EP2401351A1 - Liquide vaisselle - Google Patents

Liquide vaisselle

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Publication number
EP2401351A1
EP2401351A1 EP10703660A EP10703660A EP2401351A1 EP 2401351 A1 EP2401351 A1 EP 2401351A1 EP 10703660 A EP10703660 A EP 10703660A EP 10703660 A EP10703660 A EP 10703660A EP 2401351 A1 EP2401351 A1 EP 2401351A1
Authority
EP
European Patent Office
Prior art keywords
surfactant
agent according
cleaning agent
alkyl
surfactants
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
EP10703660A
Other languages
German (de)
English (en)
Other versions
EP2401351B1 (fr
Inventor
Detlef Buisker
Heinz-Dieter Soldanski
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
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Priority to PL10703660T priority Critical patent/PL2401351T3/pl
Publication of EP2401351A1 publication Critical patent/EP2401351A1/fr
Application granted granted Critical
Publication of EP2401351B1 publication Critical patent/EP2401351B1/fr
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the invention relates to an aqueous cleaning agent for hard surfaces, which contains a surfactant combination of fatty alcohol ether sulfate and at least one other surfactant and 10 to 40 wt .-% of a water-soluble salt.
  • This cleaning agent is preferably used for manual dishwashing.
  • Liquid aqueous hand dishwashing detergents are used in countless households. However, in particular in the case of stubborn, encrusted or burnt soiling, they are reaching the limits of their applicability, since longer soaking times and greater mechanical action of force are required in order to achieve a satisfactory cleaning result. If a quick cleaning is desired, therefore, more detergents are used, such as more alkaline cleaning sprays or abrasives. However, this is desirable neither from an economic nor ecological point of view. Another problem is the limited skin compatibility of many conventional hand dishwashing detergents as well as the additional detergents used.
  • an aqueous cleaning agent which contains a special surfactant mixture and additionally has a high concentration of common salt, beyond its saturation point, on the one hand by the abrasive action of the undissolved salt crystals has a particularly good cleaning performance especially on stubborn stains and on the other hand has very good skin compatibility even at low dilution.
  • Water-soluble salts have been used for some time in hard surface cleaners, for example, for viscosity adjustment or as components of buffer systems. But also suspended salt particles already served as abrasives. Thus, WO 2007/085410 A1 introduces a detergent composition in which salt particles can be suspended thanks to an internal structure. However, the surfactant combination of fatty alcohol ether sulfate and at least one other surfactant is not claimed here. A skin-friendly effect was not found for this agent; the cleaning performance of encrusted stains is called "satisfactory".
  • EP 958340 B1 claims a surfactant-containing antibacterial cleaning composition with abrasive particles, which should preferably be salts. However, this agent should be free of anionic surfactants. Neither a good cleaning performance on baked fat soil nor a skin-friendly effect was found. Accordingly, the subject matter of the present invention is an aqueous hard surface cleaner containing a surfactant combination of fatty alcohol ether sulfate and betaine surfactant and 10 to 40% by weight of a water-soluble salt.
  • This detergent is particularly suitable as a hand dishwashing detergent, with the stubborn, burnt or dried dirt can be removed well.
  • a further subject of the present application is accordingly the use of the cleaning agent according to the invention for the manual rinsing of dishes.
  • the cleaning agent according to the invention also has the advantage that it is washed out more slowly from a sponge than a comparable formulation with a smaller amount of salt.
  • the long shelf life in the sponge is particularly advantageous if the items to be washed are cleaned under running water, as it leads to lower losses and thus to a higher efficiency.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • the International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymer ethers, and one or more functions, For example, Surfactants - Cleansing Agents, which in turn explains it in more detail and which may also be referred to below.
  • the indication CAS means that the following sequence of numbers is a designation of the
  • composition according to the invention contains surfactants in a total amount of usually 7 to 40% by weight, preferably 12 to 35% by weight, in particular 16 to 25% by weight.
  • the surfactants are a surfactant combination of fatty alcohol ether sulfate and at least one other surfactant.
