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EP2850166A1 - Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé - Google Patents

Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé

Info

Publication number
EP2850166A1
EP2850166A1 EP13723106.4A EP13723106A EP2850166A1 EP 2850166 A1 EP2850166 A1 EP 2850166A1 EP 13723106 A EP13723106 A EP 13723106A EP 2850166 A1 EP2850166 A1 EP 2850166A1
Authority
EP
European Patent Office
Prior art keywords
pei
composition according
polymer
polyalkoxyl
chain
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
EP13723106.4A
Other languages
German (de)
English (en)
Other versions
EP2850166B1 (fr
Inventor
Stephen Norman Batchelor
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 PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 PLC, Unilever NV filed Critical Unilever PLC
Priority to EP13723106.4A priority Critical patent/EP2850166B1/fr
Publication of EP2850166A1 publication Critical patent/EP2850166A1/fr
Application granted granted Critical
Publication of EP2850166B1 publication Critical patent/EP2850166B1/fr
Active legal-status Critical Current
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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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • This invention relates to laundry detergent compositions comprising an
  • alkoxylated polyethyleneimine anti-redeposition polymer ARP
  • detergency surfactants particularly anionic and nonionic detergency surfactants.
  • Ethoxylated PEI polyethylene imine
  • the PEI(600)20EO material with all primary and secondary amino groups fully substituted by EO20 polyalkoxylation is not a good ARP for laundry detergents.
  • These alkoxylated PEIs are usually formed by direct reaction of ethylene oxide, and/or propylene oxide, and PEI as described in CA 1210009.
  • EP 2050792 discloses the preparation of a PEI plus tosylated PEG monomethyl ether as an intermediate in the preparation of a PEG-PEI-epoxy resin structure. This preparation is repeated in EP 2147733.
  • JP 2007/099929 discloses the addition of tosylated PEG monomethyl ether to PEI followed by the addition of a styrene monomer.
  • Zhang & Lonnie Chen & Lonnie (Chinese J. Chem., Vol 21 p 460-5, 2003) discusses the preparation of PEI-PEO block copolymers and their clay dispersancy.
  • the polymers are triblock polymers formed from divalently modified PEG (dimesyl). This forms a PEO crosslink between two PEI groups. Such crosslinked PEI is not desirable due to its lower weight efficiency.
  • Non-ionic containing formulations are widely used in laundry, especially for low suds formulations suitable for front loading automatic washing machines.
  • PEI tends to deposit soil onto nylon elastane based fabrics. EPEI does not suffer from the same nylon- elastane negatives as PEI and has consequently been widely used in laundry compositions. However, it would be desirable to improve the performance of EPEI as a soil suspending polymer to solve the problem of redeposition over the full range of fabrics found in a typical laundry load: cotton, polycotton, polyester and nylon-elastane.
  • a laundry detergent composition containing 5 to 30 wt% detersive surfactant selected from non-ionic and anionic surfactant and 0.05 to 4 wt%, preferably 0.1 to 2 wt%, of polyalkoxylated polyethylene imine polymer wherein the polymer is a PEI which has a molar ratio of polyalkoxyl chains to PEI of less than or equal to 3 resulting in 3 or fewer nitrogens, preferably 2 or fewer nitrogens, most preferably 1 nitrogen, bound to polyalkoxyl chains and wherein the PEI has a Mw of at least 500, preferably 1000 to 2000, more preferably less than 1500 and even about 1300. Mw is the weight average molecular weight.
  • the molecular weights are preferably determined by dynamic light scattering using a Zetasizer Nano (Malvern).
  • the fraction of (wt% non-ion ic)/(wt% anionic surfactant) is from 0.6 to 2.0 , preferably from 0.90 to 1 .2.
  • a wash method wherein the composition according to the first aspect is diluted to a level of 0.3 to 1 g/L surfactant and 5 to 150 ppm, preferably 10 to 80 ppm polymer according to the first aspect and used to launder fabrics.
  • Each polyalkoxyl chain is preferably built from ethoxy and/or propoxy groups.
  • the polyalkoxyl chain contains 5 to 50 alkoxyl repeat units, more preferably 8 to 20, most preferably 10 to 14.
  • Chains may be OH or alkyl capped, preferably methyl capped.
  • the chain is preferably provided with a reactive group at the end to be linked to the PEI. Suitable reactive groups may be selected from epoxides, alkenes, a sulfooxyethylsulfonyl reactive group (-SO 2 CH 2 CH 2 OSO 3 Na), heterocyclic reactive groups and leaving groups such as tosylate.
  • the heterocyclic reactive groups are preferably nitrogen containing aromatic rings bound to a halogen or an ammonium group, which react with NH 2 or NH groups to form a covalent bond.
  • the preformed alkoxy chain contains only 1 reactive group, the other chain end is typically alkyl capped.
  • the detergent compositions may take any suitable form.
  • they may be powders, tablets, liquids or gels and in the case of liquids they may be contained in a water soluble capsule to allow for ease of use.
  • Preferred compositions are liquids due to the compatibility of the polyalkoxylated PEI ARP materials with ingredients typically found in liquid detergents.
