EP2931862B1 - Method to prevent discoloration of colored liquids - Google Patents

Method to prevent discoloration of colored liquids Download PDF

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Publication number
EP2931862B1
EP2931862B1 EP13802950.9A EP13802950A EP2931862B1 EP 2931862 B1 EP2931862 B1 EP 2931862B1 EP 13802950 A EP13802950 A EP 13802950A EP 2931862 B1 EP2931862 B1 EP 2931862B1
Authority
EP
European Patent Office
Prior art keywords
composition
liquid
surface treatment
hard surface
textile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP13802950.9A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2931862A1 (en
Inventor
Ashraf MARZOUK
Mohamed ABDELGHANY
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
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP13802950.9A priority Critical patent/EP2931862B1/en
Priority to PL13802950T priority patent/PL2931862T3/pl
Publication of EP2931862A1 publication Critical patent/EP2931862A1/en
Application granted granted Critical
Publication of EP2931862B1 publication Critical patent/EP2931862B1/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/40—Dyes ; Pigments

Definitions

  • the present application relates to a way for protecting dye-containing liquid compositions, such as textile or hard surface treatment compositions, from discoloration.
  • Liquid detergents have traditionally been sold in opaque bottles. However, use of clear (for the present purpose used synonymously with the terms transparent and translucent) bottles can be aesthetically appealing to consumers as they can see the color of the product, its consistency, and suspended particles if they are present.
  • UV light is meant light having wavelength of about 250 to about 460 nanometers (nm).
  • UVA generally is in range 320-400 nm, UVB about 290 to 320 nm and UVC below 290 nm, down to about 250 nm.
  • UV absorbers or UV blockers can be added to the bottle material during manufacture of clear bottles to protect them from becoming brittle and to protect the ingredients inside the bottle.
  • Another approach is the addition of UV absorbers or UV blockers to the formulation.
  • WO 2000/36074 A1 discloses a translucent or transparent aqueous heavy duty liquid in a clear bottle comprising colorant dye and fluorescent dye and/or UV absorber to protect said colorant dye.
  • This object is achieved by a method of reducing destruction of blue colorant dye in a liquid textile or hard surface treatment composition in a bottle that is permeable for UV light by adding ethanol to said composition, in an amount of at least 0.01 % by wt. of the liquid composition.
  • the liquid composition is a liquid textile or hard surface treatment composition.
  • Liquid textile or hard surface treatment compositions are often intensively dyed and, in addition, are packaged in clear bottles.
  • the ethanol is added in amount of at least 0.01 % by wt. of the liquid composition. It has surprisingly been shown that already very little amounts of ethanol are sufficient to effectively reduce the destruction of a colorant dye in a liquid composition.
  • liquid composition comprises an anionic surfactant.
  • Anionic surfactants are important ingredients of many liquid compositions, especially of liquid textile or hard surface treatment compositions. It has been shown that anionic surfactants sometimes promote the destruction of colorant dyes. By adding ethanol to a colored liquid composition the colorant dye is stabilized against the UV light destruction even in the presence of anionic surfactants.
  • the colorant dye is a blue dye. It is even more preferred that the colorant dye is selected from the group consisting of Acid Blue 145, Acid Blue 9, Acid Blue 80, blue anthraquinone dyes, blue xanthene dyes and mixtures thereof. Ethanol is very effective in reducing the destruction of blue dyes being present in a liquid composition
  • the liquid composition is a transparent or translucent liquid composition since stabilization against discoloration/color change is especially necessary in this case.
  • the invention relates to method of reducing destruction of colorant dye in a liquid textile or hard surface treatment composition in a bottle that is permeable for UV light by adding ethanol to said composition.
  • ethanol is added in amount of at least 0.01 % by wt. of the composition.
  • the ethanol is added in amount of at least 0.05 % by wt. of the composition and in an even more preferred embodiment ethanol is added in amount of at least 0.1 % by wt. of the composition.
  • the ethanol is added in amount of up to 5 % by wt. of the composition, more preferably up to 1 % by wt. of the liquid composition and most preferred up to 0.5 % by wt. of the composition.
  • the invention is applicable to any type of blue colorant dye which may be destroyed by UV light.
  • Non limiting examples of such include, but are not limited to the following: Acid Blue 145, Acid Blue 9, Acid Blue 80, anthraquinone dyes, and blue xanthene dyes.
  • the colorant dyes may be present in an amount of from 0.0001% to 1% by wt. of the liquid composition and preferably in an amount of from 0.001 to 0.4% by wt. of the composition.