  • composition according to the invention can therefore additionally comprise one or more further anionic surfactants, amphoteric surfactants, nonionic surfactants and / or cationic surfactants, in particular for improving cleaning action, run-off behavior and / or drying behavior.
  • the further surfactant is particularly preferably selected from the group comprising nonionic surfactants, in particular fatty alcohol polyglycol ethers, betaine surfactants, secondary alkanesulfonates and mixtures thereof
  • alkyl ether sulfates and alkyl sulfonates and the other anionic surfactants are usually used as alkali metal, alkaline earth metal and / or mono-, di- or Trialkanolammoniumsalz and / or in the form of their with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine used in situ to be neutralized corresponding acid.
  • Particularly preferred are the sodium salts.
  • Alkyl ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally understands, under 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, ie with aliphatic straight-chain or one or more branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms.
  • Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Very particularly preferred for the purposes of the present invention are low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO, such as Na-C 12 - M fatty alcohol + 2EO sulfate.
  • EO ethylene oxide units
  • the composition according to the invention comprises one or more alkyl ether sulfates in an amount of 5 to 20% by weight, preferably 8 to 16% by weight.
  • Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the
  • R 1 is a saturated or unsaturated C 6 . 22 alkyl, preferably C 8 -i 8 alkyl, in particular a saturated C- ⁇ O -i 6 alkyl, for example, a saturated
  • X is NH, NR 4 with the d_ 4 alkyl R 4, O or S, n is a number from 1 to 10, preferably 2 to 5, in particular 3, x is 0 or 1, preferably 1,
  • R 2 , R 3 are independently a C
  • m is a number from 1 to 4, in particular 1, 2 or 3, y 0 or 1 and
  • Preferred betaines are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),
  • betaines are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).
  • a preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).
  • the agent of the invention contains one or more betaines in an amount of usually 1 to 10 wt .-%, preferably 2 to 8 wt .-%.
  • the agents according to the invention preferably also contain one or more alkylsulfonates.
  • Alkyl sulfonates usually have an aliphatic straight-chain or mono- or polysubstituted, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 11 to 18 and more preferably 14 to 17 carbon atoms.
  • suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfonates which are derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ether sulfonates (n-ether sulfonates) having a sulfonate function bonded to the polyether chain are present Ethersulfonate (i-ether sulfonates) with the alkyl-linked sulfonate function distinguishes.
  • alkanesulfonates in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-Ci 3 _i 7 -alkanesulfonate (INCI Sodium C14-17 alkyl lake sulfonates).
  • the agent according to the invention preferably contains one or more secondary alkanesulfonates in an amount of usually 1 to 10% by weight, preferably 2 to 8% by weight.
  • Nonionic surfactants When using a surfactant combination of a) alkyl ether sulfate, b) betaine and optionally c) secondary alkanesulfonate, these are preferably present in a ratio a): b): c) of 2: 1: 0 to 5: 1: 1.
  • Nonionic surfactants a) alkyl ether sulfate, b) betaine and optionally c) secondary alkanesulfonate, these are preferably present in a ratio a): b): c) of 2: 1: 0 to 5: 1: 1.
  • the agent according to the invention may additionally contain one or more nonionic surfactants, usually in an amount of 0.001 to 10 wt .-%, preferably 0.01 to 6 wt .-%, in particular 0.1 to 4 wt .-%, particularly preferably 0 , 2 to 2 wt .-%.
  • Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides.
  • Fatty alcohol polyglycol ethers are under accordance with the invention with ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, branched or unbranched, saturated or unsaturated C 10-22 alcohols with a degree of alkoxylation up to 30 to understand, preferably ethoxylated fatty alcohols with a CIO 18 Degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, particularly preferably from 1 to 8, most preferably from 2 to 5, for example Ci 2 -i 4 -Fettalkoholethoxylate with 2, 3 or 4 EO or a mixture of C 12 - 14 - fatty alcohol ethoxylates with 3 and 4 EO in a weight ratio of 1 to 1 or isotridecyl alcohol ethoxylates with 5, 8 or 12 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • the amine oxides suitable according to the invention include alkylamine oxides, in particular alkyl dimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • alkylamine oxides in particular alkyl dimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides satisfy formula II,
  • Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides.