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
  • Blends of anionic and nonionic surfactants are a preferred feature of the compositions.
  • the amount of anionic surfactant is preferably at least 5 wt%, more preferably at least 10wt%.
  • Preferred anionic surfactants are alkyl sulphonates especially alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -Ci 5 .
  • the counter ion for the anionic surfactants is may be an alkali metal, typically sodium, or another counter-ion for example MEA, TEA or ammonium can be used.
  • Suitable linear alkyl benzene sulphonate surfactants include Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14. It is further desirable that the composition comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (II):
  • R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated
  • M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • R is an alkyl chain having from 12 to 16 carbon atoms
  • M is Sodium and x averages from 1 to 3, preferably x is 3;
  • SLES anionic surfactant sodium lauryl ether sulphate It is the sodium salt of lauryl ether sulphonic acid in which the predominantly C 12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
  • SLES sodium lauryl ether sulphate
  • Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 2 o aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
  • the composition contains from 0.1 to 20 wt% preferably 1 wt% to 15 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside,
  • a non-ionic surfactant for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside
  • alkyldimethylamineoxide ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 2 o aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • composition may comprise up to 10 wt% of an amine oxide of the formula (III):
  • R 1 is a long chain moiety each CH 2 R 2 are short chain moieties.
  • R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
  • Preferred amine oxides have R 1 is Cs-Cis alkyl, and R 2 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
  • a preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Huntsman under the trade name Empigen® OB.
  • Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R 2 is H
  • R 2 may be CH 2 OH, for example: hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
  • Preferred amine oxides have the formula (IV): O " - N + (Me) 2 R 1 (IV) where R 1 is Ci 2- 16 alkyl, preferably Ci 2- i 4 alkyl; Me is a methyl group. Zwitterionic
  • a preferred zwitterionic material is a carbobetaine available from Huntsman under the name Empigen® BB. Betaines and / or amine oxides, improve particulate soil detergency in the compositions. Additional surfactants
  • surfactants than the preferred LAS, SLES, nonionic and amine oxide/ carbobetaine may be added to the mixture of detersive surfactants.
  • cationic surfactants are preferably substantially absent.
  • alkyl sulphate surfactant may be used, especially the non-ethoxylated Ci 2- 15 primary and secondary alkyl sulphates.
  • compositions may include 0.5 wt% or more of a soil release polymer which is substantive to polyester fabric.
  • a soil release polymer which is substantive to polyester fabric.
  • Such polymers typically have a fabric substantive midblock formed from propylene terephthalate repeat units and one or two end blocks of capped polyalkylene oxide, typically PEG 750 to 2000 with methyl end capping.
  • a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components in the aqueous liquid to render it isotropic.
  • suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
  • At least one or more enzymes may be present in the
  • compositions Preferably at least two, more preferably at least three different classes of enzymes are used in combination.
  • Preferred enzyme cocktails are selected from the group comprising: lipase, Phospholipase, protease, Cutinase, Amylase, Cellulase, Peroxidases/oxidase, Pectate Lyase, and Mannanase.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • the enzymes may be protected by encapsulation.
  • a lipase enzyme is included a lignin compound may be used in the composition.
  • the lignin compound comprises a lignin polymer and more preferably it is a modified lignin polymer.
  • a modified lignin polymer as used herein is lignin that has been subjected to a chemical reaction to attach chemical moieties to the lignin covalently. The attached chemical moieties are preferably randomly substituted.
  • fluorescer in the compositions.
  • these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2- d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6- morpholino-1 ,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfoslyryl)biphenyl. Bleach Catalyst
  • Compositions may comprise a weight efficient bleach system. Such systems typically do not utilise the conventional percarbonate and bleach activator approach.
  • An air bleach catalyst system is preferred.
  • Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: WO 98/39098; WO 98/39406, WO 97/48787, WO 00/29537; WO 00/52124, and WO00/60045, incorporated by reference.
  • An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N,N-bis(pyridin-2-yl-methyl)-1 -,1 -bis(pyridin-2-yl)-1 -aminoethane).
  • Suitable bispidon catalyst materials and their action are described in WO02/48301 .
