EP0998547A2 - Utilisation de polyelectrolytes comme agents sequestrants - Google Patents

Utilisation de polyelectrolytes comme agents sequestrants

Info

Publication number
EP0998547A2
EP0998547A2 EP98940181A EP98940181A EP0998547A2 EP 0998547 A2 EP0998547 A2 EP 0998547A2 EP 98940181 A EP98940181 A EP 98940181A EP 98940181 A EP98940181 A EP 98940181A EP 0998547 A2 EP0998547 A2 EP 0998547A2
Authority
EP
European Patent Office
Prior art keywords
polyelectrolytes
copolymers
use according
acid
group
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
EP98940181A
Other languages
German (de)
English (en)
Other versions
EP0998547B1 (fr
Inventor
Jaume Josa
Bernd Fabry
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0998547A2 publication Critical patent/EP0998547A2/fr
Application granted granted Critical
Publication of EP0998547B1 publication Critical patent/EP0998547B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2082Polycarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3956Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides

Definitions

  • the invention relates to the use of the polyelectrolytes as sequestering agents for the production of aqueous bleaching agents.
  • EP-A 0274885 (ICI) recommends the use of mixtures of linear and branched amine oxides for the production of viscous hypochlorite bleaches.
  • EP-A 0145084 (Uni-lever) mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose.
  • EP-A 0137551 and EP-A 0447261 (Unilever) the use of amine oxides with soap or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or alkyl benzene sulfonates as a thickening component for hypochlorite solutions, is known.
  • aqueous bleaching compositions containing sodium hypochlorite and anionic surfactants are also known.
  • the hypochlorite concentration of these agents is 0.1 to 8% by weight of active chlorine.
  • German patent DE-C1 4333100 the applicant finally proposed chlorine bleaching solutions based on hypochlorites, fatty alcohol ether sulfates, amine oxides and amine oxide phosphonic acids.
  • the use of silicates or carbonates as buffers in chlorine bleaching liquors can be found, for example, in documents US 4,623,476 (Procter & Gamble) and EP-A1 0079102 and EP-A1 0137551 (Unilever).
  • High demands are placed on bleaches of the type mentioned by the consumer: they must be compatible with textiles, ie the stains must be removed by treatment with the aggressive chemical hypochlorite without attacking the fabric. Since skin contact with the bleaching agents is not excluded, the preparations must also be as dermatologically compatible as possible.
  • hypochlorite solutions also attack metals and the dissolved metal traces can be deposited on the textile fibers during washing, which is ultimately reflected in the yellowing of the fabric. While market players are trying to prevent this redeposition by using silicates, in practice this measure does not always prove to be satisfactory.
  • the complex object of the invention was to counteract the yellowing of the laundry by the influence of heavy metal ions and to provide sequestering agents which allow the production of aqueous bleaching agents, in particular chlorine bleaching liquors, which are chlorine-stable, gentle on textiles and as skin-friendly as possible have a sufficiently high viscosity and reliably prevent the deposition of metal traces on the fabric if the stain removal capacity is high.
  • the invention relates to the use of polyelectrolytes as sequestering agents for the production of aqueous bleaching agents.
  • the invention includes the knowledge that the use of buffers such as in particular silicates, carbonates and / or phosphonates and optionally mild, chlorine-stable surfactants such as preferably alkyl ether sulfates, amine oxides, alkyl and / or alkenyl oligoglycosides and fatty acid salts to further improve the stabilization against yellowing, cleaning performance and dermatological compatibility.
  • buffers such as in particular silicates, carbonates and / or phosphonates
  • optionally mild, chlorine-stable surfactants such as preferably alkyl ether sulfates, amine oxides, alkyl and / or alkenyl oligoglycosides and fatty acid salts to further improve the stabilization against yellowing, cleaning performance and dermatological compatibility.
  • the agents according to the invention have a sufficiently high viscosity so that metering by the consumer is possible without problems.