  • Preferred sugar surfactants within the scope of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters.
  • the ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1.
  • the esters are the reaction products of one or more, preferably one, sugar with a carboxylic acid, especially a C 6-22 fatty acid.
  • Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferred 8 to 14 carbon atoms, a C
  • sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.
  • alkylpolyglycosides are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R 1 O (AO) 3 [G] x in which R 1 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a represent the average degree of alkoxylation of 0 to 20.
  • R 1 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms
  • [G] for a glycosidically linked sugar residue and x for a number from 1 to 10
  • AO for an alkyleneoxy group, for example an ethylene
  • the group (AO) 3 may also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is a to the average Automatalkoxyltechniksgrad, ie the sum of Ethoxyltechniks- and Propoxyltechniksgrad acts.
  • the alkyl radicals R 1 of the APG are linear unsaturated radicals having the specified number of carbon atoms.
  • APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred.
  • the glycosidic sugar used is preferably xylose, but especially glucose.
  • the alkyl or alkenyl radical R ' can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms.
  • Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene's oxosynthesis.
  • the alkyl or alkenyl radical R ' is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • lauryl alcohol myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • elaidyl alcohol petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • alkylpolyglycosides are, for example, C 8 -ioi and C 12 -i 4 -alkylpolyglucoside having a DP degree of 1, 4 or 1.5, in particular C 8 -alkyl-1-5-glucoside and C-1 2 -i 4 -alkyl-1,4-glucoside.
  • composition of the invention may additionally comprise one or more other anionic surfactants, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, more preferably 0.5 to 1, 5 wt .-%, for example, 1 wt .-%.
  • anionic surfactants usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, more preferably 0.5 to 1, 5 wt .-%, for example, 1 wt .-%.
  • Suitable further anionic surfactants are, in particular, aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfos
  • Suitable further anionic surfactants are also anionic gemini surfactants having a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula O 3 S (C 6 H 3 R) O (C 6 H 3 R ') SO 3 ', in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R' is R or H (Dowfax ® Dry hydrotropes Powder with C 16 alkyl radical (s); INCI Sodium Hexyldiphenyl ether sulfonates, Disodium decyl phenyl Ether disulfonates, disodium lauryl phenyl ether disulfonates, disodium cetyl phenyl ether disulfonates).
  • Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the monoesters and diesters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of sulfosuccinic acid.
  • the salts are preferably alkali 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 ammonium salts preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester di-sodium salt (lauryl EO sulfosuccinate, di-Na salt, INCI disodium laureth sulfosuccinate), which is described, for example, as Tego sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate content of 30 wt .-% is commercially available.
  • one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • the agent according to the invention contains as anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5% by weight, preferably 0, 01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 part by weight. %.
  • amphoteric surfactants are amphoteric surfactants.
  • amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the alkylamidoalkylamines are preferred within the scope of the teaching according to the invention.
  • alkylamidoalkylamines are amphoteric surfactants of the formula (IM), R 9 -CO-NR 10 - (CH 2 ), - N (R 11 HCH 2 CH 2 O) - (CH 2 ) HCH (OH) I 1 -CH 2 -Z-OM (III) in which R 9 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -i 8 -alkyl radical, preferably a saturated C 10 -i 6 alkyl radical, for example a saturated C 12 , 14- alkyl radical,
  • R 10 is a hydrogen atom H or a CI_ 4 alkyl radical, preferably H, i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
  • R 11 is a hydrogen atom H or CH 2 COOM (to M su), j is a number from 1 to 4, preferably 1 or 2, in particular 1, k is a number from 0 to 4, preferably 0 or 1,
  • Z is CO, SO 2 , OPO (OR 12 ) or P (O) (OR 12 ), where R 12 is a d_ 4 -alkyl radical or M (su), and M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.
