EP2843034A1 - Produit de nettoyage ayant un effet de détartrage - Google Patents

Produit de nettoyage ayant un effet de détartrage Download PDF

Info

Publication number
EP2843034A1
EP2843034A1 EP14182845.9A EP14182845A EP2843034A1 EP 2843034 A1 EP2843034 A1 EP 2843034A1 EP 14182845 A EP14182845 A EP 14182845A EP 2843034 A1 EP2843034 A1 EP 2843034A1
Authority
EP
European Patent Office
Prior art keywords
weight
cleaning agent
acid
agent according
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.)
Granted
Application number
EP14182845.9A
Other languages
German (de)
English (en)
Other versions
EP2843034B1 (fr
Inventor
Kadira Nedic
Andreas Brakemeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Werner and Mertz GmbH
Original Assignee
Werner and Mertz GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Werner and Mertz GmbH filed Critical Werner and Mertz GmbH
Publication of EP2843034A1 publication Critical patent/EP2843034A1/fr
Application granted granted Critical
Publication of EP2843034B1 publication Critical patent/EP2843034B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C11D3/2086—Hydroxy carboxylic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • C11D2111/14—

Definitions

  • the invention relates to a detergent with decalcification and its use in particular as a sanitary cleaner or toilet cleaner for domestic or commercial applications.
  • Typical sanitary cleaners with high leaching properties which can also be used efficiently to remove larger limescale structures, contain strong acids, e.g. Hydrochloric acid, phosphoric acid, amidosulfonic acid, formic acid, optionally also in combination or combined with weaker acids.
  • strong acids e.g. Hydrochloric acid, phosphoric acid, amidosulfonic acid, formic acid, optionally also in combination or combined with weaker acids.
  • Such sanitary cleaners are usually very acidic (pH values ⁇ 2.0) and often have skin corrosive properties.
  • the corrosive action, especially of strong acids, is often enhanced in sanitary cleaners by the additional use of surfactants, which are used for the simultaneous removal of grease and lime soap residue as well as for surface area wetting. Since many surfactants make the skin more accessible to other substances, the combination results of acids with surfactants in many cases to an increased irritating or corrosive effect of the preparation compared to a corresponding preparation without surfactants Thus, the addition of 0.1% by weight of a nonionic surfactant generally already leads to a significantly increased skin irritation or skin corrosivity compared to the base preparation without this surfactant additive, as can be demonstrated by validated in vitro skin corrosion test according to OECD 431.
  • the object of the invention is to provide a cleaning agent with kalklösenden properties, which has no or only a slight skin corrosivity despite high descaling effect.
  • the agent should also have a high Kalkseifenfernfernungshack and meet high ecological requirements.
  • detergents are proposed with an acid combination, which show high product performance and yet are user-friendly, being used as the base acids citric acid and / or lactic acid in combination with methanesulfonic acid, which at least one anionic surfactant is added.
  • methanesulfonic acid Due to its high acid strength, methanesulfonic acid is able to significantly increase the lime dissolving power or the rate of limescale removal of citric acid and / or lactic acid solutions already by adding low concentrations. Lactic acid and in particular citric acid are user-friendly due to their only moderate or weak skin irritating effect, but often have not sufficiently high lime-dissolving properties due to their only average acidity. Methanesulfonic acid, on the other hand, has skin-corrosive properties, but due to its high acidity, it increases the lime-dissolving properties of citric acid and / or lactic acid even in low concentrations. By suitable combination of the acid concentrations under control of the methanesulfonic acid fraction, the skin-irritating or corrosive effect of the descaling agent can be controlled.
  • anionic surfactants have generally good skin compatibility
  • anionic surfactants lead to a weakening of the skin corrosivity, in particular of the abovementioned acid combinations, and thus show conflicting properties as do conventional nonionic surfactants.
  • Anionic surfactants obviously also reduce the aggressiveness the acids to the skin.
