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EP0998547B1 - Utilisation de polyelectrolytes comme agents sequestrants - Google Patents

Utilisation de polyelectrolytes comme agents sequestrants Download PDF

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Publication number
EP0998547B1
EP0998547B1 EP98940181A EP98940181A EP0998547B1 EP 0998547 B1 EP0998547 B1 EP 0998547B1 EP 98940181 A EP98940181 A EP 98940181A EP 98940181 A EP98940181 A EP 98940181A EP 0998547 B1 EP0998547 B1 EP 0998547B1
Authority
EP
European Patent Office
Prior art keywords
polyelectrolytes
acid
use according
copolymers
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.)
Expired - Lifetime
Application number
EP98940181A
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German (de)
English (en)
Other versions
EP0998547A2 (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
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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

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • 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
    • C11D3/3769—(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
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the invention relates to the use of polyelectrolytes for reducing the deposition of heavy metals on textile fibers during washing with aqueous bleaches.
  • EP-A 0137551 and EP-A 0447261 (Unilever) is the use of amine oxides with soap or sarcosinate and other anionic surfactants, such as alkyl sulfates, alkyl ether sulfates, secondary alkanesulfonates or alkylbenzenesulfonates known as a thickening component for Hypochlorilantsen.
  • amine oxides with soap or sarcosinate and other anionic surfactants such as alkyl sulfates, alkyl ether sulfates, secondary alkanesulfonates or alkylbenzenesulfonates known as a thickening component for Hypochlorilantsen.
  • aqueous bleach 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.
  • 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 that allow the production of aqueous bleaching agents, in particular chlorine bleaches, which are chlorine stable, textile friendly and haulver texts as possible have sufficiently high viscosity and with high Fleckentfemungshack accordingly reliably prevent the deposition of metal traces on the tissue.
  • aqueous bleaching agents in particular chlorine bleaches, which are chlorine stable, textile friendly and haulver texts as possible have sufficiently high viscosity and with high Fleckentfemungslitis accordingly reliably prevent the deposition of metal traces on the tissue.
  • the invention includes the recognition 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 a further improvement of 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 a further improvement of the stabilization against yellowing, cleaning performance and dermatological compatibility.
  • the Mitlel invention finally have a sufficiently high viscosity, so that a dosage by the consumer is easily possible.
  • the aqueous bleaching agents may contain hydrogen peroxide, but are preferably chlorine bleaches containing alkali hypochlorite.
  • Alkali hypochlorites are lithium, kallum and especially sodium hypochlorite.
  • the hypochlorites can be used in amounts of 1.5 to 10, preferably 2 to 8 and in particular 4 to 6 wt .-% - based on the means.
  • the polyelectrolytes are used in combination with buffers which are alkali metal and / or alkaline earth metal silicates, carbonates, phosphonates or mixtures thereof.
  • the salts aid the sequestering action of the polyelectrolytes and ensure that the formulations have a constant high alkaline pH in the range of 10 to 14.
  • Typical examples are sodium silicate, potassium silicate, sodium carbonate, potassium carbonate and from the group of phosphonates, in particular those marketed under the brand Sequion® by Bozetto / IT Aminoxidphosphonklaren.
  • the buffers may be used alone or in admixtures in amounts of 0.01 to 5, preferably 0.1 to 2 and in particular 0.5 to 1 wt .-% - based on the means -.
  • the bleaching agents obtainable using polyelectrolytes according to the invention generally have a non-aqueous content of from 5 to 35 and preferably from 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, they are used at low temperatures, ie in the range of cold washing (about 15 to 25 ° C).
  • the funds are characterized not only by excellent stain removal, but reliably prevent the deposition of metal traces on the fibers and thus prevent the yellowing.
  • the actual use of the means is directed to the removal of stains in the laundry, they are suitable in principle also for other purposes in which hypochlorite solutions are used, for example for the cleaning and disinfection of hard surfaces.
  • auxiliaries and additives are further chlorine-stable surfactants or hydrotropes, such as alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, xylenesulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid N-alkylglucamides.
  • the sum of all surfactants accounts for at most 10 to 15% by weight of the total amount of ingredients in the formulation.
  • the compositions according to the invention may contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with the aid of which the pH of the formulations can be adjusted to an optimum value of 10 to 14, preferably 12.5 to 13.5.
  • compositions may contain active-chlorine-stable perfumes, optical brighteners, dyes and pigments in amounts of from 0.01% to 0.5% by weight, based on the compositions.
  • active chlorine-resistant include, for example, monocyclic and bicyclic monoterpene alcohols and their esters with acetic or propionic acid (eg isoborneal, dihydroterpene oil, isobornyl acetate, dihydroterpenyl acetate).
  • Other fragrances that are suitable for this purpose, for example, in the publications EP-A1 0622451 (Procter & Gamble) as well JP-A Sho 62/89800 Called (Raison).
  • the optical brighteners may be, for example, the potassium salt of 4,4'-bis (1,2,3-triazolyl) - (2 -) - stilbene-2,2-sulfonic acid sold under the trademark Phorwite® BHC 766 is sold.
  • Suitable color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz).
  • the resulting product may be decanted or filtered to remove foreign bodies and / or agglomerates.
  • the compositions also have a viscosity above 100 mPas - measured at 20 ° C in a Brookfield viscometer - on.
  • soiled fabric was treated with various bleach solutions.
  • the yellowing of the tissue was determined photometrically, with the initial value of the contaminated tissue as 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 CaCl 2 , the content of hydrogen carbonate 0.013 wt .-%.
  • the liquor ratio (fabric: water) was 1:50, the exposure time was 30 min at a temperature of 40 ° C.
  • Tables 1 and 2 the quantities are by weight.