  • R 1 and R 2 represent hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkyammonium, alkanolammonium or glucammonium and n represents numbers from 0 to 64.
  • Typical examples are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid and the dimer and trimer fatty acids based on unsaturated fatty acids, namely oleic acid, elaidic acid, gadoleic acid and erucic acid.
  • the dicarboxylic acids can be mono- or polyunsaturated and / or have an aromatic ring instead of the alkylene groups.
  • Typical examples are maleic acid, fumaric acid, sorbic acid, phthalic acid and terephthalic acid. Neutralization takes place when the acids mentioned are introduced into the alkaline bleaching agents. However, they can also be used directly in the form of their salts, preferably as sodium salts. The use of adipic acid or sodium adipate as the polyelectrolyte is particularly preferred.
  • (b) Low molecular weight polyvalent hydroxycarboxylic acids are malic acid, tartaric acid and in particular citric acid. These acids can also be used in the form of their alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium salts. The use of citric acid or sodium citrate as the polyelectrolyte is particularly preferred.
  • R 3 represents hydrogen or a methyl group
  • R 4 represents hydrogen or a linear or branched hydrocarbon radical having 1 to 22, preferably 2 to 12 and in particular 3 to 8 carbon atoms and m represents 0 or numbers from 1 to 10.
  • Typical examples are acrylic acid and / or methacrylic acid and their esters with methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, capro alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, Isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeosteary
  • Homopolymers or copolymers of acrylic acid, methacrylic acid and their methyl, tert-butyl or 2-ethylhexyl esters are preferably used.
  • the resulting polymers can have average molecular weights of the order of 300 to 5,000,000, preferably 10,000 to 1,000,000, preferably 50,000 to 500,000 and particularly preferably 100,000 to 250,000 daltons. This distribution of preferred molecular weights also applies to the following groups of suitable polymeric sequestering agents.
  • suitable homopolymers and copolymers of acrylic and methacrylic acid with a molecular weight in the range from 5,000 to 15,000 daltons are given in German Auslegeschrift DE-OS 1808824 (Grace).
  • Polymers which are prepared in the presence of sulfur compounds such as, for example, thioglycolic acid or 2-mercaptoethanol are also particularly suitable [cf. US 3665035 and US 3787488 (Magna)].
  • the homopolymers and copolymers which are prepared by the process of DE-AS 2632773 (Ciba) are also suitable.
  • the thioether groups formed during the polymerization are then oxidized to sulfoxide and / or sulfone groups.
  • Suitable sulfur-containing acrylic acid / acrylic acid ester polymers with hydrophobic components are also the subject of US 4008164 (Nalco).
  • Polymers containing hydroxyl groups can also be used, which are produced, for example, by copolymerizing acrylic acid with acrolein and subsequent disproportionation [cf. DE-AS 2522637], from US 3682224 (Bleyle) copolymers of methacrylic acid with vinylsulfonic acid are also known in this connection.
  • Other suitable polyacrylates or polymethacrylates are described in the following publications: GB-A1 1034680 (Commonwealth Scientific), NL-A 7400160 (Grace), BE-A 620771 (cyanamide) and US 3516916 (Grace).
  • (d) Homo- and copolymers of unsaturated dicarboxylic acids and their derivatives.
  • Unsaturated dicarboxylic acids that can be used as monomers have already been mentioned under (a).
  • maleic anhydride is preferably used because of its high reactivity and low price.
  • the products that can be produced, for example, by hydrolysis of polymaleic anhydride have a high charge intensity. Ring structures, which arise during the polymerization as a result of side reactions, also give the molecules a certain chain stiffness, which has an advantageous effect on the sequesteration.
  • Polymaleic anhydrides (PMSA) with molecular weights in the range from 300 to 5000 daltons are known, for example, from US 3810835 (Ciba).
  • Copolymers of PMSA and poly (meth) acrylic acid with molecular weights in the range from 1,000 to 50,000 are mentioned in DE-AS 2412926 (Ciba).
  • the subject of US 3650970 (Atlantic Richfield) are copolymers of maleic anhydride and styrene which are subjected to ring opening with polyethylene glycol (molecular weight 300 to 1,000) and also show a good sequestering effect.