  • Preferred alkyl-substituted amino acids are monoalkyl-substituted amino acids according to formula (IV),
  • R 13 -NH-CH (R 14 ) - (CH 2 ) U -COOM '(IV) in the R 13 is a saturated or unsaturated C 6 . 22 alkyl, preferably C 8 -i 8 alkyl, in particular a saturated C- ⁇ O -i 6 alkyl, for example, a saturated C
  • R 14 is a hydrogen atom H or a CI_ 4 alkyl radical, preferably H, u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
  • M ' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine,
  • M represents a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups may have the same or different meanings, e.g. Hydrogen and sodium or twice sodium may be
  • R 18 is the radical of one of the 20 natural ⁇ -amino acids H 2 NCH (R 18 ) COOH, and M '"is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa),
  • Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids which the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH wear at the amino nitrogen, wherein R 19 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8 -i 8 -alkyl, in particular a saturated do-i ⁇ -alkyl radical, for example a saturated C
  • the acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized in accordance with INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, more preferably cocoamidopropylbetaine.
  • amphoteric surfactants preferably contains at least one amphoteric surfactant is selected from the group comprising Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric ® TC-6), C 8 / io amidopropyl betaine (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ® 810), N-2-hydroxyethyl-N-carboxymethyl -fettklamido-ethylamine-Na (Rewoteric ® AMV) and N-caprylic / capric amidoethyl-N- ethyl ether propionate Na (Rewoteric AMVSF ®) and the betaine 3- (3-cocoamido-propyl) - dimethylammonium-2-hydroxypropanesulfonate (INCI sultaines; Rewoteric AM CAS ®) and the Alkylamidoalkylamin N
  • the agent according to the invention contains one or more
  • Amphoteric surfactants in an amount of more than 8 wt .-%.
  • the inventive composition contains one or more amphoteric surfactants in an amount of less than 2 wt .-%.
  • composition according to the invention may additionally comprise one or more cationic surfactants (cationic surfactants), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 wt .-%.
  • cationic surfactants usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 wt .-%.
  • Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R ') (R ") (R"') (R IV ) N + X ⁇ , in which R 1 to R ⁇ v are identical or different C
  • QAV quaternary ammonium compounds
  • radicals wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, such as a pyridinium or imidazolinium compound, form, and X are ⁇ halide ions, sulfate ions, hydroxide ions or similar anions ,
  • the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary
  • Suitable QUATS are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl- benzylammoniunnchlorid, CAS No. 8001-54-5), Benzalkon B (m, p-dichlorobenzyl-dinnethyl- Ci 2 -alkylamnnoniunnchlorid, CAS No. 58390-78 -6), benzoxonium chloride (benzyldodecyl-bis- (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N, N-dimethyl- benzylammoniunnchlorid, CAS No. 8001-54-5
  • Benzalkon B m, p-dichlorobenzyl-dinnethyl- Ci 2 -al
  • benzetonium chloride N , N-dimethyl-N- [2- [2- [p- (1, 1, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as N-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammoniumbronnide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No.
  • Preferred QUATS are the benzalkonium chlorides containing C 8 -C 18 alkyl radicals, in particular C ⁇ -C M-alkyl-benzyl-dimethylammonium chloride.
  • a particularly preferred QAC is the Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®).
  • anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.
  • the cleaning agent according to the invention also contains one or more water-soluble salts. These may be inorganic and / or organic salts, in a preferred embodiment it is at least one inorganic salt.
  • Inorganic salts which can be used according to the invention are preferably selected from the group comprising colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, therefore, the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. In a preferred embodiment, sodium chloride is used.
  • the organic salts which can be used according to the invention are, in particular, colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or transition metal salts of the carboxylic acids.
  • the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • the cleaning agent according to the invention preferably contains 10 to 40 wt .-%, particularly preferably 15 to 30 wt .-% of at least one water-soluble salt. It should be noted that the salt concentration in the cleaning agent according to the invention must be so high that the salt is not completely dissolved, so the saturation point is exceeded. Furthermore, a salt is preferable whose water solubility changes only slightly over a wide temperature range.
  • exclusively inorganic salts are used, most preferably sodium chloride.
  • the water content of the aqueous composition according to the invention is usually 15 to 60 wt .-%, preferably 20 to 50 wt .-%.
