EP0973857B1 - Nettoyage de cuvette de wc au moyen de compositions d'hypochlorite liquides - Google Patents

Nettoyage de cuvette de wc au moyen de compositions d'hypochlorite liquides Download PDF

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Publication number
EP0973857B1
EP0973857B1 EP98915249A EP98915249A EP0973857B1 EP 0973857 B1 EP0973857 B1 EP 0973857B1 EP 98915249 A EP98915249 A EP 98915249A EP 98915249 A EP98915249 A EP 98915249A EP 0973857 B1 EP0973857 B1 EP 0973857B1
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EP
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Prior art keywords
hypochlorite
process according
sequestering agent
bleach
potassium
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Expired - Lifetime
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EP98915249A
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German (de)
English (en)
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EP0973857A1 (fr
Inventor
Ian C. Callaghan
Timothy I. Moodycliffe
Richard W. Avery
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SC Johnson and Son Inc
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SC Johnson and Son Inc
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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
    • C11D3/361—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) 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
    • C11D3/36—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the present invention relates to a process for cleaning toilet bowls and to a composition, having bleaching and lime scale removal properties, which is particularly suitable for use in the method.
  • compositions based on hypochlorite bleach are well-known for use in cleaning hard surfaces which are subject to staining and in particular they are known for use as toilet cleaners.
  • the bowls of flushable toilets are subject to deposition of lime scale in hard water areas. This lime scale is predominantly calcium carbonate but may become discoloured by incorporation of coloured metal ions such as ions of Fe, Mn and by bacterial films and human waste deposits on the lime scale or on the surface of the toilet bowl.
  • Aqueous solutions of sodium hypochlorite usually containing a thickener to increase viscosity, are widely used in treating toilet bowls.
  • the hypochlorite bleaches the lime scale so that it is less noticeable but does not remove it.
  • the hypochlorite also acts as a disinfectant and users often rely on the odour of chlorine released by hypochlorite bleaches as confirmation that disinfection is taking place.
  • Sodium salts are generally the cheapest of the alkali and alkali metal salts (with the exception of such insoluble materials as calcium and magnesium carbonates) and in general sodium salts are used whenever a water soluble alkali metal or alkaline earth metal salt is required unless there is some known reason for using another salt.
  • hypochlorite bleaches is no exception and the commercially available toilet cleaners based on hypochlorite bleach use sodium hypochlorite.
  • Derwent WPI abstract accession number 87-032288/05 of JP-A-61-287995 discloses a two -pack cleaning composition for a flush toilet.
  • One pack comprises bleaching agent and the other pack comprises non-ionic surfactant, water-soluble inorganic salt and water-insoluble inorganic salt.
  • the bleaching agent may be NaClO, KClO, LiClO, Ca hypochlorite, or Na or K dichloroisocyanurate.
  • the use of a two pack composition will be inconvenient.
  • the abstract does not suggest that the use of hypochlorites other than NaOCI has any advantages which would justify the increased cost.
  • Derwent WPI abstract accession number 87-032283/05 of JP-A-61-287990 discloses a cleaning composition which may be used in flushing toilets, and may be in the form of a liquid, solid, paste, or granules. It comprises a chlorine bleach and and an alkali metal alkyl succinate.
  • the chlorine bleach may be calcium hypochlorite, or sodium or potassium dichloroisocyanurate.
  • the chlorine bleaches disclosed in this abstract have low solubility in water and are generally supplied commercially as solids. However an important market for chlorine bleaches is as pourable liquids which are poured by the user into the toilet bowl. For this purpose chlorine bleaches having high solubility in water are desirable, namely the water soluble hypochlorite bleaches.
  • the abstract contains nothing which suggests that the use of potassium as opposed to sodium dichloroisocyanurate gives any advantage in lime scale removal.
  • the first chlorine bleach mentioned is calcium hypochlorite the abstract does not appear to be concerned with the problems caused by the presence of calcium ions.
  • JP 61-197697 discloses a flush toilet cleaner composition
  • a flush toilet cleaner composition comprising 0.1-60 wt% water-soluble substance selected from polycarbonic acid polymers, hydroxypolycarbonic acids, polyamino sulphonic acids and their derivatives of average molecular weight of 100-1500; and 0.5-80 wt% decolourant, preferably one of the hypochlorites, percarbonates or perphthalates.
