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EP1149146B1 - Utilisation de polyacrylates modifies a l'acide phosphonique en tant que sequestrants - Google Patents

Utilisation de polyacrylates modifies a l'acide phosphonique en tant que sequestrants Download PDF

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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
Application number
EP00904959A
Other languages
German (de)
English (en)
Other versions
EP1149146A2 (fr
Inventor
Mercedes Mendoza Cruz
Adolf Arranz
Elisabet De Jorge
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 EP1149146A2 publication Critical patent/EP1149146A2/fr
Application granted granted Critical
Publication of EP1149146B1 publication Critical patent/EP1149146B1/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
    • C11D3/37—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)

Claims (9)

  1. Utilisation de polyacrylates qui ont été modifiés avec de l'acide phosphonique, le site de liaison du groupe acide phosphonique se trouvant sur la chaíne carbonée, avec des tampons, choisis dans le groupe formé par les silicates, les carbonates et/ou les phosphonates de métaux alcalins et/ou alcalino-terreux comme séquestrants pour la préparation d'agents de blanchiment aqueux.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'on utilise en outre des polyélectrolytes choisis dans le groupe formé par
    (a) les acides dicarboxyliques de bas poids moléculaire,
    (b) les acides hydroxycarboxyliques polyvalents de bas poids moléculaire,
    (c) les homopolymères et copolymères d'acides dicarboxyliques insaturés et leurs dérivés et/ou
    (d) les homopolymères et copolymères d'amides d'acides monocarboxyliques insaturés et leurs dérivés.
  3. Utilisation selon les revendications 1 et 2, caractérisée en ce qu'on utilise en outre des polyélectrolytes choisis dans le groupe formé par les poly-(N,N-bis-carboxyméthylèneacrylamides), les copolymères d'acide fumarique et d'acide vinylsulfonique, les polymères de l'acide 3-acrylamido-3-méthylpropanesulfonique, les copolymères de l'acide acrylique et de l'acide styrènesulfonique, les copolymères de l'acide acrylique avec du monophosphate de méthacrylate de 2-hydroxyéthyle, les homopolymères et les copolymères du chlorure de 3-acrylamido-3-méthylbutyltriméthylammonium, les copolymères du chlorhydrate de l'amide de diallylglycine et de l'acide acrylique, les copolymères de chlorure de diméthylallylammonium avec de l'acrylamide et/ou des polyéthylèneimines et/ou des polypropylèneimines.
  4. Utilisation selon au moins l'une quelconque des revendications 1 à 3, caractérisée en ce qu'on utilise des polyacrylates présentant un poids moléculaire dans la plage de 300 à 50000.
  5. Utilisation selon au moins l'une quelconque des revendications 1 à 4, caractérisée en ce qu'on utilise les polyacrylates en des quantités de 0,01 à 5% en poids par rapport à l'agent de blanchiment aqueux.
  6. Utilisation selon au moins l'une quelconque des revendications 1 à 5, caractérisée en ce qu'on utilise les polyacrylates dans des agents de blanchiment contenant de l'hypochlorite.
  7. Utilisation selon au moins l'une quelconque des revendications 1 à 6, caractérisée en ce qu'on utilise les polyacrylates avec des agents tensioactifs stables au chlore, qui sont choisis dans le groupe formé par les alkyléthersulfates, les oxydes d'amines, les alkyloligoglycosides et/ou les alcényloligoglycosides et/ou les sels d'acide gras.
  8. Utilisation selon au moins l'une quelconque des revendications 1 à 7, caractérisée en ce qu'on utilise les polyacrylates avec des azurants optiques stables au chlore.
  9. Utilisation selon au moins l'une quelconque des revendications 1 à 8, caractérisée en ce qu'on utilise les polyacrylates avec des parfums stables au chlore.
EP00904959A 1999-02-04 2000-01-25 Utilisation de polyacrylates modifies a l'acide phosphonique en tant que sequestrants Expired - Lifetime EP1149146B1 (fr)

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 (fr) 1999-02-04 2000-01-25 Utilisation de polyacrylates modifies a l'acide phosphonique en tant que sequestrants

Publications (2)

Publication Number Publication Date
EP1149146A2 EP1149146A2 (fr) 2001-10-31
EP1149146B1 true EP1149146B1 (fr) 2004-12-22

Family

ID=7896230

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00904959A Expired - Lifetime EP1149146B1 (fr) 1999-02-04 2000-01-25 Utilisation de polyacrylates modifies a l'acide phosphonique en tant que sequestrants

Country Status (6)

Country Link
EP (1) EP1149146B1 (fr)
AU (1) AU2666600A (fr)
CA (1) CA2297861A1 (fr)
DE (1) DE19904230A1 (fr)
ES (1) ES2233334T3 (fr)
WO (1) WO2000046328A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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
EP4428139A1 (fr) 2023-03-08 2024-09-11 Giovanni Bozzetto S.p.A. Derives de phosphonate de polyaminomethylene a faible teneur en phosphore et a proprietes sequestrantes et dispersantes, utilisations et procedes associes pour leur preparation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000011128A1 (fr) * 1998-08-19 2000-03-02 Jeyes Group Limited Compositions liquides de blanchiment
EP1001011A2 (fr) * 1998-11-11 2000-05-17 The Procter & Gamble Company Composition de blanchiment comprenant acide benzoique alkoxylé

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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 (fr) * 1996-08-12 1998-02-18 The Procter & Gamble Company Compositions de blanchiment
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000011128A1 (fr) * 1998-08-19 2000-03-02 Jeyes Group Limited Compositions liquides de blanchiment
EP1001011A2 (fr) * 1998-11-11 2000-05-17 The Procter & Gamble Company Composition de blanchiment comprenant acide benzoique alkoxylé

Also Published As

Publication number Publication date
AU2666600A (en) 2000-08-25
CA2297861A1 (fr) 2000-08-04
ES2233334T3 (es) 2005-06-16
EP1149146A2 (fr) 2001-10-31
WO2000046328A2 (fr) 2000-08-10
DE19904230A1 (de) 2000-08-10
WO2000046328A3 (fr) 2000-12-07

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