EP3545062B1 - Composition de détergent liquide - Google Patents
Composition de détergent liquide Download PDFInfo
- Publication number
- EP3545062B1 EP3545062B1 EP17794705.8A EP17794705A EP3545062B1 EP 3545062 B1 EP3545062 B1 EP 3545062B1 EP 17794705 A EP17794705 A EP 17794705A EP 3545062 B1 EP3545062 B1 EP 3545062B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid detergent
- detergent composition
- anionic surfactant
- composition according
- linear
- 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.)
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
Definitions
- the present invention relates to a liquid detergent composition that provides desirable foaming and soil removal properties. More particularly, the invention concerns a foaming aqueous detergent composition that contains:
- liquid detergent compositions according to the present invention include liquid hand dishwashing detergents and liquid hard surface cleaning compositions.
- liquid detergent compositions according to the invention readily form a cleaning liquid with a rich, creamy foam when mixed with water. After cleaning, the foam can easily be removed from cleaned surfaces by rinsing the surface with only a small amount of rinsing water.
- One way of saving water is to reuse the water and another way is to reduce the amount of water being used.
- Washing processes including laundry, dishwashing and other household cleaning processes, require large amounts of water throughout the world.
- the amount of water required in these washing process is largely determined by the amount of water needed to rinse the newly cleaned article or surface.
- large quantities of water are required to rinse off the foam residues.
- Liquid detergent compositions are widely used to clean all kinds of articles and surfaces. These liquid detergent compositions should be capable of removing all kinds of soils. Furthermore, in order to achieve a good cleaning result, redeposition of soils onto the newly cleaned articles or surfaces should be prevented.
- liquid detergent composition it is also desirable for the liquid detergent composition to provide sustained foaming in dilute cleaning liquid in the presence of the soils being cleaned. However, once an article or surface has been cleaned, this foam is no longer desired and should be removed with difficulty, e.g. by rinsing. Especially in view of the growing scarcity of consumable water it is important to provide liquid detergent compositions that on the one hand provide sustained foaming in the dilute cleaning liquid and that on the other hand provide fast and easy removal of foam residue by rinsing.
- WO 99/35237 describes a clear microemulsion liquid cleaning composition which comprises approximately by weight:
- WO 00/59454 describes a liquid lamellar cleansing composition comprising:
- WO 2006/081944 describes a low foaming aqueous liquid detergent composition comprising a carboxylic ester and/or low-degree alkoxylated derivative, surfactant and water.
- WO 2016/030226 describes a liquid detergent composition having foaming and cleaning characteristics in the main wash, yet significant foam reduction during rinse.
- the compositions comprise an anionic surfactant system, nonionic surfactant and saturated fatty acids.
- US 4017409 describes liquid household cleaner compositions comprising anionic surfactants, organic or inorganic builder salts, a suds suppressing system comprising fatty acid ester and water.
- WO 2011/075642 describes a foaming liquid detergent composition comprising:
- the inventors have developed a liquid detergent composition which is very effective in removing soil from surfaces and which, upon dilution with water, readily produces a cleaning liquid with a rich, creamy foam, which foam can easily be removed from the cleaned surface using only a limited amount of rinsing water.
- the liquid detergent composition of the present invention comprises:
- first and second anionic surfactants in the liquid detergent composition are largely responsible for the formation of a rich, creamy foam when the detergent composition is mixed with water to prepare a cleaning liquid.
- the fatty acid ester of the liquid detergent composition was found to substantially improve foam rinsability after cleaning.
- the combination of the anionic surfactants and fatty acid ester is believed to be responsible for high effectiveness of the liquid detergent composition in the removal of grease from surfaces.
- a first aspect of the present invention relates to a liquid detergent composition
- a liquid detergent composition comprising:
- sulfonate refers to a sulfonic acid residue as well as to salts of sulfonic acid residue.
- sulfurate refers to a sulfuric acid residue as well as to salts of sulfuric acid residue.
- the first anionic surfactant preferably is an ethoxylated alkyl ether sulfate according to formula (I) in which R 1 is a linear C 8 -C 20 alkyl group, more preferably a linear C 10 -C 18 alkyl group, even more preferably a linear C 12 -C 16 alkyl group, yet more preferably a linear a C12-C14 alkyl group and most preferably a C12 alkyl group.
- the liquid detergent composition preferably contains 3-25 wt.%, more preferably 5-20 wt.% and most preferably 6-18 wt.% of the first anionic surfactant.
- the integer n in formula (I) is between 1 and 6, more preferably between 1 and 4 and most preferably between 1 and 3.
- the cation M + in formula (I) preferably is an alkali metal cation, most preferably a sodium cation.