  • JP 61-197699 discloses a two separate agent type cleaner composition for a flush toilet comprising (A) a chlorine decolourant, preferably a hypochlorite; and (B) a solid- or paste-form agent consisting of 0.1 to 60% of a water-soluble organic material selected from polycarbonic acid polymers, aminopolycarbonic acids, hydroxypolycarbonic acids, polyamino phosphonic acids and their derivatives with an average molecular weight of 100-1500; and 0.1 to 30 wt% of a colouring matter which is decoloured in the coexistence with a chlorine decolourant.
  • a chlorine decolourant preferably a hypochlorite
  • a solid- or paste-form agent consisting of 0.1 to 60% of a water-soluble organic material selected from polycarbonic acid polymers, aminopolycarbonic acids, hydroxypolycarbonic acids, polyamino phosphonic acids and their derivatives with an average molecular weight of 100-1500; and 0.1 to 30 wt% of a
  • FR 2580625 discloses a composition for removing scale or inhibiting scale formation comprising a mixture of (a) an anti-scaling agent and (b) a sequestering agent.
  • a method of cleaning a flushable toilet bowl which comprises
  • the process makes use of a single pack pourable liquid composition. If it contains more than one phase then the phases should be so dispersed that they are stable on storage.
  • the composition is a homogeneous liquid phase, which may have a high viscosity.
  • the hypochlorite bleach used in the process of the present invention may be potassium hypochlorite or a mixture of potassium hypochlorite and sodium hypochlorite providing that at least 50% by weight of the hypochlorite present is potassium hypochlorite.
  • the hypochlorite bleach includes potassium hypochlorite.
  • the composition is an aqueous solution the potassium ions are not directly associated with the hypochlorite ions in solution. Where other metal cations are present in solution the quantity of potassium hypochlorite is taken to be that corresponding to matching all the available potassium with all the available hypochlorite. If there is an excess of potassium ions then the amount of hypochlorite will determine the amount of potassium hypochlorite considered to be present. If there is an excess of hypochlorite then the amount of potassium ions will determine the amount of potassium hypochlorite considered to be present.
  • At least 50% by weight of the hypochlorite present is present as potassium hypochlorite, preferably at least 60%, more preferably at least 80% of the hypochlorite is present as potassium hypochlorite.
  • Preferably all the hypochlorite is present as potassium hypochlorite and hypochlorite is the only chlorine bleaching agent present.
  • Potassium hypochlorite may be the sole hypochlorite used to manufacture the toilet cleaner composition for use in the invention.
  • the composition contains a sequestering agent to sequester metal cations especially calcium ions but also iron and manganese ions.
  • the sequestering agent is bleach-resistant i.e. it must of course be sufficiently stable in the presence of chlorine bleach to retain a useful level of sequestering activity after storage.
  • Certain polymers containing carboxylic acid groups have activity as crystal growth modifiers, i.e. they modify the growth of crystals which could lead to scale formation so that the crystals are retained in suspension and are not deposited. Such polymers are, however, not satisfactory for removing scale which has already formed.
  • the sequestering agents of the present invention have molecular weights (weight average molecular weight) of below 1500, preferably below 1000, more preferably below 500.
  • the sequestering agents will preferably contain a hatero-atom, i.e. an atom other than carbon, which atom is bonded to at least two other atoms, preferably carbon atoms.
  • a hatero-atom i.e. an atom other than carbon, which atom is bonded to at least two other atoms, preferably carbon atoms.
  • hetero-atoms are N, P, S, O, B, Si.
  • the preferred hetero-atoms are N, P, and S.
  • the sequestering agent is bleach-resistant. Sequestering agents containing nitrogen atoms are often attacked by hypochlorite. However in the compound MeN(CH 2 CO 2 Na) 2 , which is commercially available as "Biohamp DA" the N atom is protected by steric hindrance. A similar compound which contains an S atom , not an N atom, is HO 2 CCH 2 CH(CO 2 H)SCH 2 CO 2 H commercially available as "Biohamp MS".
  • a preferred class of sequestering agents are the phosphonate sequestering agents.
  • An example of a phosphonate sequestering agent is 1-hydroxyethylidene (1,1-diphosphonic acid). This is not completely stable in hypochlorite solutions.
  • preferred phosphonate sequestering agents are the salts of N-oxides of nitrilo tris(methylene phosphonic acid). The free acid has the formula
  • the sequestering agent is preferably a potassium salt of a phosphonate.
  • composition is a single pack composition. It is added to the toilet bowl as an aqueous solution from the container in which it is supplied.
  • the composition may contain a salt of a weak acid, the salt giving an alkaline pH in aqueous solution.
  • the use of such salts gives a buffering action which assists in the control of pH during manufacture of the composition.