  • the bleach catalyst may be encapsulated to reduce interaction with other components of the liquid during storage.
  • Photobleaches may also be employed.
  • a "photobleach” is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction.
  • Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches.
  • Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or AI-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
  • the phthalocyanin has 1 -4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion.
  • the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10 wt%, preferably about 0.001 to about 5 wt%.
  • composition will normally include one of more perfume components. Free oil and encapsulated perfumes may be used, and mixtures thereof.
  • a particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume.
  • Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
  • the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics.
  • the deposition aid is preferably attached to the encapsulate by means of a covalent bond,
  • compositions may contain one or more other ingredients.
  • ingredients include viscosity modifiers, foam boosting agents, preservatives (e.g.
  • compositions may further comprise colorants, pearlisers and/or opacifiers, and shading dye.
  • Shading dye can be used to improve the performance of the compositions.
  • Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself. Examples of shading dyes are alkoxylated thiophene dyes, acid violet 50, direct violet 35, direct violet 99, direct violet 9, solvent violet 13, disperse violet 28, disperse blue 165.
  • Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene
  • polycarboxylic acids and citric acid.
  • Other examples are DEQUESTTM, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALANTM.
  • the organic builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition.
  • the preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
  • a preferred sequestrant is HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid), for example sold as Dequest 2010.
  • Dequest® 2066 Diethylenetriamine penta(methylene
  • buffers are MEA, and TEA. If present they are preferably used in the composition at levels of from 1 to 15 wt%.
  • External Structurants are preferred for pH control; preferred buffers are MEA, and TEA. If present they are preferably used in the composition at levels of from 1 to 15 wt%.
  • compositions may have their rheology modified by use of a material or materials that form a structuring network within the composition.
  • Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants for example citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition.
  • compositions may comprise visual cues of solid material that is not dissolved in the composition.
  • visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid.
  • Enzymes and bleach catalysts are examples of such ingredients.
  • perfume, particularly microencapsulated perfume are examples of such ingredients.
  • the molar ratio of Tosylated PEG to Polyethyleneimine was 1 :1 .
  • the mixture was stirred overnight (16 hr) at room temperature, after which the formation of para-toluene sulphonic acid was completed as measured by TLC, the pH was then adjusted to 7.0 with cone.
  • the base laundry detergent composition used for wash testing is given in Table 2.
  • NaLAS is sodium C -i 5 alkyl benzene sulphonate.
  • NI(7EO) is R-(OCH 2 CH 2 ) n OH, where R is C12-15 alkyl, and n is 7.
  • SLES(3EO) is sodium lauryl ether sulphate with an average of 3 ethoxy groups.
  • Alkyl Betaine is Empigen® BB (ex Huntsman).
  • the composition was used to wash a mixture of white fabrics: woven cotton, micro-fibre polyester, woven polycotton and knitted nylon-elastane with a liquor to cloth ratio of 10:1 in a Linitester.
  • the fabrics were of equal area. 26° French Hard water was used. Each wash lasted 20 minutes and was followed by 2 rinses in 75 ml water. This procedure was repeated twice in the base composition given in Table 2 (i.e. without any polymer) and then the fabric was then dried.
  • the wash procedure was then repeated three more times, now with the addition of soil strips to each wash to simulate soiling.
  • the weight ratio of soil strips to the white fabrics was 8.6:1 .
  • the soil strips used were SBL 2004 Soil Ballast Fabrics (ex wfk Testgewebe GmbH ) and a Stanley Clay strip (ex Warwick Equest UK) in the weight ratio of 1 : 1 .
  • For each of these 3 repeats 3.5 wt% of polymer was also included in the composition - the water balance being correspondingly reduced.
  • the compositions were all used at 2.3 g/L.
  • ⁇ R460 R460(polymer) - R460(control)
  • PEI(1300) is the non-ethoxylated PEL
  • the polymers P1 (with 1 ethoxylated chain) and P2 (with 2 ethoxylated chains) show the best performance overall performance, with good effects on cotton, polycotton and polyester, without a large negative on nylon-elastane as seen from the totally unalkoxylated PEI.
  • ⁇ R 6o is the sum of the ⁇ R 6 o for each of the fabrics.
  • PEI(1300) reference polymer.
  • the shorter chain alkoxylated PEI provided the best results.
  • Example 3
  • Table 7 is a further detergent composition according to the invention. Table 7
  • Enzyme levels are expressed as pure protein.
  • the lipase used was Lipoclean (Novozymes); the cellulose used was CellucleanTM (Novozymes); the amylase used was StainzymeTM (Novozymes).