  • the colorant dye is a blue colorant dye since these dyes showed to be most affected by UV light.
  • the liquid composition is an aqueous liquid composition and contains water as main solvent.
  • the liquid composition is an aqueous liquid textile or hard surface treatment composition.
  • a liquid composition may contain further ingredients that further improve the applications-engineering or aesthetic properties of the liquid composition.
  • a liquid textile or hard surface treatment composition by preference additionally contains one or more substances from the group of surfactants, builder, enzymes, non-aqueous solvents, perfume, thickeners, pH adjusting agents, fluorescing agents, hydrotopes, silicone oils, anti-redeposition agents, anti-gray agents, shrinkage preventers, wrinkle protection agents, dye transfer inhibitors, corrosion inhibitors, antistatic agents, bittering agents, ironing adjuvants, electrolytes, proofing and impregnation agents, swelling and anti-slip agents, softening compounds, biocidal compounds and UV absorbers.
  • surfactants builder, enzymes, non-aqueous solvents, perfume, thickeners, pH adjusting agents, fluorescing agents, hydrotopes, silicone oils, anti-redeposition agents, anti-gray agents, shrinkage preventers, wrinkle protection agents, dye transfer inhibitors, corrosion inhibitors, antistatic agents, bittering agents, ironing adjuvants, electrolytes, proofing and impregnation agents, swelling and anti-
  • surfactants are most preferred included into a liquid textile or hard surface treatment composition.
  • compositions of the method of the invention may contain one or more surfactants selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants and mixtures thereof.
  • the preferred surfactants for use in the liquid textile or hard surface treatment composition are mixtures of anionic surfactants, mixtures of anionic surfactants and nonionic surfactants or mixtures of anionic and ampholytic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants.
  • the surfactant should comprise at least 2.5 % by wt. of the composition.
  • liquid textile or hard surface treatment composition comprises an anionic surfactant.
  • Anionic surfactants are important ingredients of liquid textile or hard surface treatment compositions because of their cleansing and emulsifying properties. Anionic surfactants are particularly good at keeping the dirt away from textile and hard surfaces, and removing oily soil residues from textile and hard surfaces.
  • liquid textile or hard surface treatment compositions may contain a surfactant of the following general formula I: R 1 -O-(AO) n -SO 3 - X + (I), wherein
  • R 1 is a linear or branched, substituted or unsubstituted alkyl-, aryl- or alkylaryl group, preferably a linear, unsubstituted alkyl group, more preferably a fatty alcohol residue.
  • Preferred residues R 1 are chosen from decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl, pentadecyl-, hexadecyl-, heptadecyl-, octadecyl-, nonadecyl-, eicosyl residues und their mixtures, wherein the residues with an even number of carbon atoms are preferred.
  • Particularly preferred residues R 1 are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl-, myristyl-, cetyl- or stearyl alcohol or from C 10 -C 20 -oxo alcohols.
  • AO is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • the index n is an integral number from 1 to 50, preferably from 1 to 20 und most preferably from 2 to 10. Particularly preferred, n is 2, 3, 4, 5, 6, 7 or 8.
  • X is a monovalent cation or the n-th part of an n-valent cation, preferred cations are alkali metal ions, especially Na + or K + , wherein Na + is particularly preferred. Further cations X+ can be chosen from NH 4 + , 1 ⁇ 2 Zn 2+ ,1 ⁇ 2 Mg 2+ ,1 ⁇ 2 Ca 2+ ,1 ⁇ 2 Mn 2+ , and their mixtures.
  • liquid textile or hard surface treatment compositions may contain a surfactant of the following general formula II: R 3 -A-SO 3 - Y + (II), wherein
  • R 3 is a linear or branched, substituted or unsubstituted alkyl-, aryl- or alkylaryl group, preferably a linear, unsubstituted alkyl group, more preferably a fatty alcohol residue.
  • Preferred residues R 1 are chosen from decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl, pentadecyl-, hexadecyl-, heptadecyl-, octadecyl-, nonadecyl-, eicosyl residues und their mixtures, wherein the residues with an even number of carbon atoms are preferred.
  • Particularly preferred residues R 1 are derived from C 12 -C 18 -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl-, myristyl-, cetyl- or stearyl alcohol or from C 10 -C 20 -oxo alcohols.
  • A is -O- or a chemical bond.
  • X is a monovalent cation or the n-th part of an n-valent cation, preferred cations are alkali metal ions, especially Na + or K + , wherein Na + is particularly preferred. Further cations X + can be chosen from NH 4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2Mg 2+ , 1 ⁇ 2Ca 2+ , 1 ⁇ 2Mn 2+ , and their mixtures.
  • formula (II) describes sulphate surfactants or sulfonate surfactants.