  • the salt may for example be potassium carbonate or potassium borate.
  • the composition is preferably applied to the toilet bowl as an aqueous solution of high viscosity so that it will cling to the interior of the toilet bowl.
  • the high viscosity may be obtained by means of a thickening system.
  • combinations of various surface active agents may be used to give a high viscosity gel -like product.
  • a cleaner with a viscosity of less than 1000 cps (centipoise second), more preferably less than 400 cps, most preferably less than 300 cps.
  • the viscosities given above are measured using a Brookfield viscometer (SP2, 12 rpm, 30 seconds, at 25°C)
  • the proportion of potassium cations in the metal cations in solution in the composition is preferably at least 10% of the total number of cations moles present, more preferably at least 30%, most preferably at least 40% of the total number of cations moles present
  • the metal cations present in the composition are preferably predominantly potassium ions.
  • the solution contains potassium ions in excess of the amount required to correspond to the hypochlorite anions present.
  • the composition is preferably prepared using a potassium compound in addition to potassium hypochlorite
  • the amount of hypochlorite bleach in the composition is preferably in the range 0.5% to 12 % wt/wt, measured as active material, more preferably 1% to 8% wt/wt.
  • the pH is preferably in the range 10-13.5, more preferably 11.5 to 13.
  • the amount of sequestering agent is preferably in the range 1 to 20% by weight, based on weight of active material , more preferably in the range 1 to 10%, most preferably 2% to 6%. wt/wt.
  • the composition may contain a perfume.
  • the perfume used must be resistant to attack by chlorine bleach, but such perfumes are commercially available.
  • the marble cube test is carried out as follows. A marble cube is washed with tap water and a paper towel is used to remove excess water. The cube is placed in a foil dish, allowed to dry in an oven overnight, and then removed and allowed to cool to ambient temperature. The cube is then weighed. A sample (100g) of the product to be tested is placed in a 250 ml conical flask. The marble cube is then placed in the product and the flask left for approximately 18 hours. The cube is then removed from the flask, rinsed thoroughly with deionized water, blotted dry with a paper towel and placed in the foil dish. The dish is placed in the oven overnight to allow the marble cube to dry. The cube was then re-weighed to determine the weight lost (if any).
  • a standard commercially available thickened sodium hypochlorite bleach was tested for its ability to remove lime scale removal using the marble cube test.
  • the bleach concentration was 10%wt/wt. No detectable loss of weight of the marble cube took place.
  • a liquid hypochlorite bleach cleaning liquid was prepared as follows. Deionized water (74.5 parts by weight) was introduced into a vessel provided with a stirrer. A sequestering agent (5 parts by weight)(pbw) was then added. The sequestering agent was a commercially product sold under the trade name "Dequest 2010". It contained 60% by weight of the active ingredient HEDP (1-hydroxyethylidene (1, 1-diphosphonic acid)). An aqueous solution of KOH( (20% by weight) was then added in an amount sufficient to give a pH of 8. Potassium carbonate (0.5 pbw) was added. Three surfactants were then added to thicken the aqueous liquid.
  • the first was sodium lauryl ether sulphate (3.5pbw of 27% active material), the second was sodium lauryl sarcosinate (1 pbw of 30% active material).
  • the third was a C12 amine oxide surfactant (4.5 pbw of 30% active material) sold under the trade name "Empigen OB”.
  • KOCI (10.5 pbw of 20% wt/wt solution) was then added, and 0.25 pbw of perfume, to give a total of 100 pbw.
  • the resulting liquid was clear, had a pH of 13.49, a viscosity of 150 cps measured using a Brookfield viscometer (SP2, 12 rpm, 30 seconds, at 25°C).,The average of two results for the marble cube test was 0.68% dissolved.
  • a thickened toilet cleaning composition was prepared as in Example 1 except that the quantity of deionized water was 65.75 pbw, the quantity of sodium lauryl ether sulphate was 7 pbw, the quantity of sodium lauryl sarcosinate was 2 pbw, and the quantity of amine oxide surfactant was 9 pbw.
  • the resulting liquid was clear, had a pH of 13.25 and a viscosity of 275 cps.
  • the marble cube test result was 0.41 % dissolved.
  • Example 2 An experiment was carried out as in Example 1 except that neither surfactants nor perfume were added and the quantity of deionized water was increased to 84 pbw to bring the total up to 100 pbw.
  • the resulting liquid was clear, had a pH of 13.70, and was water-thin.
  • the marble cube test result was 0.81 % dissolved.
