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WO2018127323A1 - Composition de nettoyage de surface dure - Google Patents

Composition de nettoyage de surface dure Download PDF

Info

Publication number
WO2018127323A1
WO2018127323A1 PCT/EP2017/079917 EP2017079917W WO2018127323A1 WO 2018127323 A1 WO2018127323 A1 WO 2018127323A1 EP 2017079917 W EP2017079917 W EP 2017079917W WO 2018127323 A1 WO2018127323 A1 WO 2018127323A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
detergent surfactant
hard surface
cleaning
composition according
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.)
Ceased
Application number
PCT/EP2017/079917
Other languages
English (en)
Inventor
Punam Bandyopadhyay
Jiji Paul Kottukapally
Uma Madhavan
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.)
Unilever NV
Conopco Inc
Original Assignee
Unilever NV
Conopco Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever NV, Conopco Inc filed Critical Unilever NV
Priority to EP17808391.1A priority Critical patent/EP3565879B1/fr
Priority to CN201780082027.1A priority patent/CN110139921B/zh
Publication of WO2018127323A1 publication Critical patent/WO2018127323A1/fr
Priority to ZA2019/03631A priority patent/ZA201903631B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid 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
    • 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to a hard surface cleaning composition.
  • dishwashing and household cleaning include cleaning of hard surfaces like e.g. utensils, dishes, sinks, platforms, kitchen tops, tiles, floors, cupboards and doors.
  • hard surfaces like these are cleaned by applying a hard surface cleaning composition in neat or diluted form followed by cleaning the hard surface with a suitable means like e.g. scrub, sponge, paper, cloth, wipes and simply by using hands, and rinsing the hard surface.
  • JP 05-072960 discloses an acidic detergent composition of pH of 1.5 to 4.0 comprising anionic surfactant which has sulfonic acid or a sulfuric acid group, water- soluble polyacrylic acid or its salt and an organic acid.
  • composition that comprises a specific combination of anionic detergent surfactant, a polymer comprising acrylic acid and water and has pH of 5.5 or lower.
  • the present invention provides a hard surface cleaning composition comprising:
  • composition is free of silicone and free of metal bleach catalyst
  • composition has pH of 5.5 or lower;
  • detergent surfactant is a combination of alkyl ether sulfate (AES) and alkyl benzene sulfonate (ABS) wherein the ratio of AES:ABS is at least 1 :1 .
  • the present invention provides a method of cleaning a hard surface comprising the steps of:
  • the present invention relates to a composition that comprises a specific combination of anionic detergent surfactant, a polymer comprising acrylic acid, water and has pH of 5.5 or lower.
  • detergent surfactant i.e. anionic, nonionic, amphoteric and cationic detergent surfactant.
  • Detergent surfactants are one of the main ingredients that are known to provide cleaning effect.
  • composition according to the present invention comprises from 5 to 60 wt%, preferably from 10 to 50 wt%, more preferably from 20 to 40 wt% and even more preferably from 30 to 35 wt% of detergent surfactant.
  • Out of the total amount of detergent surfactant is made up of a combination of, alkyl ether sulfate (AES) and alkyl benzene sulfonate (ABS).
  • AES alkyl ether sulfate
  • ABS alkyl benzene sulfonate
  • composition comprises 60 wt% detergent surfactant then at least 50% of detergent surfactant, i.e. 30 wt% of the composition in this case, is made up of AES and ABS.
  • AES is an anionic detergent surfactant of the formula Ri-(OR') n -0-S03 " M + ,
  • Ri is saturated or unsaturated C8-C16, preferably C12-C14 alkyi chain; preferably, Ri is a saturated Cs-Ci6, more preferably a saturated C12-C14 alkyi chain;
  • R' is ethylene; n is from 1 to 18; preferably from 1 to 15, more preferably from 1 to 10 and even more preferably from 1 to 5.
  • M + is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.
  • AES sodium lauryl ether sulfate
  • SLES sodium myristyl ether sulfate
  • sodium palmityl ether sulfate Preferred AES is SLES having 1 to 3 ethylene oxide units per molecule is preferred. SLES having 1 to 2 ethylene oxide units per molecule is the most preferred.
  • SLES is found in many products like e.g. soaps, shampoos, toothpaste and cleaning compositions including laundry and hard surfaces.
  • ABS is an anionic detergent surfactant that includes water soluble alkali metal salts of organic sulfonates having alkyi radicals typically containing from 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms, more preferably from 12 to 15 carbon atoms and may be unsaturated.
  • ABS examples include sodium salt of linear alkyi benzene sulfonate (LAS), alkyi toluene sulfonate, alkyi xylene sulfonate, alkyi phenol sulfonate, alkyi naphthalene sulfonate, ammonium diamylnaphthalene sulfonate and sodium dinonylnaphthalene sulfonate and mixtures with olefin sulfonate.
  • LAS linear alkyi benzene sulfonate
  • alkyi xylene sulfonate alkyi phenol sulfonate
  • alkyi naphthalene sulfonate alkyi naphthalene sulfonate
  • ABS is LAS having alkyi radicals containing from 12 to 14 carbon atoms.
  • the detergent surfactant of the composition comprises at least 50% of its total amount as a combination of AES and ABS.
  • the ratio of AES:ABS, weight by weight, is at least 1 :1 , preferably at least 2:1 , more preferably at least 3:1 , even more preferably at least 4:1 further more preferably at least 6:1 and still more preferably at least 8:1 .
  • amount of AES is more than that of ABS. Additional detergent surfactant
  • composition may further comprise one or more additional detergent surfactant, i.e. in addition to AES and ABS, as part of the detergent surfactant.
  • additional detergent surfactant can be selected from anionic, nonionic, cationic, and amphoteric types of detergent surfactant.
  • anionic detergent surfactant other than SLES and LAS are sodium lauryl sulfate, ammonium lauryl sulfate, soap, diethanolamine lauryl sulphate.
  • nonionic detergent surfactant examples include the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 1 1 EO per mole of alcohol.
  • a higher alcohol e.g.
  • lauryl alcohol condensed with 5, 7 and 9 moles of ethylene oxide (laureth 5, laureth 7 and laureth 9).
  • Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-Cio-C2o alkanoic acid esters having a HLB of 8 to 15 like e.g. polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate may also be employed as the nonionic detergent surfactant.
  • These surfactants are commercially available from Imperial Chemical Industries under the trade name TweenTM.
  • Preferred nonionic detergent surfactant are laureth 5, laureth 7 and laureth 9.
  • Illustrative examples of cationic detergent surfactant are quaternary ammonium salts characterised in that the ammonium salt has the general formula: R-i R2R3R 4 N + X " , wherein Ri is a C12-C18 alkyl group, each of R2, R3 and R 4 independently is a C1-C3 alkyl group and X is an inorganic anion.
  • Ri is preferably a Ci 4 -Ci6 straight chain alkyl group, more preferably C16.
  • R2-R 4 are preferably methyl groups.
  • the inorganic anion is preferably chosen from halide, sulphate, bisulphate or OH " .
  • a quaternary ammonium hydroxide is considered to be a quaternary ammonium salt. More preferably the anion is a halide ion or sulphate, most preferably a chloride, bromide or sulphate. Cetyl trimethylammonium bromide is a specific example of a suitable compound.