- the second anionic surfactant in the liquid detergent composition of the present invention preferably comprises one or more linear C 8-22 alkylbenzene sulfonates, more preferably one or more linear C 8-18 alkylbenzene sulfonates, even more preferably one or more linear C 10-16 alkylbenzene sulfonates.
- the alkylbenzene sulfonate is linear dodecylbenzene sulfonate.
- the liquid detergent composition contains at least 3 wt.%, more preferably at least 4 wt.%, even more preferably at least 5 wt.% and most preferably at least 6 wt.% of one or more linear C 8-22 alkylbenzene sulfonates.
- the alkylbenzene sulfonate preferably is selected from alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, potassium alkylbenzene sulfonate, ammonium alkylbenzene sulfonate and combinations thereof. Most preferably, the alkylbenzene sulfonate is sodium alkylbenzene sulfonate.
- the benzene-ring of the alkylbenzene sulfonates that is comprised in the liquid detergent composition may carry additional substituents besides the alkyl substituent and the sulfonate substituent. Consequently, the present invention also encompasses the use of, for instance, alkyl toluene sulfonate, alkyl xylene sulfonate and alkyl phenol sulfonate. Most preferably, the benzene-ring of the alkylbenzene sulfonates does not carry any other substituents besides the C 8-22 alkyl substituent and the sulfonate substituent.
- the alkyl sulfate preferably is a linear C 10-16 alkyl sulfate, most preferably a linear dodecyl sulfate.
- the alkyl sulfate preferably is selected from alkyl sulfuric acid, sodium alkyl sulfate, potassium alkyl sulfate, ammonium alkyl sulfate, diethanol amine alkyl sulfate and combinations thereof. Most preferably, the alkyl sulfate is sodium alkyl sulfate.
- the liquid detergent composition preferably contains 3-25 wt.%, more preferably 4-18 wt.% and most preferably 5-15 wt.% of the second anionic surfactant.
- the combination of the first and second anionic surfactant is preferably present in the liquid detergent composition in a concentration of at least 15 wt.%, more preferably of at least 18 wt.% and most preferably of at least 20 wt.%.
- the weight ratio of the first anionic surfactant to the second anionic surfactant in the liquid detergent composition typically is less than 3:1, more preferably less than 2.5:1 and most preferably less 2:1.
- the first anionic surfactant and the second anionic surfactant are typically present in the liquid detergent composition in a weight ratio of the first anionic surfactant to the second anionic surfactant that exceeds 1:3, preferably exceeds 1:2, more preferably exceeds 1:1.5.
- the fatty acid ester according to formula (II) is preferably comprised in the liquid detergent composition in a concentration of 0.2-2 wt.%, more preferably of 0.25-1.7 wt.% and most preferably of 0.3-1.5 wt.%.
- R 3 in formula (II) preferably represents a linear C 1 -C 4 alkyl group, more preferably R 3 is selected from methyl or ethyl. Most preferably, R 3 is methyl.
- R 2 in formula (II) represents a linear C 8-16 alkyl group, more preferably a linear C 10-16 alkyl group.
- the fatty acid ester is selected from the group consisting of methyl decanoate, methyl dodecanoate, methyl tetradecanoate, methyl hexadecanoate and combinations thereof. Most preferably, the fatty acid ester is methyl decanoate.
- the liquid detergent composition according to the present invention comprises at least 0.2 wt. % methyl dodecanoate, more preferably at least 0.25 wt.% methyl dodecanoate, and most preferably at least 0.3 wt.% methyl dodecanoate.
- the water content of the liquid detergent composition preferably is at least 60 wt.%, more preferably at least 62 wt.% and most preferably at least 68 wt.%.
- the pH of the liquid detergent composition typically is between 4.5 and 6.5, more preferably between 5 and 6.5, and most preferably between 5.5 and 6.
- the liquid detergent composition may suitably contain one or more ingredient selected from the group consisting of fragrances, antimicrobial agents, pH modifiers, viscosity modifiers, dyes, enzymes, hydrotropes and combinations thereof.
- the liquid detergent composition may be packaged in the form of any commercially available bottle for storing the liquid.
- the bottle containing the liquid can be of different sizes and shapes to accommodate different volumes of the liquid composition; preferably between 0.25 and 2 L, more preferably between 0.25 and 1.5 L and even between 0.25 and 1 L.
- the bottle is preferably provided with a dispenser, which enables the consumer an easier mode of dispersion of the liquid detergent composition. Spray or pump-dispensers may also be used.
- Another aspect of the present invention relates to a process for cleaning and rinsing a surface comprising the steps of:
- the liquid detergent composition may be applied as such, directly to the surface.
- the composition is preferably diluted with water in a ratio of between 1:1 to 1:10.
- the composition may be applied by any known ways such as by using a scrub, sponge paper, cloth, wipes or any other direct application.
- the applied composition may be cleaned using a cleaning implement such as a scrub, sponge, paper, cloth or wipes.