  • the scouring capacity of the cleaning agent achieved with such anionic surfactants is significantly higher than the otherwise identically composed cleaning agent which, however, hitherto contains conventional nonionic surfactants whose use increases the skin corrosivity of an acidic cleaning agent. Furthermore, the achieved Kalkseifenlinatesti the cleaning agent when using anionic surfactants is often above that of the otherwise identical composition with conventional nonionic surfactants.
  • the cleaning agent according to the invention therefore contains an anionic surfactant or more anionic surfactants. It is also possible to provide mixtures with nonionic and / or amphoteric surfactants
  • the concentration of citric acid and / or lactic acid with added methanesulfonic acid is advantageously adjusted to give a pH of ⁇ 2.0.
  • a strong acidic aqueous detergent having a pH ⁇ 1.5 and especially pH ⁇ 1.0 for the undiluted product, e.g. preferably 0.6 or 0.8, provided.
  • the detergents according to the invention are not skin corrosive according to the validated test method OECD 431.
  • Citric acid or lactic acid may be present in the range up to 30% by weight, in particular up to 20% by weight, preferably up to 15% by weight, and at 0.5 to 8% by weight, in particular up to 5% by weight, preferred to 3% by weight of methanesulfonic acid are combined.
  • the proportion of citric acid may be 4 to 20% by weight, in particular 5 to 12% by weight.
  • Citric acid is preferably used in a proportion of 6 to 10% by weight, in particular 6 to 8% by weight
  • a proportion of from 1 to 10% by weight, in particular from 4 to 10% by weight and more preferably up to about 8% by weight is preferably used
  • the concentration of methanesulfonic acid may be up to 8 wt .-% and is preferably limited to a maximum of 5 wt .-%, in particular to about 3 wt .-%.
  • the proportion of methanesulfonic acid is preferably 0.5 to 2.95% by weight, for example 2.5 to 2.95% by weight. Another preferred range is about 1.5 to 2.95% by weight.
  • organic or inorganic acids may be present in a cleaning agent according to the invention, for example formic acid, acetic acid, gluconic acid, glycolic acid, succinic acid, adipic acid, maleic acid, tartaric acid, malic acid, amidosulfonic acid or phosphoric acid and mixtures thereof.
  • the agent according to the invention contains only citric acid and / or lactic acid and methanesulfonic acid
  • Anionic surfactants according to the invention may be aliphatic sulfates such as fatty alcohol sulfates, iso-alcoholic sulphates (C8-C18), fatty alcohol ether sulphates (C8-C18), dialkyl ether sulphates, monoglyceride sulphates and aliphatic sulphonates such as alkanesulphonates, olefinsulphonates, ether sulphonates, ester sulphonates and lignosulphonates.
  • aliphatic sulfates such as fatty alcohol sulfates, iso-alcoholic sulphates (C8-C18), fatty alcohol ether sulphates (C8-C18), dialkyl ether sulphates, monoglyceride sulphates and aliphatic sulphonates such as alkanesulphonates, olefinsulphonates, ether sulphonates, ester sulphonates and lignosulphon
  • alkylbenzenesulfonates sulfosuccinates (sulfosuccinic acid esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • a detergent according to the invention contains an anionic surfactant or more anionic surfactants from the group of fatty alcohol sulfates or iso-alcohol sulfates (C8-C14) and fatty alcohol ether sulfates (C8-C14) and mixtures of these. Preference is given to n-octylsulfate or iso-octylsulfate.
  • Fatty alcohol sulphates or iso-alcohol sulphates are products of sulphation reactions on corresponding alcohols
  • fatty alcohol ether sulphates are products of sulphation reactions on alkoxylated alcohols.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain Alcohols (C8-C18)
  • n moles of ethylene oxide and one mole of alcohol give, depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation.
  • alkoxylation consists of using mixtures of the alkylene oxides, preferably of the mixture of ethylene oxide and propylene oxide.
  • Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 3 EO, for example 2 EO
  • the anionic surfactants are usually used as salts, but also as acid.
  • the salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, Sodium, potassium or ammonium salts, particularly preferably sodium or potassium salts, most preferably sodium salts such as octyl sulfate Na salt.
  • the total concentration of an anionic surfactant or surfactants in the cleaning agent is preferably in the range up to 5 wt .-%, preferably up to 3 wt .-%, particularly preferably up to 1 wt .-%, such as 0.75 to 0.95 wt .-%.
  • the surfactants are preferably selected from the group of fatty alcohol sulfates or iso-alcohol sulfates (C8-C14) and fatty alcohol ether sulfates (C8-C14), in particular n-octyl sulfate (C8).
  • the cleaning agent may comprise mixtures of these