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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 détergente de lessive contenant 5 à 30 % en poids d'agent tensioactif détersif sélectionné parmi un agent tensioactif non ionique et anionique, et 0,05 à 4 % en poids de polymère de polyéthylène-imine polyalcoxylé dans lequel les chaînes polyalcoxyle sont directement liées aux atomes d'azote dans le PEI et chaque chaîne présente un groupe terminal présentant un poids moléculaire inférieur à 100. Selon l'invention, le polymère est un PEI qui présente un rapport molaire des chaînes polyalcoxyle, y compris le groupe terminal, au PEI inférieur ou égal à 3, résultant en 3 ou moins, de préférence 2 ou moins, le plus préférablement 1 atome(s) d'azote lié(s) à des chaînes polyalcoxyle, et le PEI présente un Mw d'au moins 500, de préférence de 1000 à 2000, plus préférablement inférieur à 1500 et même d'environ 1300.
EP13723106.4A 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé Active EP2850166B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13723106.4A EP2850166B1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP12168345 2012-05-16
EP13152414 2013-01-23
EP13723106.4A EP2850166B1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé
PCT/EP2013/059939 WO2013171210A1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé

Publications (2)

Publication Number Publication Date
EP2850166A1 true EP2850166A1 (fr) 2015-03-25
EP2850166B1 EP2850166B1 (fr) 2015-10-21

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EP (1) EP2850166B1 (fr)
CN (1) CN104334707B (fr)
BR (1) BR112014026932B1 (fr)
ES (1) ES2556490T3 (fr)
IN (1) IN2014MN02280A (fr)
WO (1) WO2013171210A1 (fr)
ZA (1) ZA201407332B (fr)

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CN104334707B (zh) 2017-08-22
EP2850166B1 (fr) 2015-10-21
ZA201407332B (en) 2016-05-25
IN2014MN02280A (fr) 2015-10-09
WO2013171210A1 (fr) 2013-11-21
BR112014026932B1 (pt) 2021-08-31
CN104334707A (zh) 2015-02-04
BR112014026932A8 (pt) 2021-04-13
ES2556490T3 (es) 2016-01-18
BR112014026932A2 (pt) 2017-06-27

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