- Yet another aspect of the invention relates to the use of the fatty acid ester as defined herein before in liquid detergent compositions comprising the first and second anionic surfactants as defined herein before, for accelerating foam removal during rinsing of a surface that has been treated using the liquid detergent composition.
- Liquid detergent compositions were prepared on the basis of the formulations shown in Table 1.
- Table 1 Ingredients In wt.% Ref 1 2 3 4 5 Sodium lauryl ether sulfate 2 EO 12 12 12 12 12 12 Sodium lauryl benzene sulfonate 8 8 8 8 8 Methyl laurate 0 0.1 0.5 1 2.0 2.5 Water Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest
- Table 2 Amount of foam (ml) Ref 1 2 3 4 5 Initial foam 180 177 158 169 162 144 After 1 st rinse 172 170 145 146 115 92 After 2 nd rinse 127 129 106 88 48 25 After 3 rd rinse 69 45 29 8 6 3 After 4 th rinse 27 9 2 1 2 0 After 5 th rinse 10 2 After 6 th rinse 3 After 7 th rinse 1
- Liquid detergent compositions were prepared on the basis of the formulations shown in Table 3.
- Table 3 Ingredients Wt.% Ref 1 2 3 A Sodium lauryl ether sulfate 2 EO 12 12 12 12 12 Sodium lauryl benzene sulfonate 8 8 8 8 Methyl decanoate 1 Methyl dodecanoate 1 Methyl hexadecanoate 1 Octanol 1 Water Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest Rest
- Table 4 Amount of foam (ml) Ref 1 2 3 A Initial foam 180 177 169 152 186 After 1 st rinse 172 167 146 156 172 After 2 nd rinse 127 122 88 121 150 After 3 rd rinse 69 48 8 57 108 After 4 th rinse 27 10 1 13 58 After 5 th rinse 10 2 4 26 After 6 th rinse 3 1 14 After 7 th rinse 1 6
- Liquid detergent formulations were prepared on the basis of the formulations shown in Table 5.
- Formulation B is based on example 2 in Table 1 of WO 2006/081944 .
- Table 5 Ingredients Wt.% 1 B Sodium lauryl ether sulfate 2 EO 12 - Sodium lauryl benzene sulfonate 8 10.22 Neodol 25-9 - 9.5 Methyl laurate 0.5 0.5 Na-citrate - 1.5 TEA - 1 Citric acid - 0.1 Water Rest Rest Rest
- Table 6 Amount of foam (ml) 1 B Initial foam 158 187 After 1 st rinse 145 183 After 2 nd rinse 106 177 After 3 rd rinse 29 127 After 4 th rinse 2 73 After 5 th rinse - 23 After 6 th rinse - 3
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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)
- Cosmetics (AREA)
Claims (15)
- Composition de détergent liquide comprenant :a) un premier tensioactif anionique qui est un alkyléthersulfate éthoxylé selon la formule (I) :
R1-(OCH2CH2)nOSO3 -M+
où R1 représente un groupe alkyle linéaire en C8-C22 ou ramifié ;n est un nombre entier dans l'intervalle de 1-8 ;M+ représente un cation de métal alcalin ou d'ammonium ;b) un second tensioactif anionique choisi dans le groupe consistant en alkylbenzènesulfonates en C8-22, alkylsulfates en C8-22 et combinaisons de ceux-ci ;c) de 0,1 à 2,5 % en masse rapporté à la masse totale de la composition de détergent liquide d'un ester d'acide gras selon la formule (II) :
R2-C(O)-O-R3
où R2 représente un groupe alkyle linéaire en C8-22 ;R3 représente un groupe alkyle linéaire en C1-C4 ou ramifié ;d) au moins 50 % en masse rapporté à la masse totale de la composition de détergent liquide d'eau ;où le premier tensioactif anionique et le second tensioactif anionique constituent ensemble de 12 à 30 % en masse rapporté à la masse totale de la composition de détergent liquide. - Composition de détergent liquide selon la revendication 1, dans laquelle R1 représente un groupe alkyle linéaire en C10-C18.
- Composition de détergent liquide selon la revendication 1 ou 2, où n est de 1 à 4, de préférence de 1 à 3.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où la composition contient 3-25 % en masse du premier tensioactif anionique.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où la composition contient 3-25 % en masse du second tensioactif anionique.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où le second tensioactif anionique est choisi parmi des alkylbenzènesulfonates linéaires en C8-22.
- Composition de détergent liquide selon la revendication 6, où la composition contient au moins 3 % en masse d'un ou plusieurs alkylbenzènesulfonates linéaires en C8-22.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où le rapport massique du premier tensioactif anionique au second tensioactif anionique est inférieur à 3:1 et supérieur à 1:3.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où l'ester d'acide gras est présent dans une concentration de 0,2 à 2 % en masse.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où R3 dans la formule (II) représente un groupe alkyle linéaire en C1-C4.
