EP1149146B1 - Verwendung von phosphonsäure-modifizierten polyacrylaten als sequestriermittel - Google Patents
Verwendung von phosphonsäure-modifizierten polyacrylaten als sequestriermittel Download PDFInfo
- Publication number
- EP1149146B1 EP1149146B1 EP00904959A EP00904959A EP1149146B1 EP 1149146 B1 EP1149146 B1 EP 1149146B1 EP 00904959 A EP00904959 A EP 00904959A EP 00904959 A EP00904959 A EP 00904959A EP 1149146 B1 EP1149146 B1 EP 1149146B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- copolymers
- polyacrylates
- use according
- alcohol
- 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
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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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3784—(Co)polymerised monomers containing phosphorus
-
- 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 phosphacrylic modified polyacrylates as Sequestering agent for the production of aqueous bleaching agents.
- liquid bleaching agents preferably based on hypochlorite
- hypochlorite a detergent to remove particularly difficult stains.
- these must be compatible with the textile, ie the stain removal by treatment with the aggressive chemical hypochlorite should be carried out without attacking the tissue. Since skin contact with the bleaching agents is not excluded, the preparations must also be dermatologically compatible as far as possible.
- hypochtorite solutions can dissolve iron and manganese ions from the walls of the washing machine during the washing process, which subsequently catalyze photochemical reactions and lead to yellowing of the laundry. While the market tries to prevent this redeposition by using polyarylates [ DE 19730650 A1 (Henkel)], in practice this measure does not always prove to be satisfactory.
- the complex object of the invention has been the yellowing of the laundry to prevent metal deposits on the tissue and to use sequestrants
- aqueous bleaching agents especially chlorine bleach allow, with high stain removal ability, chlorine stable, gentle on textiles and are as skin-friendly as possible and have a sufficiently high viscosity.
- the invention relates to the use of polyacrylates which have been modified with phosphonic acid, the Linking point of the phosphonic acid group is located on the carbon chain with buffers selected from the group consisting of alkali and / or Alkaline earth metal silicates, carbonates and / or phosphonates, as Sequestering agent for the production of aqueous bleaching agents.
- the invention includes the finding that the use of other polyelectrolytes, buffers and, if necessary, chlorine-stable Surfactants and optical brighteners to further improve the stabilization against Yellowing, cleaning performance and dermatological tolerance.
- Polymers based on esters of acrylic acid with a characteristic chain building block of the formula (I) are referred to as polyacrylates, - [CH 2 -CH (COOR 1 )] - (I) in which R 1 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.
- Typical examples are polymers of acrylic acid and their esters with methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical hydrofluoric acid and dermal fatty alcohols, and technical hydrofluoric acid and dermal fatty alcohols based on, and technical hydroformylation
- Homopolymers or copolymers of acrylic acid and their methyl, tert-butyl or 2-ethylhexyl esters are preferably used.
- the resulting polyacrylates are modified with phosphonic acid, the point of attachment of the phosphonic acid group being on the carbon chain.
- the polymers obtained can have average molecular weights of the order of 300 to 50,000, preferably 1000 to 30,000 and in particular 5,000 to 10,000 daltons.
- the polyacrylates can be used in amounts of 0.01 to 5% by weight, based on the aqueous bleaching agents.
- the aqueous bleaching agents can contain hydrogen peroxide, preferably they are however, chlorine bleaching solutions containing alkali hypochlorite.
- alkali hypochlorites are To understand lithium, potassium and especially sodium hypochlorite.
- the hypochlorites can in Amounts of 1.5 to 10, preferably 2 to 8 and in particular 4 to 6 wt .-% - based on the Medium - can be used.
- the phosphonic acid-modified polyacrylates used in combination with buffers which are alkali and / or alkaline earth silicates, carbonates, phosphonates or mixtures thereof.
- the salts support the Sequestering effect of the polyelectrolytes and ensure that the preparations are constant have a highly 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 the amine oxidephosphonic acids, such as those sold under the brand Sequion® are sold by Bozetto / IT, e.g.
- 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 wt .-% - based on the means - are used.
- the bleaches obtainable using polyacrylates 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 for low temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C). Draw the funds are not only characterized by excellent stain removal, but also reliably prevent them Deposition of metal traces on the fibers and thus prevent yellowing. Although the actual use of the funds is aimed at removing stains from the laundry, They are generally also suitable for other purposes in which hypochlorite solutions are used find, for example, for cleaning and disinfection of hard surfaces.