  • a detergent according to the invention comprises, for example, citric acid or lactic acid in the range of about 4 to 8% by weight in combination with about 0.5 to 2.95% by weight of methanesulfonic acid, the content of anionic surfactant being about 0.75 to 0.95 wt .-% is.
  • the pH value is ⁇ 1.5 and the cleaning agent is not skin corrosive according to OECD 431
  • Another object of the invention is the use of anionic surfactants for damping the skin corrosive action of a strongly acidic decalcifying agent
  • the agent based on citric acid and / or lactic acid with methanesulfonic acid as stated above, is constructed, in addition to the attenuation of skin corrosive / skin irritating Effect also achieved a high lime and Kalkseifenlinatecrypt the acid mixtures especially with n-octyl sulfate (C8).
  • the descaling agent according to the invention is particularly suitable for use as a sanitary or toilet cleaner.
  • the cleaning agent according to the invention may comprise one or more of customary auxiliaries and additives, preferably selected from the group comprising water-soluble solvents, dyes, fragrances, disinfectants and preservatives, corrosion inhibitors, complexing agents for alkaline earth ions, sequestering agents and enzymes
  • customary auxiliaries and additives preferably selected from the group comprising water-soluble solvents, dyes, fragrances, disinfectants and preservatives, corrosion inhibitors, complexing agents for alkaline earth ions, sequestering agents and enzymes
  • suitable emulsifiers are added.
  • the cleaning agent may contain one or more water-soluble, organic solvents, preferably from the group of alcohols or glycols or glycol ethers.
  • the amounts preferably added are from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight.
  • Suitable water-soluble solvents are e.g. the alcohols ethanol, n-propanol, isopropanol, furthermore the ether compounds of ethylene glycol or diethylene glycol or propylene glycol or dipropylene glycol with methanol, ethanol, n- and iso-propanol, n- and iso-butanol, e.g.
  • Ethylene glycol butyl ether (BG), diethylene glycol ethyl ether (EDG), diethyl-glycol butyl ether (BDG), propylene glycol methyl ether (PM), propylene glycol n-butyl ether (PnB, 3-butoxy-2-butanol), dipropylene glycol methyl ether (DPM), dipropylene glycol n-propyl ether ( DPnP), dipropylene glycol n-butyl ether (DPnB) It is also possible to use the diether compounds of the glycols and alcohols mentioned, as well as mixtures of the solvents mentioned.
  • the cleaning agent may contain one or more perfumes, preferably in an amount of from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight, particularly preferably from 0.1 to 0.3% by weight, and / or one or more dyes, preferably in an amount of from 0.0001 to 0.1% by weight, preferably from 0.0005 to 0.05% by weight, particularly preferably from 0.001 to 0.01% by weight
  • a particular form of cleaning is the disinfection.
  • the cleaning agent therefore contains one or more antimicrobial agents. Disinfection is understood as the killing of infectious germs. The extent of disinfection depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial content or increasing dilution of the agent for use.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, phenoxyethanol, lactic acid (if not already present as active ingredient), benzoic acid, salicylic acid and optionally antimicrobial quaternary surface-active compounds.
  • the cleaning agent may contain one or more metal corrosion inhibitors, preferably in an amount of from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, particularly preferably from 0.5 to 2% by weight
  • Suitable corrosion inhibitors are, for example, the following substances: cyclohexylamines, diammonium phosphates, dilithium oxalates, dimethylamino methylpropanol, dipotassium oxalates, dipotassium phosphates, disodium phosphates, disodium pyrophosphates, disodium tetrapropenyl succinates, hexoxyethyl diethylammonium, phosphates, nitromethanes, potassium silicates, sodium aluminates, sodium hexametaphosphates, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • the cleaning agent may also contain one or more complexing agents, preferably in an amount of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, particularly preferably from 0.5 to 3% by weight
  • complexing agents are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, for example clouding.
  • the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents.
  • the complexing agents support the cleaning effect.
  • Suitable are, for example, the following according to INCI designated complexing agents: Aminotrimethylene phosphonic acid, beta-alanines diacetic acid, calcium disodium EDIA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDIA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetra- methylene Phosphonate, Pentasodium Pentetate,