- Composition de détergent liquide selon la revendication 10, où R3 représente un groupe méthyle.
- Composition de détergent liquide selon l'une quelconque des revendications précédentes, où l'ester d'acide gras est un ester d'acide gras et R2 dans la formule (II) représente un groupe alkyle linéaire en C8-16.
- Composition de détergent liquide selon la revendication 10, où l'ester d'acide gras est un ester d'acide gras choisi dans le groupe consistant en décanoate de méthyle, dodécanoate de méthyle, tétradécanoate de méthyle, hexadécanoate de méthyle et des combinaisons de ceux-ci.
- Procédé de nettoyage et rinçage d'une surface comprenant les étapes de :a) application sur une surface de la composition de détergent liquide selon l'une quelconque des revendications 1 à 13 ;b) nettoyage de la surface avec un outil de nettoyage ; etc) rinçage de la surface avec de l'eau.
- Utilisation de l'ester d'acide gras selon la revendication 1 dans des compositions de détergents liquides comprenant le premier tensioactif anionique selon la revendication 1 et le second tensioactif anionique selon la revendication 1, pour accélérer l'élimination de mousse pendant le rinçage d'une surface qui a été traitée en utilisant la composition de détergent liquide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16200420 | 2016-11-24 | ||
| PCT/EP2017/077583 WO2018095695A1 (fr) | 2016-11-24 | 2017-10-27 | Composition de détergent liquide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3545062A1 EP3545062A1 (fr) | 2019-10-02 |
| EP3545062B1 true EP3545062B1 (fr) | 2020-02-19 |
Family
ID=57394451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17794705.8A Active EP3545062B1 (fr) | 2016-11-24 | 2017-10-27 | Composition de détergent liquide |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3545062B1 (fr) |
| CN (1) | CN109983108A (fr) |
| AR (1) | AR110217A1 (fr) |
| CL (1) | CL2019001327A1 (fr) |
| WO (1) | WO2018095695A1 (fr) |
| ZA (1) | ZA201902304B (fr) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12448587B2 (en) | 2020-12-07 | 2025-10-21 | Conopco Inc. | Hard surface cleaning composition |
| CN116529348B (zh) | 2020-12-07 | 2025-11-25 | 联合利华知识产权控股有限公司 | 硬表面清洁组合物 |
| CN116601276B (zh) * | 2020-12-14 | 2025-02-07 | 联合利华知识产权控股有限公司 | 组合物 |
| WO2023025739A1 (fr) | 2021-08-25 | 2023-03-02 | Unilever Ip Holdings B.V. | Composition de détergent |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU71583A1 (fr) | 1975-01-02 | 1976-11-11 | Procter & Gamble Europ | |
| ZA974226B (en) * | 1996-05-17 | 1998-12-28 | Procter & Gamble | Detergent composition |
| EP0816480A1 (fr) * | 1996-06-26 | 1998-01-07 | The Procter & Gamble Company | Compositions détergentes liquides peu moussantes |
| US5905064A (en) | 1998-01-08 | 1999-05-18 | Colgate-Palmolive Co. | Microemulsion cleaning compositions |
| US6150312A (en) | 1999-04-05 | 2000-11-21 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Liquid composition with enhanced low temperature stability comprising sodium tricedeth sulfate |
| US7205268B2 (en) | 2005-02-04 | 2007-04-17 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Low-foaming liquid laundry detergent |
| CA2784780C (fr) * | 2009-12-17 | 2018-01-16 | Stepan Company | Compositions detergentes a pouvoir moussant pour travaux legers, leurs procedes de fabrication et d'utilisation |
| CN106574217B (zh) * | 2014-08-29 | 2019-05-31 | 荷兰联合利华有限公司 | 液体洗涤剂组合物 |
-
2017
- 2017-10-27 CN CN201780071005.5A patent/CN109983108A/zh active Pending
- 2017-10-27 EP EP17794705.8A patent/EP3545062B1/fr active Active
- 2017-10-27 WO PCT/EP2017/077583 patent/WO2018095695A1/fr not_active Ceased
- 2017-11-23 AR ARP170103260A patent/AR110217A1/es active IP Right Grant
-
2019
- 2019-04-11 ZA ZA2019/02304A patent/ZA201902304B/en unknown
- 2019-05-15 CL CL2019001327A patent/CL2019001327A1/es unknown
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201902304B (en) | 2020-08-26 |
| AR110217A1 (es) | 2019-03-06 |
| EP3545062A1 (fr) | 2019-10-02 |
| WO2018095695A1 (fr) | 2018-05-31 |
| CN109983108A (zh) | 2019-07-05 |
| CL2019001327A1 (es) | 2019-08-09 |
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