- auxiliaries and additives include , for example, other chlorine-stable surfactants or hydrotropes, such as 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, by means of which the pH of the recipes can be adjusted to an optimal value of 10 to 14, preferably 12.5 to 13.5.
- Suitable optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
- derivatives of 4,4'-diamino-2,2'-stifbenedisulfonic acid (fiavonic acid) are suitable, such as, in particular, the salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6 -amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
- the potassium salt of 4,4'-bis (1,2,3-triazolyl) - (2-) - stilbin-2,2-sulfonic acid which is sold under the brand name Phorwite® BHC 766, is particularly preferred.
- the agents contain the optical brighteners in amounts of 1 and 5% by weight, preferably between 2 and 3% by weight. Blue dyes may also be present in small amounts.
- a particularly preferred dye is Tinolux® (Ciba-Geigy).
- Suitable active chlorine-stable fragrances are: Citronellol (3,7-dimethyl-6-octen-1-ol), Dimethyloctanol (3,7-Dimethyloctanol-1), Hydroxycitnonellol (3,7-Dimethyloctane-1,7-diol) , Mugol (3,7-dimethyl-4,6-octatrien-3-ol), mirsenol (2-methyl-6-methylene-7-octen-2-ol), terpinolene (p-mentho-1,4 (8 ) -diene), ethyl 2-methylbutyrate, phenylpropyl alcohol, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8, -hexamethylcyclopental-2-benzopyran, tonalid ( 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene), rose oxide,
- the color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz) in question.
- the manufacture of the agents according to the invention are carried out by stirring. If necessary, the product obtained be decanted or filtered to remove foreign bodies and / or agglomerates.
- the Agents also have a viscosity - measured at 20 ° C in a Brookfield viscometer (Spindle 1, 60 rpm) - below 100, preferably below 50 mPas.
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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)
Description
Claims (9)
- Verwendung von Polyacrylaten, die mit Phosphonsäure modifiziert wurden, wobei sich die Verknüpfungsstelle der Phosphonsäure-Gruppe an der Kohlenstoffkette befindet, zusammen mit Puffern, die ausgewählt sind aus der Gruppe, die gebildet wird von Alkali- und/oder Erdalkalisilicaten, -carbonaten und/oder phosphonaten, als. Sequestriermittel zur Herstellung von wäßrigen Bleichmitteln.
- Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß man zusätzlich Polyelektrolyte einsetzt, die ausgewählt sind aus der Gruppe, die gebildet wird von(a) niedermolekularen Dicarbonsäuren,(b) niedermolekularen mehrwertigen Hydroxycarbonsäuren,(c) Homo- und Copolymeren ungesättigter Dicarbonsäuren und deren Derivate und/oder(d) Homo- und Copolymeren ungesättigter Monocarbonsäureamide und deren Derivate.
- Verwendung nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß man zusätzlich Polyelektrolyte einsetzt, die ausgewählt sind aus der Gruppe, die gebildet wird von Poly-(N.N-biscarboxy-methylenacrylamiden), Copolymeren aus Fumarsäure und Vinylsulfonsäure, Polymeren der 3-Acrylami-do-3-methylpropansulfonsäure, Copolymeren aus Acrylsäure und Styrolsulfonsäure, Copolymeren von Acrylsäure mit 2-Hydroxyethyimethacrytat-Monophosphat, Homound Copolymeren des 3-Acrylamido-3-methylbutyltrimethylammoniumchlorids, Copolymeren aus Diallylglycinamid-Hydro-chlorid und Acrylsäure, Copolymeren von Dimethylallyiammoniumchlorid mit Acrylamid und/oder Polyethylen- und/oder -propyleniminen.
- Verwendung nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Polyacrylate mit einem Molekulargewicht im Bereich von 300 bis 50.000 einsetzt.
- Verwendung nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Polyacrylate in Mengen von 0,01 bis 5 Gew.-% - bezogen auf die wäßrigen Bleichmittel - einsetzt.
- Verwendung nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Polyacrylate in hypochlorithaltigen Bleichmitteln einsetzt.