  • copolymers of maleic anhydride with sulfonated styrene [FR-A 2322831 (Betz)], vinyl acetate [US 3755264 (Amicon)], methacrylic acid / styrene [US 4065607 (Pfitzner)], allyl acetate [US 4001134 (Grace)] and / or acrolein [DE-AS 2404192 (Ciba)].
  • These substances are preferably compounds which are produced either by (co) polymerizing the monomers or by polymer-analogous hydrolysis of poly (meth) acrylamide or poly (meth) acrylonitrile.
  • the production of a polyacrylamide with a molecular weight in the range from 500 to 5,000 daltons using thioglycolic acid as regulator and alkaline hydrolysis of 60 to 90% of the amide groups is described, for example, in US 4001161 (cyanamide).
  • a polymer of similar composition is obtained according to US 3492240 (Nalco).
  • the product contains 20 to 50% amide groups and 50 to 80% carboxy groups and a molecular weight in the range of 20,000 to 40,000.
  • CA 982341 also discloses a hydrolyzed polyacrylonitrile which has 20 to 30% amide groups, 70 to 80% acid groups and a molecular weight of 5,000 to 40,000. Graft polymers of acrylamide or acrylonitrile on starch or vinyl alcohol and their hydrolysis products [cf. NL 66/5265 (ICI)].
  • polyelectrolytes Other anionic or cationic polyelectrolytes.
  • polyelectrolytes poly- (N, N-bis-carboxy-methylene acrylamide) [cf. GB-A 1310613 (Chemed)] copolymers of fumaric acid and vinyl sulfonic acid [cf. US 3879288, US 3706717 (Siegele)], polymers of 3-acrylamido-3-methylpropanesulfonic acid [cf. US 3709815, US 3928196 (Calgon)], copolymers of acrylic acid and styrene sulfonic acid [cf.
  • the aqueous bleaching agents may contain hydrogen peroxide, but they are preferably chlorine bleaching liquors containing alkali hypochlorite.
  • Alkali hypochlorites are to be understood as lithium, potassium and in particular sodium hypochlorite.
  • the hypochlorites can be used in amounts of 1.5 to 10, preferably 2 to 8 and in particular 4 to 6% by weight, based on the composition. buffer
  • the polyelectrolytes are used in combination with buffers which are alkali and / or alkaline earth metal silicates, carbonates, phosphonates or mixtures thereof.
  • the salts support the sequestering effect of the polyelectrolytes and ensure that the preparations have a constantly highly alkaline pH in the range from 10 to 14.
  • Typical examples are sodium silicate, potassium silicate, sodium carbonate, potassium carbonate and from the group of the phosphonates, in particular the amine oxide phosphonic acids sold by Bozetto / IT under the brand Sequion®.
  • the buffers can be used alone or in mixtures in amounts of 0.01 to 5, preferably 0.1 to 2 and in particular 0.5 to 1% by weight, based on the composition.
  • Alkyl ether sulfates are known anionic surfactants which are obtained by sulfation of nonionic surfactants of the alkylpolyglycol ether type and subsequent neutralization.
  • the alkyl ether sulfates which are suitable for the purposes of the agents according to the invention follow the formula (III)
  • R 5 represents an alkyl radical having 12 to 18, in particular 12 to 14, carbon atoms
  • q represents numbers 2 to 5, in particular 2 to 3
  • X represents sodium or potassium.
  • Typical examples are the sodium salts of sulfates of the Ci2 / i4-coconut alcohol-2, -2,3- and -3-EO adduct.
  • the alkyl ether sulfates can have a conventional or narrow homolog distribution.
  • the alkyl ether sulfates are preferably used in amounts of 1 to 8, preferably 1.5 to 6 and in particular 2 to 4% by weight, based on the composition.
  • amine oxides are also known substances, which are occasionally attributed to the cationic, but usually the nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and are oxidized in the presence of hydrogen peroxide.
  • the amine oxides which are suitable for the purposes of the invention follow the formula (IV)
  • R 6 is a linear or branched alkyl radical having 12 to 18 carbon atoms and R 7 and R 8 independently of one another are R 6 or an optionally hydroxyl-substituted alkyl radical having 1 to 4 carbon atoms.
  • Amine oxides of the formula (IV) are preferably used in which R 6 and R 7 are C1214 or C12 / 18 coconut alkyl radicals and R 8 is a methyl or a hydroxyethyl radical.
  • R 6 represents a C12 / 14 or C12 / 18 cocoalkyl radical and R 7 and R 8 have the meaning of a methyl or hydroxyethyl radical.