  • R 3 preferably is a linear or branched unsubstituted alkylaryl residue.
  • X is a monovalent cation or the n-th part of an n-valent cation, preferred cations are alkali metal ions, especially Na + or K + , wherein Na + is particularly preferred. Further cations X+ can be chosen from NH 4 + , 1 ⁇ 2Zn 2+ ,1 ⁇ 2 Mg 2+ ,1 ⁇ 2 Ca 2+ ,1 ⁇ 2 Mn 2+ , and their mixtures.
  • Such most preferred surfactants are chosen from linear or branched alkyl benzene sulfonates of formula C-2 in which R' and R" together have 9 to 19, preferably 11 to 15 and most preferably 11 to 13 C-atoms.
  • a particularly preferred representative of this formula can be described by formula II-Ba:
  • the anionic surfactant is present at a level of from 1 % up to 20 % by weight of said composition and, preferably, at a level of from 2 % up to 15 % by weight of said composition.
  • the liquid textile or hard surface treatment composition may also contain a non-ionic surfactant as additional ingredient at a level up to 5 % by weight of the liquid textile or hard surface treatment composition.
  • the nonionic surfactant that can be used are by preference alkoxylated, advantageously ethoxylated, in particular primary alcohols having by preference 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) per mol of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position, or can contain mixed linear and methyl-branched residues, such as those that are usually present in oxo alcohol residues.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO, 5 EO, or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C 12-18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 7 EO.
  • the degrees of ethoxylation indicated represent statistical averages, which can correspond to an integral or a fractional number for a specific product.
  • Preferred alcohol ethoxylates exhibit a restricted distribution of homologs (narrow range ethoxylates, NRE).
  • Non-ionic active detergent species that contain EO and PO groups together in the molecule are also usable according to the present invention.
  • mixed alkoxylated nonionic active detergent species in which EO and PO units are distributed statistically rather than in block fashion. Such products are obtainable by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
  • These non-ionic surfactants are obtainable, for example, under the commercial name Dehydol® (from Cognis).
  • Ampholytic surfactants can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be a straight chain or a branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.
  • a preferred ampholytic surfactant is cocamidopropyl betaine.
  • the textile or hard surface treatment composition additionally contains a perfume composition in order to impart a pleasant scent to the laundry treated therewith and to the textile or hard surface treatment composition itself.
  • the liquid textile or hard surface treatment composition contains a perfume composition in a quantity of usually up to 3 wt.%, preferably 0.05 to 2 wt.%, particularly 0.1 to 1.5 wt.% and particularly preferably 0.2 to 1 wt.%, in each case based on the total liquid textile or hard surface treatment composition.
  • the perfume composition can contain individual fragrance compounds, for example the synthetic products of the type of the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Preferably, however, mixtures of various fragrances are used which together produce an attractive scent.
  • the perfume composition can also contain natural fragrance compounds as may be obtained from plant sources.
  • the perfume composition of the textile or hard surface treatment composition can also contain at least one aromatherapy component such as an essential oil.
  • the fabric washing liquid composition comprises an encapsulated perfume and a free perfume. The use of pro-fragrances in the perfume composition may be also advantageous.
  • hard surfaces for example comprise surfaces of stone or ceramic materials, rigid plastics materials, glass, porcelain or metal.
  • Hard surfaces may be, for example, tableware, walls, tiles, work surfaces, painted surfaces, flooring or sanitary articles.
  • the textile or hard surface treatment composition is manufactured using usual and known methods and processes.
  • the constituents of the textile or hard surface treatment composition can be simply mixed in agitator vessels, the water, non-aqueous solvent, ethanol and surfactants usefully being prepared first. After cooling under stirring, if necessary at all, the further constituents are then added in portions.
  • Table 1 below shows the composition of three liquid hard surface treatment compositions E1 to E3. Quantities are indicated in wt% of active matter. Table 1: E1 E2 E3 Alkyl benzene sulfonic acid, sodium salt 13 2 2 Cocamidopropyl betaine 1.5 -- -- Sodium lauryl ether sulfate (2 EO) 4 4 4 Perfume 0.2 0.4 0.33 Acid Blue 9 0.004 0.004 -- Acid Yellow 23 0.0014 -- -- Blue anthraquinone dye -- -- 0.008 NaCl 0.2 2.5 2.5 Na 2 CO 3 -- 0.2 0.2 Bitrex® 0.001 -- -- Ethanol 0.1 0.12 0.12 Water to make 100 wt.%