  • the agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the agent according to the invention in any form established according to the prior art.
  • enzymes preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the agent according to the invention in any form established according to the prior art.
  • solutions of the enzymes advantageously as concentrated as possible , low in water and / or added with stabilizers.
  • the method is based on the recommendation for quality assessment for bathroom cleaners (IKW, version 2002) and the recommendation for quality assessment of acidic toilet cleaners (IKW, version 1999)
  • the plates are then immersed for 10 minutes in a defined volume of the decalcifying liquid (a 4-fold determination is carried out for statistical verification of the method). After thorough rinsing of the patten with demineralized water and renewed drying at 105 ° C, the weight loss of each marble slab is determined by weighing. The measured values from the multiple determinations are averaged and recorded. The amount of marble removed (CaCO 3 ) corresponds to the lime-release capacity of the bath cleaner.
  • the temperature of the decalcifying liquid and the marble slabs should be between 20 and 23 ° C during the experiment
  • Kalkseifenlieresti is based on the recommendation for quality evaluation for bathroom cleaners (IKW, version 2002)
  • a defined amount of a dirt suspension is applied. This consists of calcium stearate (lime soap), dye (carbon black) and a solvent
  • the tile is dried at 180 ° C.
  • the solvent evaporates and the molten lime soap remains after cooling with its bound soot back as a solid, smooth layer. Weighing determines the amount of dirt applied.
  • the soiled surface is divided with a stencil into twelve equal rectangular fields (3 rows of 4 fields each). The three rows are now wetted with the various sanitary cleaner.
  • the contact time of the cleaners on the 4 fields of a row varies from 10 min, 7.5 min, 5 min to 2.5 min.
  • the skin irritation test according to OECD 431 reliably identifies potential skin corrosive effects of substances or preparations.
  • This in vitro method uses epidermal 3D skin culture models from recultured human skin
  • the test substance / preparation acts simultaneously on a negative control (distilled water) and a positive control (8 mol / l potassium hydroxide) on the skin tissue.
  • a negative control distilled water
  • a positive control 8 mol / l potassium hydroxide
  • the enzyme activity in the skin tissue is determined via a color reaction.
  • Increasing skin tissue damage (“corrosion") leads to a decrease in enzyme activity or dye production.
  • the specific thresholds for residual enzyme activity or dye production are not reached after 3 minutes and 1 hour, the test substance is classified as "corrosive to the skin”. If these limit values are exceeded, the test substance is correspondingly classified as "non-corrosive to the skin”.
  • exemplary sanitary cleaners are preferably suitable for surface decalcification in the sanitary sector, eg for tiles, sinks, toilet bowls, urinals or fittings.
  • the cleaner in appropriate dilutions with water (1: 1 to 1: 3), the cleaner is of advantage in kettles, coffee machines, etc. for the removal of calcium deposits.
  • decalcifier no. 1 has a high calendering power based on the combination of lactic acid and methanesulfonic acid. Its lime soap dissolving power, however, remains very low due to lack of surfactants
  • the anionic surfactant maintains the high laking power of the otherwise identical but surfactant-free descaling agent. It also increases the Kalkseifenlettesstinum at the same time much stronger than the otherwise identical cleaning agent with a conventional nonionic surfactant addition also results only on addition of the anionic surfactant non-corrosive property.
  • the decalcifying agent No. 4 has a high laking ability in combination with non-corrosive property despite the pH of 0.6.
  • a comparison of the cleaning agents No. 5 and No. 6 shows the superior effect of an anionic surfactant in relation to a nonionic surfactant in terms of laking and lime soap and non-skin corrosive properties.
  • the skin irritation effect of detergent No. 6 is further reduced in comparison with descaling agent No. 4.
EP14182845.9A 2013-08-30 2014-08-29 Produit de nettoyage ayant un effet de détartrage Active EP2843034B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102013217325.3A DE102013217325A1 (de) 2013-08-30 2013-08-30 Reinigungsmittel mit Entkalkungswirkung