  • the amine oxides are preferably used in amounts of 1.5 to 6, preferably 2 to 4,% by weight, based on the composition.
  • alkyl and / or alkenyl oligoglycosides are known nonionic surfactants which follow the formula (V)
  • R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 9 can also differ from primary alcohols with 12 to 22 preferably derive from 12 to 14 carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, alaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures.
  • Alkyl oligoglucosides based on hydrogenated Ci2 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
  • the glycosides are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.
  • the agents according to the invention can contain fatty acid salts of the formula (VI) as further surfactants,
  • R 10 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
  • Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their mixtures as they occur in the pressure splitting of technical fats and oils. Salts of technical coconut or tallow fatty acids are preferably used.
  • the fatty acids which are neutralized in situ when they are introduced into the mixture can also be used instead of the salts.
  • Those agents according to the invention preferably contain, as an optional component, fatty acid salts in which a particular low foam level is desired.
  • the soaps are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the.
  • the bleaches obtainable using polyelectrolytes according to the invention generally have a nonaqueous fraction of 5 to 35 and preferably 8 to 15% by weight and are preferably suitable for the treatment of textile fabrics, such as yarns, fabric webs and in particular Textiles. Usually takes place their application at low temperatures, ie in the region of the cold wash (ca. 15 to 25 C C).
  • the agents are not only characterized by excellent stain removal, they also reliably prevent metal traces from being deposited on the fibers and thus prevent yellowing. Although the actual use of the agents is to remove stains from laundry, they are suitable basically also for other purposes in which hypochlorite solutions are used, for example for cleaning and disinfecting hard surfaces.
  • auxiliaries and additives which may be used are, for example, other chlorine-stable surfactants or hydro tropes, such as, for example, alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid-N alkylglucamides.
  • the sum of all surfactants preferably makes up at most 10 to 15% by weight of the total amount of ingredients in the formulation.
  • the agents according to the invention can contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with the aid of which the pH of the recipes can be adjusted to an optimal value of 10 to 14, preferably 12.5 to 13.5.
  • the agents can contain active chlorine-stable fragrances, optical brighteners, dyes and pigments in a total amount of 0.01 to 0.5% by weight, based on the agents.
  • the fragrances known to be active chlorine-resistant include, for example, monocyclic and bicyclic monoterpene alcohols and their esters with acetic or propionic acid (for example isobomeal, dihydroterpene oil, isobornyl acetate, dihydroterpenyl acetate).
  • Other fragrances that are suitable for this purpose are mentioned, for example, in the publications EP-A1 0622451 (Procter & Gamble) and JP-A Sho 62/89800 (Raison).
  • the optical brighteners can be, for example, the potassium salt of 4,4'-bis (1, 2,3-triazolyl) - (2 -) - stilbin-2,2-sulfonic acid, which is sold under the Phorwite® BHC brand 766 is distributed.
  • Possible color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz).
  • the preparation is made by stirring. If necessary, the product obtained can be decanted or filtered to remove foreign bodies and / or agglomerates.
  • the agents also have a viscosity above 100 mPas - measured at 20 ° C in a Brookfield viscometer.
  • soiled tissue was treated with various bleaching solutions.
  • the yellowing of the tissue was determined photometrically, the initial value of the soiled tissue serving as the standard (100%).
  • the measurements were carried out in a liquor with a metal ion content of 300 ppb Fe and 100 ppb Mn; the water hardness was 1000 ppm CaCb, the hydrogen carbonate content was 0.013% by weight.
  • the liquor ratio (tissue: water) was 1:50, the exposure time was 30 minutes at a temperature of 40 ° C.
  • Tables 1 and 2 the quantities are understood as% by weight.