- Verwendung nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Polyacrylate zusammen mit chlorstabilen Tensiden einsetzt, die ausgewählt sind aus der Gruppe, die gebildet wird von Alkylethersulfaten, Aminoxiden, Alkyl- und/oder Alkenyloligoglykosiden und/oder Fettsäuresalzen.
- Verwendung nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Polyarylate zusammen mit chlorstabilen optischen Aufhellern einsetzt.
- Verwendung nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man die Polyarylate zusammen mit chlorstabilen Duftstoffen einsetzt.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1999104230 DE19904230A1 (de) | 1999-02-04 | 1999-02-04 | Verwendung von phosphonsäure-modifizierten Polyacrylaten als Sequestriermittel |
DE19904230 | 1999-02-04 | ||
PCT/EP2000/000533 WO2000046328A2 (de) | 1999-02-04 | 2000-01-25 | Verwendung von phosphonsäure-modifizierten polyacrylaten als sequestriermittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1149146A2 EP1149146A2 (de) | 2001-10-31 |
EP1149146B1 true EP1149146B1 (de) | 2004-12-22 |
Family
ID=7896230
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00904959A Expired - Lifetime EP1149146B1 (de) | 1999-02-04 | 2000-01-25 | Verwendung von phosphonsäure-modifizierten polyacrylaten als sequestriermittel |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1149146B1 (de) |
AU (1) | AU2666600A (de) |
CA (1) | CA2297861A1 (de) |
DE (1) | DE19904230A1 (de) |
ES (1) | ES2233334T3 (de) |
WO (1) | WO2000046328A2 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005059048A1 (de) * | 2005-12-08 | 2007-06-14 | Henkel Kgaa | Reinigungsmittel für harte Oberflächen |
DE102007034539A1 (de) * | 2007-07-20 | 2009-01-22 | Henkel Ag & Co. Kgaa | Schonendes Bleichmittel |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000011128A1 (en) * | 1998-08-19 | 2000-03-02 | Jeyes Group Limited | Liquid bleaching compositions |
EP1001011A2 (de) * | 1998-11-11 | 2000-05-17 | The Procter & Gamble Company | Bleichmittelzusammensetzung enthaltende Alkoxyliertenbenzoesäure |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4333100C1 (de) * | 1993-09-29 | 1994-10-06 | Henkel Kgaa | Bleich- und Desinfektionsmittel |
JP3075659B2 (ja) * | 1993-10-13 | 2000-08-14 | 日本パーオキサイド株式会社 | 次亜塩素酸塩水溶液の安定化剤 |
EP0824145A1 (de) * | 1996-08-12 | 1998-02-18 | The Procter & Gamble Company | Bleichmittelzusammensetzungen |
DE19700799C2 (de) * | 1997-01-13 | 1999-02-04 | Henkel Kgaa | Wäßrige Textilbleichmittel |
GB9706653D0 (en) * | 1997-04-02 | 1997-05-21 | Johnson & Son Inc S C | Chlorine bleach toilet cleaner with sequestering agent |
-
1999
- 1999-02-04 DE DE1999104230 patent/DE19904230A1/de not_active Withdrawn
-
2000
- 2000-01-25 ES ES00904959T patent/ES2233334T3/es not_active Expired - Lifetime
- 2000-01-25 EP EP00904959A patent/EP1149146B1/de not_active Expired - Lifetime
- 2000-01-25 WO PCT/EP2000/000533 patent/WO2000046328A2/de active IP Right Grant
- 2000-01-25 AU AU26666/00A patent/AU2666600A/en not_active Abandoned
- 2000-02-02 CA CA 2297861 patent/CA2297861A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000011128A1 (en) * | 1998-08-19 | 2000-03-02 | Jeyes Group Limited | Liquid bleaching compositions |
EP1001011A2 (de) * | 1998-11-11 | 2000-05-17 | The Procter & Gamble Company | Bleichmittelzusammensetzung enthaltende Alkoxyliertenbenzoesäure |
Also Published As
Publication number | Publication date |
---|---|
WO2000046328A2 (de) | 2000-08-10 |
WO2000046328A3 (de) | 2000-12-07 |
ES2233334T3 (es) | 2005-06-16 |
DE19904230A1 (de) | 2000-08-10 |
AU2666600A (en) | 2000-08-25 |
EP1149146A2 (de) | 2001-10-31 |
CA2297861A1 (en) | 2000-08-04 |
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