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP13802950.9A 2012-12-17 2013-12-09 Method to prevent discoloration of colored liquids Revoked EP2931862B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13802950.9A EP2931862B1 (en) 2012-12-17 2013-12-09 Method to prevent discoloration of colored liquids
PL13802950T PL2931862T3 (pl) 2012-12-17 2013-12-09 Sposób zapobiegania przebarwieniu zabarwionych cieczy

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12197548 2012-12-17
EP13802950.9A EP2931862B1 (en) 2012-12-17 2013-12-09 Method to prevent discoloration of colored liquids
PCT/EP2013/075965 WO2014095459A1 (en) 2012-12-17 2013-12-09 Method to prevent discoloration of colored liquids

Publications (2)

Publication Number Publication Date
EP2931862A1 EP2931862A1 (en) 2015-10-21
EP2931862B1 true EP2931862B1 (en) 2020-04-29

Family

ID=47427243

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13802950.9A Revoked EP2931862B1 (en) 2012-12-17 2013-12-09 Method to prevent discoloration of colored liquids

Country Status (4)

Country Link
EP (1) EP2931862B1 (pl)
ES (1) ES2793525T3 (pl)
PL (1) PL2931862T3 (pl)
WO (1) WO2014095459A1 (pl)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3081626A3 (en) 2015-04-13 2016-11-02 Henkel AG & Co. KGaA Method to prevent discoloration of colored liquids
CN115066484A (zh) * 2020-01-29 2022-09-16 联合利华知识产权控股有限公司 洗衣洗涤剂产品