Landscapes

  • 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)

Abstract

L'invention concerne l'utilisation de polyélectrolytes comme agents séquestrants pour préparer des agents de blanchiment. On obtient, notamment conjointement avec des tampons et des tensioactifs résistants au chlore, des préparations, de préférence des solutions de chlorure décolorant, protégeant le tissu du jaunissement.
EP98940181A 1997-07-17 1998-07-08 Utilisation de polyelectrolytes comme agents sequestrants Expired - Lifetime EP0998547B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19730650A DE19730650C2 (de) 1997-07-17 1997-07-17 Verfahren zur Vermeidung der Ablagerung von Schwermetallionen auf Textilfasern
DE19730650 1997-07-17
PCT/EP1998/004243 WO1999003960A2 (fr) 1997-07-17 1998-07-08 Utilisation de polyelectrolytes comme agents sequestrants

Publications (2)

Publication Number Publication Date
EP0998547A2 true EP0998547A2 (fr) 2000-05-10
EP0998547B1 EP0998547B1 (fr) 2011-08-24

Family

ID=7836002

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98940181A Expired - Lifetime EP0998547B1 (fr) 1997-07-17 1998-07-08 Utilisation de polyelectrolytes comme agents sequestrants

Country Status (8)

Country Link
EP (1) EP0998547B1 (fr)
AT (1) ATE521688T1 (fr)
DE (1) DE19730650C2 (fr)
ES (1) ES2370113T3 (fr)
HU (1) HUP0002896A3 (fr)
PL (1) PL338184A1 (fr)
SK (1) SK552000A3 (fr)
WO (1) WO1999003960A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6537960B1 (en) * 2001-08-27 2003-03-25 Ecolab Inc. Surfactant blend for use in highly alkaline compositions
DE102011120675B4 (de) 2011-12-02 2023-09-28 Pinion Gmbh Getriebeeinheit

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1079275A (en) 1965-04-23 1967-08-16 Ici Ltd Water treatment compositions
US3492240A (en) 1965-06-24 1970-01-27 Nalco Chemical Co Method for reducing scale in boilers
US3879288A (en) 1970-07-01 1975-04-22 Frederick Herman Siegele Process of inhibiting scale formation on walls of structures containing an aqueous system
US3706717A (en) 1970-07-01 1972-12-19 American Cyanamid Co Copolymers of fumaric acid and allyl sulfonic acid
US3700599A (en) * 1970-09-25 1972-10-24 Economics Lab Composition for mechanically cleaning hard surfaces
CA982341A (en) 1971-09-20 1976-01-27 James R. Stanford Waterflood process using low molecular weight acrylic acid polymers as scale inhibitors
GB1411463A (en) * 1973-03-01 1975-10-22 Citrex Sa Detergent compositions
US4001161A (en) 1975-06-13 1977-01-04 American Cyanamid Company Low molecular weight hydrolyzed polyacrylamide and use thereof as scale inhibitor in water systems
US4048066A (en) 1976-11-17 1977-09-13 Chemed Corporation Method of inhibiting scale
DE2903980C2 (de) * 1979-02-02 1986-08-07 Henkel KGaA, 4000 Düsseldorf Aktivchlorhaltige Mittel
EP0062858A1 (fr) * 1981-04-03 1982-10-20 Diversey Corporation Produit de nettoyage à circulation utilisable à basse température
US4474677A (en) * 1981-11-06 1984-10-02 Lever Brothers Company Colored aqueous alkalimetal hypochlorite compositions
GB8325541D0 (en) 1983-09-23 1983-10-26 Unilever Plc Liquid thickened bleaching composition
GB8332271D0 (en) 1983-12-02 1984-01-11 Unilever Plc Bleaching composition
US4623476A (en) 1984-03-30 1986-11-18 The Procter & Gamble Company Stable suspension of pigments in aqueous hypochlorite bleach compositions
US4681696A (en) * 1984-06-19 1987-07-21 Chemed Corporation Solid stabilized active halogen-containing detergent compositions and methods
CA1334389C (fr) * 1986-03-26 1995-02-14 Ernest H. Brumbaugh Composition anti-taches pour lave-vaisselle
GB8630845D0 (en) 1986-12-24 1987-02-04 Ici Plc Bleaching compositions
DE3810107A1 (de) * 1987-04-03 1988-10-13 Sandoz Ag Phosphatfreies bzw. -armes fluessiges mittel fuer das maschinelle geschirrspuelen
GB9005873D0 (en) 1990-03-15 1990-05-09 Unilever Plc Bleaching composition
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
US5419847A (en) * 1993-05-13 1995-05-30 The Procter & Gamble Company Translucent, isotropic aqueous liquid bleach composition
DE4333100C1 (de) 1993-09-29 1994-10-06 Henkel Kgaa Bleich- und Desinfektionsmittel
US5451644A (en) * 1994-01-14 1995-09-19 Rohm And Haas Company Aqueous process for preparing water soluble polymers of monoethylenically unsaturated dicarboxylic acids
DE19512898A1 (de) * 1995-04-06 1996-10-10 Bayer Ag Iminodisuccinat-enthaltende Polymere
DE19528843A1 (de) * 1995-08-04 1997-02-06 Cht R Beitlich Gmbh Verfahren zur Stabilisierung von alkalischen peroxidenthaltenden Bleichflotten für die Bleiche von Zellstoffen und anderen Faserstoffen
US6297209B1 (en) * 1996-05-10 2001-10-02 The Clorox Company Sequesterants as hypochlorite bleach enhancers
DE19700799C2 (de) 1997-01-13 1999-02-04 Henkel Kgaa Wäßrige Textilbleichmittel
DE19731881C1 (de) * 1997-07-24 1998-10-22 Henkel Kgaa Verwendung von Elektrolytgemischen als Sequestriermittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9903960A2 *

