 21 s -1 at 25 °C.
- LAS linear alkyl benzene sulfonate
- SLES sodium dodecyl benzene sulfonate
- the viscosity is measured using an Anton Paar Physica - DSR 301 measuring head Automated Sample Changer (ASC), geometry - CC27, DIN concentric cylinder.
- ASC Automated Sample Changer
- the formulation may be packaged in any suitable form of container.
- the formulation is packaged in a plastic bottle with a detachable closure or pouring spout.
- the bottle may be rigid or deformable and may optionally comprise a dosing device to deliver set amounts of liquids when in use.
- a deformable bottle offers the advantage that it allows the bottle to be squeezed to aid dispensing of the liquid formulation.
- clear bottles may be formed from Polyethylene terephthalate (PET). Polyethylene or clarified polypropylene may also be used.
- PET Polyethylene terephthalate
- the container is clear enough so that the liquid formulation with any visual cues therein, is visible from the outside.
- the bottle may also be provided with one or more labels.
- the bottle may be provided with a shrink wrap sleeve which is desirably at least partially transparent, for example, at least 50% of the area of the sleeve is transparent.
- the adhesive used to secure any transparent label to the bottle should preferably not adversely affect the transparency of the bottle.
- Aqueous alkaline hand dishwash liquid detergent formulations were prepared using the components listed in Table 1 over a range of pH concentrations by mixing the ingredients listed therein. The components were diluted further with demineralised water to give the concentration levels indicated in Table1.
- Table 1 COMPONENTS IN LIQUID DETERGENT FORMULATION WEIGHT % WEIGHT % WEIGHT % WEIGHT % pH of Formulation 7.0 8.4 9.2 9.5 10.5 Demineralised Water 82.12 78.59 77.59 76.99 78.09 LAS Acid (Detal) 3.94 3.94 3.94 3.94 3.94 NaOH 1.37 - - - - Sodium hydrogen carbonate (NaHCO 3 ) - 4.50 4.50 4.50 - Sodium Carbonate (Na 2 CO 3 ) - 0.40 1.40 2.00 5.40 SLES 1EO (Texapon N701) 11.80 11.80 11.80 11.80 11.80 11.80 CIT:MIT low salt: Microcare IT 0.00090 0.00090 0.00090 0.00090 0.000
- aqueous alkaline hand dishwash liquid detergent formulations were added in the order set out in Table 1 in which the amounts given define the amount of reagent required in the final formulation based on 100% reagent supplied.
- a 25% solution by weight of each aqueous alkaline hand dishwash liquid detergent formulation listed in Table 1 was prepared using a 3 : 1 weight ratio of water: detergent.
- Soiled brushed stainless steel tiles were prepared by coating the tiles with a three way soil monitor, that is a mixture of fat, protein, and starch and then baked at 100 °C for 1 hour. A number of tiles were then soaked in each of the five aqueous alkaline hand dishwash liquid detergent formulations before cleaning.
- Cleaning was carried out using a custom Martindale Abrasion rig called a WIRA.
- a piece of ballerina cloth was affixed to the cleaning head which was placed in contact with a tile specially designed to simulate a dish surface and to give highly repeatable cleaning results. Cleaning was achieved by moving the cleaning head in a lissajous motion. The soak time prior to the cleaning process was measured using a count-down timer before starting the abrasion rig. Cleaned tiles were rinsed with demineralised water and left to dry overnight before investigating the results of the cleaning process.
- Table 2 Aqueous alkaline hand dishwash liquid detergent formulation pH. Percentage of soil removed, Viscosity of liquid hand wash formulation measured at a shear rate of 21 s -1. (Pa.s). 7 35.00 0.008 8.4 41.50 12.500 9.2 48.00 5.740 9.5 47.50 3.120 10.5 53.25 2.660
- the increase in pH of the aqueous alkaline hand dishwash liquid detergent formulation created by introducing a mixture of carbonate and hydrogen carbonate enabled a formulation to be achieved with a pH above 9, sufficient for un-built hand dish wash formulations.
- a viscosity of at least 1.5_Pa.s is preferred.
- compositions therefore provide an aqueous alkaline hand dishwash liquid detergent formulation which is able to meet the cleaning requirements of obstinate soiling and which still provides the required rheology parameters required of hand dish wash formulations using pH adjustment, buffering and thickening system in the form of a combination of sodium carbonate and sodium hydrogen carbonate.
- Aqueous alkaline hand dishwash liquid detergent formulations were prepared using the components listed in Table 3 over a range of ratios of linear alkyl benzene sulfonate (LAS Acid) to sodium dodecyl benzene sulfonate, at pH 9.5, by mixing the ingredients listed therein. The components were diluted further with demineralised water to give the concentration levels indicated in Table 3.
