EP1000133B1 - Utilisation de melanges electrolytiques comme agents sequestrants - Google Patents

Utilisation de melanges electrolytiques comme agents sequestrants Download PDF

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Publication number
EP1000133B1
EP1000133B1 EP98940230A EP98940230A EP1000133B1 EP 1000133 B1 EP1000133 B1 EP 1000133B1 EP 98940230 A EP98940230 A EP 98940230A EP 98940230 A EP98940230 A EP 98940230A EP 1000133 B1 EP1000133 B1 EP 1000133B1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
salts
mixtures
acid
alkyl
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
EP98940230A
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German (de)
English (en)
Other versions
EP1000133A1 (fr
Inventor
Jaume Josa
Bernd Dr. 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 EP1000133A1 publication Critical patent/EP1000133A1/fr
Application granted granted Critical
Publication of EP1000133B1 publication Critical patent/EP1000133B1/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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D1/30—Sulfonation products derived from lignin
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the invention relates to the use of selected electrolyte mixtures as sequestering agents Manufacture of aqueous bleaches.
  • 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 (Unilever) 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, is known as a thickening component for hypochlorite solutions.
  • aqueous bleaching agent compositions containing sodium hypochlorite and anionic surfactants are also known. However, 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).
  • the complex object of the invention has been the yellowing of the laundry counteract by the influence of heavy metal ions and available sequestrants places that allow the production of aqueous bleaching agents, especially chlorine bleach, which are also chlorine stable. are gentle on textiles and are as compatible with the skin as possible have high viscosity and with high stain removal capacity, the deposition of Prevent metal traces on the fabric reliably.
  • the invention includes the knowledge that the use of 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, the cleaning performance and dermatological tolerance.
  • the agents according to the invention have due to the gel-forming effect of the lignin sulfonals, the viscosity is sufficiently high so that dosing by the consumer is easily possible.
  • lignin sulfonates are the alkali, alkaline earth, ammonium.
  • Aluminum or zinc salts To understand ligninsulfonic acid, for example, in the sulfite digestion of wood as a reaction product of natural lignin and sulphurous acid. Those that come into consideration in the sense of the invention Lignin sulfonates can average molecular weights of 500 to 200,000, preferably 10,000 to 50,000 daltons, the number of sulfonic acid groups can be based on one Phenylpropane unit are in the range of 1 to 5.
  • the aqueous bleaching agents can contain hydrogen peroxide, but they are preferably chlorine bleach containing alkali hypochlorite.
  • Alkali hypochlorites include lithium, To understand potassium and especially sodium hypochlorite.
  • the hypochlorites can be found in amounts of 1.5 to 10, preferably 2 to 8 and in particular 4 to 6% by weight, based on the composition, are used become.
  • the lignin sulfonates are used together with at least one further electrolyte salt.
  • it can be alkali and / or alkaline earth silicates, carbonates. act citrates or mixtures thereof; typical examples are sodium silicate. Potassium silicate. Sodium. Potassium carbonate, sodium citrate, Potassium citrate and magnesium citrate.
  • polyelectrolytes of the type are used as electrolyte salts of the polyacrylates used. These include not only the homopolymers of acrylic acid, but also methacrylic acid and its esters with lower linear or branched alcohols with 1 to 8 Understand carbons.
  • the generic term polyacrylates also includes the copolymers of the named Substances.
  • the average molecular weight of the polyacrylates can vary over a wide range scatter and is between 300 and 5,000,000, preferably 1,000 to 1,000,000, in particular 50,000 to 500,000 and particularly preferably 100,000 to 250,000 Daltons.
  • phosphonates are used as electrolyte salts. These include both inorganic phosphonates (also known as secondary phosphites) of the formula (I), HP (O) (OM 1 ) 2 (I) in which M represents an alkali or alkaline earth metal, aluminum or zinc, preferably sodium, and also organic phosphonates of the formula (II), R 1 P (O) (OR 2 ) 2 (II)
  • R 1 and R 2 independently of one another represent hydrogen or linear or branched, optionally functionalized hydrocarbon radicals having 1 to 22, preferably 4 to 12 carbon atoms, with the proviso that R 1 and R 2 cannot simultaneously be hydrogen.
  • organic phosphonates are methylphosphonate, ethylphosphonate, butylphosphonate, 2-ethylhexylphosphonate and amino-functionalized phosphonates such as, for example, aminomethylenephosphonate or aminoethylenephosphonate.
  • a further group of suitable phosphonates are species which are linked to one another via functional groups, such as, for example, nitrilotris (methylene phosphonate) or nitrilotris (ethylene phosphonate).
  • amine oxide phosphonic acids such as those offered by Bozetto / IT under the name Sequion®.
  • the electrolyte salts support the sequestering effect of the lignin sulfonates and ensure that the Preparations have a constantly high alkaline pH in the range from 10 to 14 Lignin sulfonates and the electrolyte salts can be in a weight ratio of 95: 5 to 5:95, preferably 80 : 20 to 20: 80 and in particular 60: 40 to 40: 60.
  • the amount of the Electrolyte mixtures containing lignin sulfonates and electrolyte salts can be 0.01 to 5, preferably 0.1 up to 2 and in particular 0.5 to 1% by weight, based on the composition.
  • the bleaches obtainable using the electrolyte mixtures according to the invention have usually a non-aqueous content of 5 to 35 and preferably 8 to 15 wt .-% on and are preferably suitable for the treatment of textile fabrics, such as yarns, Fabric and especially textiles. They are usually used at low levels Temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C). The funds are not just outstanding excellent stain removal, but reliably prevent the deposition of Traces of metal on the fibers and thus also prevent yellowing. Although the real one Use of the agent aimed at removing stains during washing, 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 hydrotropes, such as alkyl sulfates and alkyl sulfonates.
  • 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, isobomylacetate, dihydroterpenylacetate).
  • 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.
  • 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 chlorine bleaches.
  • 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 CaCl 2 , 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.
  • Table 1 The results are summarized in Table 1; the quantities are understood as% by weight.
  • Examples 1 to 8 according to the invention are examples V1 and V2 serve for comparison.