Publications (2)

Publication Number Publication Date
EP2843034A1 true EP2843034A1 (fr) 2015-03-04
EP2843034B1 EP2843034B1 (fr) 2018-01-31

Family

ID=51421965

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14182845.9A Active EP2843034B1 (fr) 2013-08-30 2014-08-29 Produit de nettoyage ayant un effet de détartrage

Country Status (2)

Country Link
EP (1) EP2843034B1 (fr)
DE (1) DE102013217325A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019067560A1 (fr) * 2017-09-26 2019-04-04 Ecolab Usa Inc. Compositions antimicrobiennes et virocides acides/anioniques et leurs utilisations
WO2020205360A1 (fr) 2019-04-02 2020-10-08 The Clorox Company Procédé de fabrication de substrats multicouches comprenant des couches en sandwich et du polyéthylène
US11472164B2 (en) 2018-12-21 2022-10-18 The Clorox Company Multi-layer substrates comprising sandwich layers and polyethylene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014641A1 (fr) * 1993-11-29 1995-06-01 The Procter & Gamble Company Compositions pour l'elimination de depots calcaires
WO2007092800A2 (fr) * 2006-02-03 2007-08-16 Advanced Technology Materials, Inc. COMPOSITION D'ELIMINATION DE RESIDU POST-CMP A FAIBLE pH ET PROCEDE D'UTILISATION
CN101372649A (zh) * 2008-09-24 2009-02-25 北京洛娃日化有限公司 一种酸性浴室清洁剂
WO2009124314A1 (fr) * 2008-04-04 2009-10-08 Ecolab Inc. Composition d’élimination du tartre et des résidus de savon qui contient de l’acide méthane sulfonique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2156147T3 (es) * 1994-02-03 2001-06-16 Procter & Gamble Composiciones para eliminar incrustaciones de cal.
FR2939146B1 (fr) * 2008-11-28 2012-11-16 Arkema France Utilisation d'acide alcane sulfonique pour elimination de la rouille
MX349860B (es) * 2011-04-14 2017-08-16 Basf Se Metodo para disolver y/o inhibir el deposito de incrustaciones sobre una superficie de un sistema.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014641A1 (fr) * 1993-11-29 1995-06-01 The Procter & Gamble Company Compositions pour l'elimination de depots calcaires
WO2007092800A2 (fr) * 2006-02-03 2007-08-16 Advanced Technology Materials, Inc. COMPOSITION D'ELIMINATION DE RESIDU POST-CMP A FAIBLE pH ET PROCEDE D'UTILISATION
WO2009124314A1 (fr) * 2008-04-04 2009-10-08 Ecolab Inc. Composition d’élimination du tartre et des résidus de savon qui contient de l’acide méthane sulfonique
CN101372649A (zh) * 2008-09-24 2009-02-25 北京洛娃日化有限公司 一种酸性浴室清洁剂

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019067560A1 (fr) * 2017-09-26 2019-04-04 Ecolab Usa Inc. Compositions antimicrobiennes et virocides acides/anioniques et leurs utilisations
CN111107744A (zh) * 2017-09-26 2020-05-05 埃科莱布美国股份有限公司 酸性/阴离子抗微生物组合物和杀病毒组合物以及其用途
US11026422B2 (en) 2017-09-26 2021-06-08 Ecolab Usa Inc. Acid/anionic antimicrobial and virucidal compositions and uses thereof
US11937602B2 (en) 2017-09-26 2024-03-26 Ecolab Usa Inc. Solid acid/anionic antimicrobial and virucidal compositions and uses thereof
US11950595B2 (en) 2017-09-26 2024-04-09 Ecolab Usa Inc. Acid/anionic antimicrobial and virucidal compositions and uses thereof
US11472164B2 (en) 2018-12-21 2022-10-18 The Clorox Company Multi-layer substrates comprising sandwich layers and polyethylene
US11826989B2 (en) 2018-12-21 2023-11-28 The Clorox Company Multi-layer substrates comprising sandwich layers and polyethylene
US11858238B2 (en) 2018-12-21 2024-01-02 The Clorox Company Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene
WO2020205360A1 (fr) 2019-04-02 2020-10-08 The Clorox Company Procédé de fabrication de substrats multicouches comprenant des couches en sandwich et du polyéthylène