  • Example 3 An experiment was carried out as in Example 3 except that the sequestering agent was the N-oxide of nitrilo tris(methylene phosphonic acid) in its potassium salt form (12pbw) commercially available as "Briquest 3010-25K” from Albright & Wilson, and containing 25% of active material. The amount of water was adjusted to 77 pbw.
  • the sequestering agent was the N-oxide of nitrilo tris(methylene phosphonic acid) in its potassium salt form (12pbw) commercially available as "Briquest 3010-25K" from Albright & Wilson, and containing 25% of active material. The amount of water was adjusted to 77 pbw.
  • the product was clear, had a pH of 13.5, and was water thin.
  • the marble-cube test result was 0.67% dissolved.
  • the product was clear, had a pH of 13.5, and was water thin.
  • the marble cube test result was 0.61 % dissolved.
  • the product was dear, had a pH of 13.4, and was water thin.
  • the marble cube test result was 0.06% dissolved.
  • the product had some lime scale activity but was not as active as the products containing phosphonic acid sequestering agents.
  • Example 3 An experiment was carried out as in Example 3 but using a mixture of the sequestering agent of example 1 ("Dequest 2010) (2.50 pbw) and that of Example 6 ("Biohamp DA" (1.50 pbw).
  • the product was clear, had a pH of 13.8, and was water thin.
  • the marble cube test result was 0.33% dissolved.
  • Example 4 An experiment was carried out as in Example 4 except that the KOCI was replaced by NaOCI (14 pbw of 15% wt/wt solution) with the amount of deionized water adjusted to 73.5 ppw.
  • the composition still contained potassium ions as a result of neutralization with KOH and the use of potassium carbonate.
  • the product was clear, had a pH of 12.90, and was water thin.
  • the marble cube test result was 0.55 % dissolved.
  • the product was clear, had a pH of 12.8, and was water thin.
  • the marble cube test result was 0.16% dissolved.
  • the product was clear, had a pH of 13.5 and was water thin.
  • the marble cube test result was 0,23 % dissolved.
  • Example 3 An experiment was carried out as in Example 3 except that the neutralizations to pH 8 and pH 13 were carried out using NaOH instead of KOH, sodium carbonate 0.5pbw) was added instead of potassium carbonate, and NaOCL (14 pbw of 15% wt/wt solution) was used instead of KOCI. The quantity of deionized water was adjusted to 80.5 pbw.
  • the product was clear, had a pH of 12.90 and was water thin.
  • the marble cube test result was 0.26 % dissolved.
  • Example 3 shows the superiority of the product based on KOH and KOCI when used with phosphonate sequestering agents.
  • Example 4 An experiment was carried out as in Example 4 but with the changes set out in Example 11, and the amount of deionized water adjusted to 73.5 pbw.
  • the product was clear, had a pH of 12.7 and was water thin.
  • the marble cube test result was 0.31% dissolved.
  • Example 4 shows the benefits of the product based on KOH and KOCI when used with phosphonate sequestering agents.
  • Example 5 An experiment was carried out as in Example 5 but with the changes set out in Example 11, and with the amount of deionized water adjusted to 77 pbw.
  • the product was clear, had a pH of 12.85 and was water thin.
  • the marble cube test result was 0.29% dissolved.
  • Example 5 shows the superiority of the product based on potassium salts when used with phosphonate sequestering agents.
  • Example 6 An experiment was carried out as in Example 6 but with the changes set out in Example 11, and the deionized water content adjusted to 82.5 pbw.
  • the product was clear, had a pH of 12.95 and was water thin.
  • the marble cube test result was 0.06 % dissolved.

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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)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (19)

  1. Procédé pour le nettoyage d'une cuvette de toilettes rinçable qui comprend les étapes consistant
    a) à verser à l'intérieur de la cuvette de toilettes à partir d'un récipient une composition liquide aqueuse comprenant un agent blanchissant d'hypochlorite dans laquelle au moins 50 % en poids de l'hypochlorite présent est de l'hypochlorite de potassium ; et un agent séquestrant organique résistant à l'agent blanchissant ayant un poids moléculaire inférieur à 1500 qui séquestre le calcium, et
    b) à rincer ensuite les toilettes.
  2. Procédé selon la revendication 1, dans lequel au moins 60 % de l'hypochlorite présent sont de l'hypochlorite de potassium.
  3. Procédé selon la revendication 1, dans lequel la totalité de l'hypochlorite est présent dans la forme d'hypochlorite de potassium.