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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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (11)

  1. Utilisation de mélanges d'électrolytes contenant :
    a) des ligninosulfonates et
    b) au moins un autre sel d'électrolyte choisi dans le groupe qui est formé des polyacrylates, des phosphonates, des silicates, des carbonates et des citrates, en tant qu'agent séquestrant en vue la préparation d'agents de blanchiment aqueux contenant de l'hypochlorite.
  2. Utilisation selon la revendication 1,
    caractérisée en ce qu'
    on met en oeuvre des sets de métal alcalin, de métal alcalino-terreux, d'ammonium, d'aluminium et/ou de zinc de l'acide ligninosulfonique.
  3. Utilisation selon l'une quelconque des revendications 1 et 2,
    caractérisée en ce qu'
    on met en oeuvre des ligninosulfonates ayant un poids moléculaire moyen dans la zone de 500 à 200.000 daltons.
  4. Utilisation selon l'une quelconque des revendications 1 à 3,
    caractérisée en ce qu'
    on met en oeuvre des acides phosphoriques d'amino-oxydes comme phosphonates électrolytiques.
  5. Utilisation selon les revendications 1 à 4,
    caractérisée en ce qu'
    on met en oeuvre comme sets d'électrolyte de polyacrylate des homo- ou des copolymères de l'acide acrylique, de l'acide méthacrylique ainsi que leurs esters avec des alcools inférieurs linéaires ou ramifiés ayant de 1 à 8 atomes de carbone.
  6. Utilisation selon la revendication 5,
    caractérisée en ce qu'
    on met en oeuvre des polyacrylates ayant un poids moléculaire moyen allant de 300 à 5.000.000 daltons.
  7. Utilisation selon l'une quelconque des revendications 1 à 6,
    caractérisée en ce qu'
    on met en oeuvre comme sels d'électrolytes le silicate de sodium, le silicate de potassium, le carbonate de potassium, le citrate de sodium, le citrate de polassium, le citrate de magnésium ou leurs mélanges.
  8. Utilisation selon l'une quelconque des revendications 1 à 7,
    caractérisée en ce qu'
    on met en oeuvre les ligninosulfonates et les sels d'électrolytes dans un rapport en poids de 95:5 à 5:95.
  9. Utilisation selon l'une quelconque des revendications 1 à 8,
    caractérisée en ce qu'
    on met en oeuvre les mélanges d'électrolytes en quantités allant de 0,01 à 5 % en poids, rapporté aux agents de blanchiment aqueux.
  10. Utilisation selon l'une quelconque des revendications 1 à 9,
    caractérisée en ce qu'
    on met en oeuvre les mélanges d'électrolytes conjointement avec des agents tensioactifs stables au chlore choisis dans le groupe formé des sulfates d'éther d'alkyle, des amino-oxydes, des alkyl- et/ou alkenyloligoglycosides, et/ou des sels d'acide gras;
  11. Utilisation selon l'une quelconque des revendications 1 à 10,
    caractérisée en ce qu'
    on met en oeuvre les mélanges d'électrolytes conjointement avec des parfums stables au chlore.
EP98940230A 1997-07-24 1998-07-15 Utilisation de melanges electrolytiques comme agents sequestrants Expired - Lifetime EP1000133B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19731881A DE19731881C1 (de) 1997-07-24 1997-07-24 Verwendung von Elektrolytgemischen als Sequestriermittel
DE19731881 1997-07-24
PCT/EP1998/004398 WO1999005245A1 (fr) 1997-07-24 1998-07-15 Utilisation de melanges electrolytiques comme agents sequestrants