- LAS Acid linear alkyl benzene sulfonate
- sodium dodecyl benzene sulfonate at pH 9.5
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)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Claims (14)
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse comprenant :i) de 9 à 20 % en masse calculé sur une quantité totale de formulation d'un système de tensioactif ; dans laquelle de 2 à 5 % en masse calculé sur une quantité totale de formulation du système de tensioactif comprennent un alkylbenzènesulfonate linéaire ; et de 7 à 17 % en masse calculé dans une quantité totale de formulation du système de tensioactif comprennent un alkyléthersulfate ; et dans laquelle moins de 1 % en masse calculé sur une quantité totale de formulation du système de tensioactif comprend un tensioactif non-ionique ; et dans laquelle le rapport massique d'alkylbenzènesulfonate linéaire (comme acide LAS) à alkyléthersulfate est inférieur ou égal à 1 : 2,2 ; etii) dans laquelle le pH de la formulation se trouve dans l'intervalle de 9,1 à 11 ;iii) dans laquelle la formulation comprend de plus un système d'ajustement du pH, tampon et épaississant qui comprend au moins 5 % en masse de la formulation totale, dans laquelle le système comprend un ou plusieurs constituants choisis dans le groupe consistant en carbonate de sodium, hydrogénocarbonate de sodium, carbonate de potassium et hydrogénocarbonate de potassium ; etiv) dans laquelle la formulation présente une viscosité dans l'intervalle de 1,5 à 6,0 Pa.s lorsqu'elle est mesurée à une vitesse de cisaillement de 21 s-1 à 25°C ; etdans laquelle la viscosité est mesurée en utilisant un cylindre concentrique Anton Paar Physica - Automated Sample Changer (ASC) à tête de mesure DSR 301, géométrie - CC27.DIN.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon la revendication 1, dans laquelle l'alkylbenzènesulfonate linéaire présente de 6 à 20 atomes de carbone dans son groupe alkyle.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon la revendication 1 ou 2, dans laquelle l'alkylbenzènesulfonate linéaire est un alkylbenzènesulfonate linéaire de sodium.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 3, dans laquelle l'alkyléthersulfate présente de 8 à 22 atomes de carbone dans son groupe alkyle.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 4, dans laquelle l'alkyléthersulfate est un alkyléthersulfate de sodium, encore mieux, SLES 1EO.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 5, dans laquelle le pH se trouve dans l'intervalle de 9,2 à 10,8.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 6, dans laquelle le pH de la formulation se trouve dans l'intervalle de 9,2 à 9,8.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 7, dans laquelle le système d'ajustement du pH, tampon et épaississant consiste en un mélange de carbonate de sodium et d'hydrogénocarbonate de sodium.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 8, dans laquelle le système d'ajustement du pH, tampon et épaississant comprend un maximum de 10 % en masse de la formulation totale.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 8, dans laquelle le système d'ajustement du pH, tampon et épaississant comprend de 5 à 7 % en masse de la formulation totale.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 10, dans laquelle la formulation comprend au moins 65 % en masse d'eau.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 11, dans laquelle la formulation présente un rapport massique d'alkylbenzènesulfonate linéaire à alkyléthersulfate dans l'intervalle de 1 : 2,2 à 1 : 5,0.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 12, dans laquelle la formulation présente un rapport massique d'alkylbenzènesulfonate linéaire à alkyléthersulfate dans l'intervalle de 1 : 2,2 à 1 : 4,0, encore mieux la formulation comprend un rapport massique d'alkylbenzènesulfonate linéaire à alkyléthersulfate dans l'intervalle de 1 : 22 à 1 : 3,5.
- Formulation de détergent liquide pour la vaisselle à la main alcaline aqueuse selon l'une quelconque des revendications 1 à 13, dans laquelle la formulation présente une viscosité dans l'intervalle de 1,75 à 5,5 Pa.s, de préférence de 2,0 à 5,5 Pa.s et encore mieux de 2,5 à 4,5 Pa.s.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14168231 | 2014-05-14 | ||
PCT/EP2015/058969 WO2015172993A2 (fr) | 2014-05-14 | 2015-04-24 | Formulation détergente liquide alcaline aqueuse pour le lavage de la vaisselle à la main |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3143111A2 EP3143111A2 (fr) | 2017-03-22 |
EP3143111B1 true EP3143111B1 (fr) | 2019-06-05 |
Family
ID=50735899
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15717911.0A Active EP3143111B1 (fr) | 2014-05-14 | 2015-04-24 | Formulation alcaline aqueuse de détergent liquide de lave-vaisselle à main |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP3143111B1 (fr) |
CN (1) | CN106459834B (fr) |
AR (1) | AR100381A1 (fr) |
CL (1) | CL2016002855A1 (fr) |
EA (1) | EA031574B1 (fr) |
MY (1) | MY181451A (fr) |
WO (1) | WO2015172993A2 (fr) |
ZA (1) | ZA201607156B (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102017100121A1 (de) * | 2017-01-04 | 2018-07-05 | Franz Ferk | Haarbehandlungsmittel zur topischen Applikation |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5952285A (en) * | 1990-04-10 | 1999-09-14 | Albright & Wilson Limited | Concentrated aqueous surfactant compositions |
AR017744A1 (es) * | 1999-02-08 | 2001-09-12 | Procter & Gamble | Glicoles polimericos y dioles para composiciones detergentes mejoradas para el lavado de vajilla |
DE102012217139A1 (de) * | 2012-09-24 | 2014-03-27 | Henkel Ag & Co. Kgaa | Pastenförmiges Handgeschirrspülmittel |
-
2015
- 2015-04-24 CN CN201580025065.4A patent/CN106459834B/zh active Active
- 2015-04-24 EP EP15717911.0A patent/EP3143111B1/fr active Active
- 2015-04-24 MY MYPI2016704125A patent/MY181451A/en unknown
- 2015-04-24 EA EA201692295A patent/EA031574B1/ru not_active IP Right Cessation
- 2015-04-24 WO PCT/EP2015/058969 patent/WO2015172993A2/fr active Application Filing