  • benzalkonium halides also known as alkyldimethylbenzylammonium halides.
  • alkyldimethylbenzylammonium chlorides or ADBAC.
  • a preferred class of bezalkonium chlorides is given in the formula below.
  • Amphoteric detergent surfactant can be of amide, betaine, and amine oxide type, i.e. cocoamidopropyl betaine, coco amido propyl amine oxide, cocodiethanol amide and cocomonoethanol amide.
  • Preferred amphoteric detergent surfactant is cocoamidopropyl betaine.
  • these additional detergent surfactant can be used in an amount from 0.1 to 30 wt%, preferably from 1 to 25 wt%, more preferably from 3 to 20 wt%, even more preferably from 5 to 15 wt% and further more preferably from 8 to 13 wt%.
  • 25 wt% of additional detergent surfactant means that if the composition comprises 60 wt% detergent surfactant, the 60 wt% is made up of 35 wt% AES and ABS with the remaining 25 wt% being additional detergent surfactant.
  • the composition further comprises a polymer comprising acrylic acid.
  • the polymer can be a homopolymer or a copolymer.
  • the composition may comprise a combination of homopolymer and a copolymer comprising acrylic acid.
  • polymer in combination with detergent surfactant of the composition enhances cleaning. It also enhances foaming capacity, i.e. volume of foam, of the composition.
  • foaming capacity i.e. volume of foam
  • homopolymer of acrylic acid are, hydrophobically modified acrylic based polymer emulsion commercially available under trade name AcusolTM 805s and acrylic acid homopolymer commercially available under trade name AcusolTM 445.
  • Preferred homopolymer is acrylic acid homopolymer.
  • copolymer comprising acrylic acid are, polymer of acrylic and methacrylic acid esters commercially available under trade name AcusolTM 845, copolymer of acrylic acid and maleic anhydride commercially available under trade name AcusolTM 497N and acrylic/maleic acid copolymer commercially available under trade name AcusolTM 505N.
  • Preferred copolymer comprising acrylic acid is polymer of acrylic and methacrylic acid esters.
  • the total amount of polymer comprising acrylic acid that can be present in the composition ranges from 0.5 to 4 wt%, preferably from 0.8 to 3.5 wt%, more preferably from 1 to 3.2 wt%, even more preferably from 1 .3 to 3 wt% and further more preferably from 1 .5 to 2.8 wt%.
  • the composition further comprises water.
  • the amount of water ranges preferably from 40 to 94 wt%, more preferably from 50 to 90 wt%, even more preferably from 60 to 80 wt% and further more preferably from 65 to 75 wt%.
  • the composition is free of silicone. It has been found that silicone compromises the soil tolerance of the composition. Silicone is meant to include any derivative thereof. Free of silicone is defined as not more than 1 .5 wt% silicone on total composition. Preferably the composition comprises not more than 1 wt%, more preferably not more than 0.5 wt% silicone. Even more preferably the composition is essentially free of silicone and does not comprise any silicone.
  • the composition is free of metal bleach catalyst.
  • Free of metal bleach catalyst is defined as not more than 0.05 wt% metal bleach catalyst.
  • the composition is essentially free of metal bleach catalyst and does not comprise any metal bleach catalyst.
  • the composition is free of any bleach as this may be considered too harsh for use as a hand dish wash composition.
  • Bleach includes compounds containing chlorine like e.g. hypochlorite, hydrogen peroxide, ozone and the like. Free of bleach is defined as not more than 1 .5 wt% bleach on total composition.
  • the composition comprises not more than 1 wt%, more preferably not more than 0.5 wt% bleach. Even more preferably the composition is essentially free of bleach and does not comprise any bleach. pH of the composition
  • a polymer as described above, in combination with detergent surfactant of the composition was found to enhance cleaning. It also enhanced the foaming capacity, i.e. volume of foam, of the composition. However, these effects were found to be pH dependent and were obtained only when the pH of the composition was 5.5 or lower.
  • the pH of composition is 5.5 or lower, preferably lower than 5.0, more preferably lower than 4.5, even more preferably lower than 4.0 and further more preferably lower than 3.5.
  • the pH was adjusted using conventional pH adjusters like citric acid and sodium hydroxide.
  • the hard surface cleaning composition comprises:
  • composition has an acidic pH of 5 or lower;
  • At least 50% of the total amount of surfactant is a combination of AES and ABS wherein the ratio of AES:ABS is at least 1 :1 .
  • the composition may be used as is, i.e. neat, or it may be diluted before use.
  • the composition is typically applied in its neat form directly to the surface.
  • the composition may be diluted with water in a ratio 1 :1 to 1 :10.
  • composition may further comprise optional ingredients like e.g. such as colorants, preservatives, antimicrobial agents, perfumes, sequesterants and hydrotropes and polymer like e.g. POLYOXTM WSR N60K, which aid in the cleaning or sensory performance.
  • optional ingredients like e.g. such as colorants, preservatives, antimicrobial agents, perfumes, sequesterants and hydrotropes and polymer like e.g. POLYOXTM WSR N60K, which aid in the cleaning or sensory performance.
  • the present invention relates to a method of cleaning a hard surface comprising steps of:
  • the composition may be applied to a hard surface by using any suitable means like e.g. by using a scrub, sponge, paper, cloth, wipes or simply by using hands for directly applying the composition.
  • the hard surface can then be cleaned using the same suitable means.
  • compositions shown in examples 1 , 2 and 3 were prepared as described below and using amounts of SLES, LAS and polymer comprising acrylic acid as shown in the respective compositions in examples 1 , 2 and 3 below. All the compositions contained balance water to 100 wt% and contained minors like perfume color.
  • the soil used for testing is a mix of wheat flour (Aashirvaad Select Superior Sharbati Atta from ITC), sunflower oil (Sunpure, MK Agrotech Pvt Ltd), oleic acid (Loba Chemie), and stearic acid (SD fine chemicals Ltd).
  • the typical composition of the soil is provided in Table 1.
  • Table 1 Composition of soil
  • Stearic acid and oleic acid were added to sunflower oil and heated till stearic acid melted. Water heated to 60°C was added to wheat flour and mixed thoroughly so as to avoid any lumps. The oil mixture was then added to wheat flour and mixed thoroughly. Finally remaining amount of boiling water was added to the mixture and stirred so as to break all the lumps. This mixture was then heated on a hot plate and allowed to bubble for 3 to 4 minutes. Finally, the mixture was left to cool at room temperature before using it for the studies.
  • control a composition that contained 18 wt% of detergent surfactant containing SLES and LAS in 1 :1 ratio was used.
  • the initial foam volume of the control when measured by the method described above, was found to be 210 mL and was considered as 100%.
  • compositions as per the present invention despite using reduced detergent surfactant (13 wt%) than that contained in the control (18 wt%), provided as efficacious cleaning, i.e. soil tolerance, as that provided by the control.
  • the compositions of the present invention were also found to provide as much foaming capacity, i.e. volume of foam, as that provided by the control.
  • Example 4 Effect of silicone on soil tolerance
  • PDMS polvdimethylsiloxane