Also Published As

Publication number Publication date
DE19730650C2 (de) 1999-12-02
ES2370113T3 (es) 2011-12-12
HUP0002896A2 (hu) 2001-01-29
EP0998547B1 (fr) 2011-08-24
SK552000A3 (en) 2000-07-11
WO1999003960A3 (fr) 1999-04-08
DE19730650A1 (de) 1999-01-28
WO1999003960A2 (fr) 1999-01-28
PL338184A1 (en) 2000-10-09
HUP0002896A3 (en) 2001-11-28
ATE521688T1 (de) 2011-09-15

Similar Documents

Publication Publication Date Title
EP0966514B1 (fr) Agents de blanchiment aqueux
DE2232353B2 (de) Wasch- und Reinigungsmittelmischung mit verbesserter Hemmwirkung bezüglich Farbstoffübertragung
DE2527702A1 (de) Waschmittel mit verbesserter schmutzabloesefaehigkeit
EP1972683B1 (fr) Polymères amphotères en tant qu'additifs antisalissure dans des produits de lavage
DE3531756A1 (de) Wasch- und weichmachungsmittelzusammensetzung
DE4333100C1 (de) Bleich- und Desinfektionsmittel
DE19731881C1 (de) Verwendung von Elektrolytgemischen als Sequestriermittel
DE19853845A1 (de) Wäßriges Bleichmittelkonzentrat
DE19730650C2 (de) Verfahren zur Vermeidung der Ablagerung von Schwermetallionen auf Textilfasern
WO2000077134A2 (fr) Utilisation de polyethylenes partiellement oxydes en tant qu'auxiliaires de repassage dans des assouplissants textiles liquides aqueux
DE10153768A1 (de) Hydroxymischether mit Polymeren
EP1149146B1 (fr) Utilisation de polyacrylates modifies a l'acide phosphonique en tant que sequestrants
EP0998546B1 (fr) Utilisation de melanges d'electrolytes comme agents sequestrants
DE69633113T2 (de) Reinigungsmittelzusammensetzungen
DE19845456A1 (de) Syndetstückseifen
DE19624843C2 (de) Verwendung wäßriger Bleichzusammensetzungen
EP0918841B1 (fr) Agents de blanchiment aqueux
EP1080175A1 (fr) Agent de blanchiment aqueux
EP0912696B1 (fr) Agents de blanchiment et de desinfection aqueux
EP0872541A2 (fr) Détergent liquide pour lavage doux sous forme de microémulsion
EP1050575A2 (fr) Compositions détergentes alcalines comprenant des alkylbenzènes sulfonates et des alcanolamines

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000107

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE DK ES FI FR GB IT NL PT SE

17Q First examination report despatched

Effective date: 20010607

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE DK ES FI FR GB IT NL PT SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 59814497

Country of ref document: DE

Effective date: 20111020

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2370113

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20111212

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111226

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120525

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 59814497

Country of ref document: DE

Effective date: 20120525

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20120731

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 521688

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20140611

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20140702

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20140708

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20140718

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59814497

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160202

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150708

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150731

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150709