- 2015-05-12 AR ARP150101445A patent/AR100381A1/es active IP Right Grant
-
2016
- 2016-10-17 ZA ZA2016/07156A patent/ZA201607156B/en unknown
- 2016-11-10 CL CL2016002855A patent/CL2016002855A1/es unknown
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
WO2015172993A2 (fr) | 2015-11-19 |
ZA201607156B (en) | 2018-05-30 |
EA201692295A1 (ru) | 2017-06-30 |
CN106459834A (zh) | 2017-02-22 |
CL2016002855A1 (es) | 2017-02-24 |
AR100381A1 (es) | 2016-09-28 |
CN106459834B (zh) | 2019-03-22 |
EA031574B1 (ru) | 2019-01-31 |
MY181451A (en) | 2020-12-22 |
WO2015172993A3 (fr) | 2016-01-07 |
EP3143111A2 (fr) | 2017-03-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP4133044B1 (fr) | Composition de détergent pour laver la vaisselle à la main | |
JP2022089915A (ja) | 高濃縮液体配合物における粘弾性を制御するためのeo/poブロックコポリマー界面活性剤の使用 | |
CN104893870A (zh) | 一种不含磷化物的家用自动洗碗机洗涤剂及其制备方法 | |
NZ208156A (en) | Built single-phase liquid detergent compositions containing stabilised enzymes | |
CN107267303A (zh) | 一种洗碗机专用的餐具洗涤粉剂及其制备方法 | |
US11072763B2 (en) | Cleaning composition | |
US20200123468A1 (en) | Cleaning composition | |
JP2019108556A (ja) | 等方性液体洗剤組成物の低温安定性のためのモノアルコール | |
LU85391A1 (fr) | Composition detergente liquide a une seule phase,stabilisee,chargee d'adjuvant de detergence et contenant des enzymes,et procede de lavage utilisant cette composition | |
CN113604296B (zh) | 一种兼具低刺激性、高清洁力和低温稳定性的洗涤剂组合物 | |
CA2910949A1 (fr) | Composition de nettoyage a usages multiples a faible ph | |
EP3143111B1 (fr) | Formulation alcaline aqueuse de détergent liquide de lave-vaisselle à main | |
JP6093280B2 (ja) | 硬質表面用液体洗浄剤組成物 | |
AU2012325190B2 (en) | Cleansing composition | |
US20190153358A1 (en) | Laundry Compositions Having Broad Spectrum Stain Removal | |
JP7478532B2 (ja) | 卵汚れ用固体洗浄剤組成物及び洗浄方法 | |
AU2014395161B2 (en) | Aqueous liquid dishwashing composition | |
JP6093279B2 (ja) | 硬質表面用液体洗浄剤組成物 | |
CN111518631A (zh) | 一种乳化功能增强且易漂洗的洗涤剂组合物 | |
EP3292191B1 (fr) | Compositions de détergent alkalines | |
KR101811404B1 (ko) | 자동 식기 세척기용 액상 세제 조성물 | |
DE102012210993A1 (de) | Verbesserung des Glanzes auf Edelstahl | |
JP2018184494A (ja) | 食器用洗浄剤 | |
WO2024088608A1 (fr) | Combinaison d'adjuvants pour compositions détergentes liquides | |
EP2883949A1 (fr) | Composition lave-vaiselle à main aqueuse renfermant un tensioactif et de l'amylase |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
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 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20161013 |
|
AK | Designated contracting states |
Kind code of ref document: A2 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 |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20180308 |
|
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: 20181218 |
|
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 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1139974 Country of ref document: AT Kind code of ref document: T Effective date: 20190615 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015031368 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20190605 |
|
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: ES 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: 20190605 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: 20190605 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: 20190605 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: 20190605 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: 20190905 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: 20190605 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: 20190605 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190605 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: 20190906 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: 20190905 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: 20190605 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1139974 Country of ref document: AT Kind code of ref document: T Effective date: 20190605 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190605 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: 20191007 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: 20190605 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: 20190605 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: 20190605 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: 20190605 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: 20190605 |
|
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: 20190605 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: 20191005 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015031368 Country of ref document: DE |
|
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: 20190605 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190605 Ref country code: PL 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: 20190605 |
|
26N | No opposition filed |
Effective date: 20200306 |
|
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: 20190605 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602015031368 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190605 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
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: 20200430 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200424 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200430 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200430 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20201103 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200430 |
|
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: 20200430 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200424 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200424 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200424 |
|
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: 20190605 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: 20190605 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190605 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230428 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230421 Year of fee payment: 9 |