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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)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une composition de nettoyage de surface dure comprenant : • 5 à 60 % massiques d'un tensioactif détergent, • 0,5 à 4 % massiques d'un polymère comprenant de l'acide acrylique et • de l'eau ; la composition étant exempte de silicone et de catalyseur de blanchiment métallique ; la composition présentant un pH égal ou inférieur à 5,5 ; et au moins 50 % de la quantité totale de tensioactif détergent correspondant à une combinaison d'alkyl éther sulfate et de sulfonate d'alkylbenzène, le rapport entre l'alkyl éther sulfate et le sulfonate d'alkylbenzène étant au moins égal à 1/1. L'invention concerne également un procédé de nettoyage d'une surface dure comprenant les étapes consistant : a. à appliquer sur une surface dure ladite composition sous forme pure ou diluée, b. à nettoyer la surface dure et c. à rincer la surface dure.
PCT/EP2017/079917 2017-01-09 2017-11-21 Composition de nettoyage de surface dure Ceased WO2018127323A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP17808391.1A EP3565879B1 (fr) 2017-01-09 2017-11-21 Composition de nettoyage d'une surface dure
CN201780082027.1A CN110139921B (zh) 2017-01-09 2017-11-21 硬表面清洁组合物
ZA2019/03631A ZA201903631B (en) 2017-01-09 2019-06-06 A hard surface cleaning composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17150663 2017-01-09
EP17150663.7 2017-01-09