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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)

Claims (11)

  1. Utilisation de polyélectrolytes pour réduire le dépôt d'ions de métaux lourds sur des fibres textiles au cours du lavage avec des agents de blanchiment aqueux, caractérisée en ce qu'on met en oeuvre des polyélectrolytes qui sont choisis parmi le groupe qui est formé par :
    (a) des acides dicarboxyliques à bas poids moléculaire ;
    (b) des acides hydroxycarboxyliques polyvalents à bas poids moléculaire ;
    (c) des monopolymères et des copolymères d'esters d'acides monocarboxyliques insaturés qui dérivent de monomères répondant à la formule (II)
    Figure imgb0012
     dans laquelle R3 représente un atome d'hydrogène ou un groupe méthyle, R4 représente un radical d'hydrocarbure linéaire ou ramifié contenant de 1 à 22 atomes de carbone et m représente des nombres de 1 à 10 ;
    (d) des homopolymères et des copolymères d'amides d'acides monocarboxyliques insaturés et de leurs dérivés ; et/ou
    (e) des copolymères d'acide fumarique et d'acide vinylsulfonique et/ou des copolymères d'acide acrylique et d'acide styrènesulfonique.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'on met en oeuvre, à titre de polyélectrolytes du groupe (a), des acides dicarboxyliques à bas poids moléculaire répondant à la formule (I)
    Figure imgb0013
     dans laquelle R1 et R2 représentent un atome d'hydrogène, un métal alcalin et/ou un métal alcalino-terreux, l'ammonium, un alkylammonium, un alcanolammonium ou un glucammonium et n représente des nombres de 0 à 64.
  3. Utilisation selon la revendication 1, caractérisée en ce qu'on met en oeuvre, à titre de polyélectrolytes du groupe (b), de l'acide citrique et/ou du citrate de sodium.
  4. Utilisation selon la revendication 1, caractérisée en ce qu'on met en oeuvre, à titre de polyélectrolytes du groupe (d), des homopolymères et des copolymères du polyacrylamide et/ou du polyméthacrylamide.
  5. Utilisation selon la revendication 1, caractérisée en ce qu'on met en oeuvre des polyélectrolytes qui sont choisis parmi le groupe qui est formé par des poly-(N,N-bis-carboxyméthylènacrylamides), des copolymères d'acide fumarique et d'acide vinylsulfonique, des polymères d'acide 3-acrylamido-3-méthylpropanesulfonique, des copolymères d'acide acrylique et d'acide styrènesulfonique, des copolymères d'acide acrylique avec du monophosphate de 2-méthacrylate d'hydroxyéthyle, des homopolymères et des copolymères de chlorure de 3-acrylamido-3-méthylbutyltriméthylammonium, des copolymères de chlorhydrate de diallylglycinamide et d'acide acrylique, des copolymères de chlorhydrate de diméthylallylammonium avec de l'acrylamide, et/ou des polyéthylène- et/ou polypropylène-imines.
  6. Utilisation selon la revendication 1 ou selon l'une quelconque des revendications 4 ou 5, caractérisée en ce qu'on met en oeuvre des polyélectrolytes dont le poids moléculaire se situe dans la plage de 300 à 5 000 000.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'on met en oeuvre les polyélectrolytes dans des quantités de 0,01 à 5 % en poids, rapportés aux agents de blanchiment aqueux.
  8. Utilisation selon l'une quelconque des revendications 1 à 7, caractérisée en ce qu'on met en oeuvre les polyélectrolytes dans des agents de blanchiment contenant de l'hypochlorite.
  9. Utilisation selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'on met en oeuvre les polyélectrolytes conjointement avec des tampons qui sont choisis parmi le groupe qui est formé par des silicates, des carbonates et/ou des phosphonates de métaux alcalins et/ou de métaux alcalino-terreux.
  10. Utilisation selon l'une quelconque des revendications 1 à 9, caractérisée en ce qu'on met en oeuvre les polyélectrolytes conjointement avec des agents tensioactifs stables en présence de chlore, qui sont choisis parmi le groupe qui est formé par des alkyléthersulfates, des oxydes d'amines, des alkyl-et/ou alcényl-oligoglycosides et/ou des sels d'acides gras.
  11. Utilisation selon l'une quelconque des revendications 1 à 10, caractérisée en ce qu'on met en oeuvre les polyélectrolytes conjointement avec des substances odoriférantes stables en présence de chlore.
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
DE19730650 1997-07-17
DE19730650A DE19730650C2 (de) 1997-07-17 1997-07-17 Verfahren zur Vermeidung der Ablagerung von Schwermetallionen auf Textilfasern
PCT/EP1998/004243 WO1999003960A2 (fr) 1997-07-17 1998-07-08 Utilisation de polyelectrolytes comme agents sequestrants

Publications (2)

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

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EP98940181A Expired - Lifetime EP0998547B1 (fr) 1997-07-17 1998-07-08 Utilisation de polyelectrolytes comme agents sequestrants

Country Status (8)

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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

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DE19731881C1 (de) * 1997-07-24 1998-10-22 Henkel Kgaa Verwendung von Elektrolytgemischen als Sequestriermittel

Also Published As

Publication number Publication date
EP0998547A2 (fr) 2000-05-10
HUP0002896A2 (hu) 2001-01-29
WO1999003960A2 (fr) 1999-01-28
ES2370113T3 (es) 2011-12-12
ATE521688T1 (de) 2011-09-15
DE19730650C2 (de) 1999-12-02
PL338184A1 (en) 2000-10-09
HUP0002896A3 (en) 2001-11-28
SK552000A3 (en) 2000-07-11
WO1999003960A3 (fr) 1999-04-08
DE19730650A1 (de) 1999-01-28

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