Also Published As

Publication number Publication date
DE102013217325A1 (de) 2015-03-05
EP2843034B1 (fr) 2018-01-31

Similar Documents

Publication Publication Date Title
DE69827845T2 (de) Reinigungsmittel für Keramik- und Porzellanoberflächen sowie hierfür geeignete Verfahren
DD295865A5 (de) Fluessiges reinigungsmittel
EP2494025A1 (fr) Produit de nettoyage antimicrobien pour surfaces dures
EP2970828B1 (fr) Nettoyants pour surfaces dures contenant des esters d'acide phosphorique d'un alkylalcool à modification polyéther
CH663623A5 (de) Saures, fluessiges, das vergussmaterial nicht angreifendes reinigungsmittel fuer keramikplatten.
DE112006001146T5 (de) Haushaltsreinigungszusammensetzung
DE2840463C2 (de) Verwendung eines flüssigen Mittels zum Reinigen harter Oberflächen
DE2336291A1 (de) Fluessiges wasch- und reinigungsmittel
EP2843034B1 (fr) Produit de nettoyage ayant un effet de détartrage
DE69819671T2 (de) Flüssige Reinigungszusammensetzungen und deren Verwendung
EP1335965B1 (fr) Traitement de surfaces pour ameliorer temporairement le comportement a l'enlevement de salissures
EP1619237B1 (fr) Produits de nettoyage concentres aqueux pour carreaux et plaques rugueux de préférence profilés
DE60308824T2 (de) Reinigungs- und instandhaltungszusammensetzung für steinoberflächen
DE19750456A1 (de) Mittel zum Reinigen von harten Oberflächen
DE202013103933U1 (de) Reinigungsmittel mit Entkalkungswirkung
JP3441885B2 (ja) トイレ用洗浄剤組成物
EP4066644A1 (fr) Nettoyant désinfectant, son procédé de production et son utilisation
DE60104512T2 (de) Kalkseifendispergator sowie diesen enthaltenden Wasch- und Reinigungsmittelzusammensetzung
DE102017106717A1 (de) Desinfektions- und Reinigungsmittel
DE2314449A1 (de) Alkalische detergenszubereitung
JP3208223B2 (ja) 硬表面用洗浄剤組成物
EP1232236B1 (fr) Utilisation de formulations destinees au traitement de surfaces permettant l'amelioration temporaire du comportement de decollage des salissures
DE2445710A1 (de) Waschmittelmischung und verfahren zur herstellung derselben
EP3835399B1 (fr) Agent de nettoyage pour surfaces dures
DE2731152C2 (de) Reinigungsmittel für Gegenstände mit harter Oberfläche

Legal Events

Date Code Title Description
17P Request for examination filed

Effective date: 20140829

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

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

R17P Request for examination filed (corrected)

Effective date: 20150902

RBV Designated contracting states (corrected)

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

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170914

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

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: 967405

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180215

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: 502014007078

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

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: 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: 20180131

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: 20180131

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: 20180430

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: 20180131

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: 20180131

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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: 20180531

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: 20180131

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: 20180131

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: 20180430

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: 20180131

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: 20180131

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: 20180501

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: 20180131

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: 20180131

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: 20180131

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: 20180131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014007078

Country of ref document: DE

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: 20180131

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: 20180131

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: 20180131

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: 20180131

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

26N No opposition filed

Effective date: 20181102

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: 20180131

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: 20180131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180829

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

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: 20180829

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: 20180131

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: 20180131

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140829

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: 20180131

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180829

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: 20180131

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20230823

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230831

Year of fee payment: 10

Ref country code: AT

Payment date: 20230818

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230821

Year of fee payment: 10

Ref country code: DE

Payment date: 20230907

Year of fee payment: 10

Ref country code: BE

Payment date: 20230822

Year of fee payment: 10