  • the agent according to the invention may advantageously additionally comprise one or more water-soluble organic solvents, usually in an amount of from 0.1 to 10% by weight, preferably from 1 to 8% by weight.
  • the solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or cold stabilizer. It acts solubilizing, prevents the formation of liquid-crystalline phases and contributes to the formation of clear products.
  • the viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can cause excessive viscosity drop. Finally, as the amount of solvent increases, the clouding and clearing point of the composition according to the invention decreases.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C-. 2 o-hydrocarbons, preferably C 2 -i 5 -hydrocarbons, with at least one hydroxy group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms.
  • Preferred solvents are the - optionally etherified on one side with a CI_ 6 alkanol - C 2 - 6 alkylene glycols and poly-C 2 - 3 -alkylene on average 1 to 9 identical or different, preferably identical, alkylene glycol per molecule as well as the CI_ 6 Alcohols, preferably ethanol, n-propanol or iso-propanol, especially ethanol.
  • solvents are the etherified on one side with a CI_ 6 alkanol poly-C. 2 3 - alkylene glycol ethers having on average 1 to 9, preferably 2 to 3, ethylene or propylene glycol groups, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).
  • the solvent is selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol and mixtures thereof.
  • Highly preferred solvents are the C 2 - 3 alcohols ethanol, n-propanol and / or iso-propanol, in particular ethanol.
  • solubilizer in particular for perfume and dyes, for example, alkanolamines and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical can be used in addition to the solvents described above.
  • compositions according to the invention may contain further ingredients.
  • these include, for example, other surfactants, water-insoluble organic and / or inorganic abrasives, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization and other customary in manual dishwashing detergents and additives, such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors , Preservatives, bittering agents, organic salts, disinfectants, enzymes, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume, enzymes), pH adjusters and skin feel enhancing or nourishing additives.
  • other surfactants such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors , Preservatives, bittering agents, organic salts, disinfectants, enzymes, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume, enzymes), pH adjusters and skin feel enhancing or nourishing additives.
  • (Builder) usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to
  • the additives mentioned are dispensed with.
  • composition according to the invention may additionally comprise one or more polymers
  • polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • but particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with CI_ 4 -alkanols, esters (INCI Acrylates Copolymer), to which about Copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Cio- 30- alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C
  • . 4 alkanols formed esters include.
  • the content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%, in particular between 1 and 5 wt .-% and most preferably between 1, 5 and 4% by weight, for example between 2 and 2.5% by weight.
  • the agent is free of polymeric thickeners.
  • one or more dicarboxylic acids and / or salts thereof can be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described, for example, in US Pat Trade name Sokalan DSC is available.
  • the use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1, 3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.
  • a change in the dicarboxylic acid (salt) content can - especially in amounts above 2 wt .-% - contribute to a clear solution of the ingredients. Also, within certain limits, influencing the viscosity of the mixture by this means is possible. Furthermore, this component influences the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30% by weight.
  • the agent according to the invention is preferably free from dicarboxylic acid (salts).
  • one or more further can - especially in hand dishwashing detergents and cleaning agents for hard surfaces - conventional auxiliaries and additives, in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, respectively. this containing mixtures, for example the Euperlane ® Fa.
  • conventional auxiliaries and additives in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, respectively. this containing mixtures, for example the Euperlane ® Fa.
  • the pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, wherein - in particular with the desired hand tolerance - a range from 4 to 9, preferably 5 to 8, in particular 5.5 to 7.5, is preferred.
  • acids such as mineral acids or citric acid
  • alkalis such as sodium or potassium hydroxide
  • the agent according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0 , 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0.1 to 0.5 wt .-%, for example, 0.2 wt .-%.
  • buffer substances which are at the same time complexing agents or even chelating agents (INCI chelating agents).
  • Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium conduction rates, for example trisodium citrate 2 H 2 O and tripotassium citrate H 2 O.
  • composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes. Due to the contained surfactant combination, it is characterized by a good drainage and drying behavior, thanks to the abrasive action of the salts it contains, it also has a very good cleaning performance, even on stubborn and baked stains, and finally, it also has a high skin friendliness.
  • compositions according to the invention were prepared, the compositions of which are shown in the table below.