Publications (2)

Publication Number Publication Date
EP1000133A1 EP1000133A1 (fr) 2000-05-17
EP1000133B1 true EP1000133B1 (fr) 2002-04-24

Family

ID=7836783

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98940230A Expired - Lifetime EP1000133B1 (fr) 1997-07-24 1998-07-15 Utilisation de melanges electrolytiques comme agents sequestrants

Country Status (7)

Country Link
EP (1) EP1000133B1 (fr)
DE (1) DE19731881C1 (fr)
ES (1) ES2175751T3 (fr)
HU (1) HUP0004799A3 (fr)
PL (1) PL338248A1 (fr)
SK (1) SK942000A3 (fr)
WO (1) WO1999005245A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19730650C2 (de) * 1997-07-17 1999-12-02 Henkel Kgaa Verfahren zur Vermeidung der Ablagerung von Schwermetallionen auf Textilfasern
NZ538649A (en) 2005-03-07 2006-10-27 Inst Geolog Nuclear Sciences Estimating strengths of wooden supports using gamma rays
WO2007121785A1 (fr) * 2006-04-24 2007-11-01 Ecolab Inc. Composition destinee a stabiliser des solutions alcalines contenant du chlore
EP2164944B1 (fr) * 2007-07-17 2013-03-06 Ecolab INC. Solutions de nettoyage concentrées stabilisées et leurs procédés de préparation
DE102007034539A1 (de) * 2007-07-20 2009-01-22 Henkel Ag & Co. Kgaa Schonendes Bleichmittel
US8859259B2 (en) 2010-02-14 2014-10-14 Ls9, Inc. Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
CN103131544A (zh) * 2011-11-22 2013-06-05 上海立昌环境工程有限公司 一种可生物降解型脱脂剂的制备及其应用
EP2836593A1 (fr) 2012-04-13 2015-02-18 REG Life Sciences, LLC Production microbienne d'alcanolamides et d'amidoamines et leurs utilisations

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60139799A (ja) * 1983-12-28 1985-07-24 ライオン株式会社 漂白剤
US4798675A (en) * 1987-10-19 1989-01-17 The Mogul Corporation Corrosion inhibiting compositions containing carboxylated phosphonic acids and sequestrants
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
US5104584A (en) * 1990-06-22 1992-04-14 The Clorox Company Composition and method for fabric encrustation prevention comprising a lignin derivative
JPH04370196A (ja) * 1991-06-17 1992-12-22 Dai Ichi Kogyo Seiyaku Co Ltd 過酸化水素漂白浴の安定化剤
JP2588345B2 (ja) * 1992-09-16 1997-03-05 花王株式会社 着色液体洗浄漂白剤組成物
US5780412A (en) * 1995-08-09 1998-07-14 The Sherwin-Williams Company Alkaline-stable hard surface cleaning compounds combined with alkali-metal organosiliconates

Also Published As

Publication number Publication date
PL338248A1 (en) 2000-10-09
HUP0004799A2 (hu) 2001-04-28
DE19731881C1 (de) 1998-10-22
SK942000A3 (en) 2000-07-11
HUP0004799A3 (en) 2002-11-28
ES2175751T3 (es) 2002-11-16
EP1000133A1 (fr) 2000-05-17
WO1999005245A1 (fr) 1999-02-04

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