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2359818A (en) 2000-03-01 2001-09-05 Reckitt & Colmann Prod Ltd Hard surface cleaning composition
WO2003006074A2 (en) 2001-07-13 2003-01-23 Gaymar Industries, Inc. Support device with integrated pressure adjustment device and method of use
US20050245429A1 (en) 2004-04-28 2005-11-03 Watson Randall A Antioxidant compositions
WO2006004876A1 (en) 2004-06-29 2006-01-12 The Procter & Gamble Company Laundry detergent compositions with efficient hueing dye
WO2006029188A1 (en) 2004-09-08 2006-03-16 The Procter & Gamble Company Laundry treatment compositions with improved odor
WO2009059872A1 (en) 2007-11-09 2009-05-14 L'oreal Fragrancing composition comprising a combination of a benzotriazole compound, a uva screening agent of the dibenzoylmethane type and a particular uvb screening system
US20100120655A1 (en) 2007-01-26 2010-05-13 Cognis Ip Management Gmbh Clear Aqueous Detergents and Cleaning Agents
US8470755B1 (en) 2012-03-23 2013-06-25 The Procter & Gamble Company Liquid cleaning and disinfecting compositions comprising a zinc inorganic salt

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FR2136913B1 (pl) * 1971-05-07 1973-05-11 Colgate Palmolive Co
AU1535897A (en) * 1996-01-18 1997-08-11 Colgate-Palmolive Company, The Filled package of light duty liquid cleaning composition
US6630437B1 (en) * 1998-12-16 2003-10-07 Unilever Home & Personal Care Usa , Division Of Conopco, Inc. Transparent/translucent liquid compositions in clear bottles comprising colorant and fluorescent dye or UV absorber
US6241788B1 (en) * 1999-11-16 2001-06-05 Betzdearborn Inc. Method of stabilizing dye solutions and stabilized dye compositions
US6756350B1 (en) * 1999-12-29 2004-06-29 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Transparent/translucent bottles

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2359818A (en) 2000-03-01 2001-09-05 Reckitt & Colmann Prod Ltd Hard surface cleaning composition
WO2003006074A2 (en) 2001-07-13 2003-01-23 Gaymar Industries, Inc. Support device with integrated pressure adjustment device and method of use
US20050245429A1 (en) 2004-04-28 2005-11-03 Watson Randall A Antioxidant compositions
WO2006004876A1 (en) 2004-06-29 2006-01-12 The Procter & Gamble Company Laundry detergent compositions with efficient hueing dye
WO2006029188A1 (en) 2004-09-08 2006-03-16 The Procter & Gamble Company Laundry treatment compositions with improved odor
US20100120655A1 (en) 2007-01-26 2010-05-13 Cognis Ip Management Gmbh Clear Aqueous Detergents and Cleaning Agents
WO2009059872A1 (en) 2007-11-09 2009-05-14 L'oreal Fragrancing composition comprising a combination of a benzotriazole compound, a uva screening agent of the dibenzoylmethane type and a particular uvb screening system
US8470755B1 (en) 2012-03-23 2013-06-25 The Procter & Gamble Company Liquid cleaning and disinfecting compositions comprising a zinc inorganic salt

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ALLEN NORMAN S, FATINIKUN KENNETH 0, DAVIES A KEITH, PARSONS BARRY J, PHILLIPS GLYN 0: "FACTORS INFLUENCING THE PHOTOFADING OF COMMERCIAL ANTHRAQUINONE DYES IN SOLUTION", DYES AND PIGMENTS, vol. 2, 1981, pages 219 - 229, XP055981073
ANONYMOUS: "Brilliant blue FCF", WIKIPEDIA, 29 October 2021 (2021-10-29), pages 1 - 7, XP055981082
ANONYMOUS: "Concentrated Dishwashing Detergent Product Description", MINTEL RECORD ID :1284218, April 2010 (2010-04-01), pages 1 - 37, XP055981063
HAJRATWALA B., ET AL.: "The stability of FD&C blue no.1", BRITISH LIBRARY, pages 50 - 86, XP055981079
M. VAN AARDT ET AL.: "Effectiveness of Poly(ethylene terephthalate) and High-Density Polythylene in Protection of Milk Flavor", J. DAIRY SCI., vol. 84, 2001, pages 1341 - 1347, XP026990318

Also Published As

Publication number Publication date
EP2931862A1 (en) 2015-10-21
PL2931862T3 (pl) 2020-10-19
WO2014095459A1 (en) 2014-06-26
ES2793525T3 (es) 2020-11-16

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