  • the quantities are in wt .-%.
  • the hand dishwashing detergents obtained were stable, pourable and readily dosed and had good cleaning, drainage and drying behavior.
  • a comparative formulation V1 was prepared which was similar in composition to E7 but did not contain sodium chloride.
  • Cocoamidopropylbetaine 2.50 3.33 3.10 3.10 3.00 3.00 3.00
  • compositions of the invention showed improved skin compatibility compared to the comparison means V1.
  • an elbow flexion test was performed.
  • the formulations E7 and V1 were each used in 25% dilution.
  • the application in the elbow was made by the subjects themselves 2x daily for a total of 6 minutes.
  • the skin reactions were assessed before the next application.
  • the skin at the elbow was examined by measuring skin moisture and barrier function (TEWL). During the entire test period, the application site was not creamed.
  • TEWL skin moisture and barrier function
  • the comparator V1 induced slight to very severe scaling, mild to very strong erythema (redness) and a slight fissure. In addition, subjects often reported itching, burning and tightness during and after washing.
  • Sponge load life was determined by the following procedure:

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Abstract

La présente invention a pour objet un détergent aqueux pour les surfaces dures, qui contient une combinaison d'agents tensioactifs à base de sulfate d'éther d'alcool gras et d'au moins un autre agent tensioactif, comme de 10 à 40 % en poids d'un sel soluble dans l'eau, qui peut être utilisé pour effectuer le nettoyage de la vaisselle à la main et qui convient particulièrement à l'élimination des taches rebelles, brûlées ou séchées et qui protège la peau.
EP10703660.0A 2009-02-26 2010-02-17 Liquide vaisselle Active EP2401351B1 (fr)

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DE102009001186A DE102009001186A1 (de) 2009-02-26 2009-02-26 Handgeschirrspülmittel
PCT/EP2010/051948 WO2010097316A1 (fr) 2009-02-26 2010-02-17 Liquide vaisselle

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KR (1) KR101730190B1 (fr)
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US20120071379A1 (en) * 2010-09-21 2012-03-22 Denis Alfred Gonzales Liquid cleaning composition
GB201108912D0 (en) * 2011-05-27 2011-07-13 Reckitt Benckiser Nv Composition
DE102012222186A1 (de) * 2012-12-04 2014-06-05 Henkel Ag & Co. Kgaa Strukturiertes Reinigungsmittel mit Fließgrenze
WO2014200656A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant de streptomyces umbrinus
WO2014200657A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant destreptomyces xiamenensis
WO2014200658A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase issue de promicromonospora vindobonensis
EP3011020A1 (fr) 2013-06-17 2016-04-27 Danisco US Inc. Alpha-amylase issue d'un membre de la famille des bacillaceae
CN105452434B (zh) * 2013-07-19 2018-09-28 狮王株式会社 擦拭用液体洗涤剂
US20160160199A1 (en) 2013-10-03 2016-06-09 Danisco Us Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
WO2015050724A1 (fr) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases faisant partie d'un sous-ensemble d'exiguobacterium, et procédés d'utilisation correspondants
MX2016006489A (es) 2013-11-20 2016-08-03 Danisco Us Inc Alfa-amilasas variantes que tienen susceptibilidad reducida a la escision por proteasas y metodos de uso.
KR102166027B1 (ko) * 2013-11-22 2020-10-15 주식회사 엘지생활건강 액체 세제 조성물
DE102013224454A1 (de) 2013-11-28 2015-05-28 Henkel Ag & Co. Kgaa Handgeschirrspülmittel mit verbesserter Reichweite
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PL2401351T3 (pl) 2016-03-31
KR20110124247A (ko) 2011-11-16
EP2401351B1 (fr) 2015-10-07
US8329631B2 (en) 2012-12-11
DE102009001186A1 (de) 2010-09-02
WO2010097316A1 (fr) 2010-09-02
US20110312868A1 (en) 2011-12-22
WO2010097316A9 (fr) 2011-10-20
ES2558437T3 (es) 2016-02-04
KR101730190B1 (ko) 2017-04-25

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