Publications (1)

Publication Number Publication Date
WO2018127323A1 true WO2018127323A1 (fr) 2018-07-12

Family

ID=57755227

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/079917 Ceased WO2018127323A1 (fr) 2017-01-09 2017-11-21 Composition de nettoyage de surface dure

Country Status (4)

Country Link
EP (1) EP3565879B1 (fr)
CN (1) CN110139921B (fr)
WO (1) WO2018127323A1 (fr)
ZA (1) ZA201903631B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112251299A (zh) * 2020-10-21 2021-01-22 沈阳脱普生活用品服务有限公司上海分公司 高浓缩清洁剂及其制备方法
CN116529349B (zh) * 2020-12-07 2024-08-27 联合利华知识产权控股有限公司 硬表面清洁组合物
CN112961738A (zh) * 2021-02-05 2021-06-15 上海佐航新材料科技有限公司 一种新型碱性硬地面清洗剂及其制备方法

Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH0572960A (ja) 1991-09-11 1993-03-26 Toppan Printing Co Ltd ホログラフイツク光学素子の作製方法
US5962398A (en) * 1997-01-14 1999-10-05 Lever Brothers Company Isotropic liquids incorporating anionic polymers which are not hydrophobically modified
US20110230385A1 (en) * 2008-06-17 2011-09-22 Colgate Palmolive Company Light duty liquid cleaning compositions and methods of manufacture and use thereof
US20120208739A1 (en) * 2011-02-16 2012-08-16 Robert Richard Dykstra Liquid cleaning compositions
WO2013107778A1 (fr) * 2012-01-18 2013-07-25 Unilever Plc Compositions pour traitement capillaire

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US5364551A (en) * 1993-09-17 1994-11-15 Ecolab Inc. Reduced misting oven cleaner
US20070253926A1 (en) * 2006-04-28 2007-11-01 Tadrowski Tami J Packaged cleaning composition concentrate and method and system for forming a cleaning composition
WO2009062994A1 (fr) * 2007-11-14 2009-05-22 Basf Se Procédé de fabrication d'une dispersion d'épaississant
CN103328623B (zh) * 2010-12-13 2015-04-01 艺康美国股份有限公司 防污地板清洁剂
US9127235B2 (en) * 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0572960A (ja) 1991-09-11 1993-03-26 Toppan Printing Co Ltd ホログラフイツク光学素子の作製方法
US5962398A (en) * 1997-01-14 1999-10-05 Lever Brothers Company Isotropic liquids incorporating anionic polymers which are not hydrophobically modified
US20110230385A1 (en) * 2008-06-17 2011-09-22 Colgate Palmolive Company Light duty liquid cleaning compositions and methods of manufacture and use thereof
US20120208739A1 (en) * 2011-02-16 2012-08-16 Robert Richard Dykstra Liquid cleaning compositions
WO2013107778A1 (fr) * 2012-01-18 2013-07-25 Unilever Plc Compositions pour traitement capillaire

Also Published As

Publication number Publication date
CN110139921B (zh) 2021-09-07
EP3565879A1 (fr) 2019-11-13
EP3565879B1 (fr) 2020-08-05
CN110139921A (zh) 2019-08-16
ZA201903631B (en) 2020-12-23

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