  4. Procédé selon la revendication 1, dans lequel l'agent séquestrant présente un poids moléculaire inférieur à 1000.
  5. Procédé selon la revendication 1, dans lequel l'agent séquestrant présente un poids moléculaire inférieur à 500.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent séquestrant contient un hétéro-atome.
  7. Procédé selon la revendication 6, dans lequel l'hétéro-atome est lié à au moins deux atomes de carbone.
  8. Procédé selon la revendication 7, dans lequel l'hétéro-atome est N, P ou S.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent séquestrant présente une constante de stabilité pour le calcium dans l'intervalle de 3 à 12.
  10. Procédé selon la revendication 9, dans lequel la constante de stabilité se trouve dans l'intervalle de 4 à 11.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent séquestrant est un agent séquestrant de phosphanate.
  12. Procédé selon la revendication 11, dans lequel l'agent séquestrant de phosphanate est un sel d'un N-oxyde de nitrilotris(acide méthylènephosphonique).
  13. Procédé selon l'une quelconque des revendications précédentes, dans lequel la proportion d'ions potassium dans les cations métalliques en solution dans la composition est d'au moins 10 % du nombre total de moles de cations présentes.
  14. Procédé selon la revendication 13, dans lequel la proportion d'ions potassium est d'au moins 40 % du nombre total de moles de cations présentes.
  15. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition contient des ions potassium en excès de la quantité nécessaire pour correspondre aux ions hypochlorite présents.
  16. Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité d'agent blanchissant d'hypochlorite dans la composition se trouve dans l'intervalle de 0,5 % à 12 % en poids mesurée comme matière active.
  17. Procédé selon l'une quelconque des revendications précédentes, dans lequel le pH se trouve dans l'intervalle de 10 à 13,5.
  18. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition contient de 1 à 20 % en poids d'agent séquestrant, rapportés au poids de matière active.
  19. Composition nettoyante d'agent blanchissant d'hypochlorite liquide aqueuse pouvant être versée, en un seul paquet, caractérisée en ce que la composition nettoyante aqueuse comprend un agent blanchissant d'hypochlorite, dans laquelle au moins 50 % en poids de l'hypochlorite comprennent de l'hypochlorite de potassium ; et un agent séquestrant organique résistant à l'agent blanchissant ayant un poids moléculaire inférieur à 1500 qui séquestre le calcium.
EP98915249A 1997-04-02 1998-04-02 Nettoyage de cuvette de wc au moyen de compositions d'hypochlorite liquides Expired - Lifetime EP0973857B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9706653 1997-04-02
GBGB9706653.4A GB9706653D0 (en) 1997-04-02 1997-04-02 Chlorine bleach toilet cleaner with sequestering agent
PCT/US1998/006571 WO1998044082A1 (fr) 1997-04-02 1998-04-02 Nettoyage de cuvette de wc au moyen de compositions d'hypochlorite liquides

Publications (2)

Publication Number Publication Date
EP0973857A1 EP0973857A1 (fr) 2000-01-26
EP0973857B1 true EP0973857B1 (fr) 2002-10-02

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EP (1) EP0973857B1 (fr)
AT (1) ATE225394T1 (fr)
CA (1) CA2285907C (fr)
DE (1) DE69808445T2 (fr)
DK (1) DK0973857T3 (fr)
ES (1) ES2180160T3 (fr)
GB (1) GB9706653D0 (fr)
WO (1) WO1998044082A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9727299D0 (en) * 1997-12-23 1998-02-25 Jeyes Group Plc Lavatory cleansing blocks
DE19904230A1 (de) * 1999-02-04 2000-08-10 Henkel Kgaa Verwendung von phosphonsäure-modifizierten Polyacrylaten als Sequestriermittel
EP1894990A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Dose d'unité de la composition pâteuse pour des articles sanitaires

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61287990A (ja) * 1985-06-17 1986-12-18 花王株式会社 洗浄剤組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4200606A (en) * 1978-12-22 1980-04-29 The Procter & Gamble Company Method for sanitizing toilets
JP2822031B2 (ja) * 1985-02-28 1998-11-05 花王株式会社 水洗便器用清浄剤組成物
JPS61197699A (ja) * 1985-02-28 1986-09-01 花王株式会社 ２剤型水洗便器用着色清浄剤組成物
FR2580625B1 (fr) * 1985-04-18 1991-06-28 Oreal Composition detartrante et/ou inhibitrice de la formation de tartre, destinee notamment au nettoyage des surfaces emaillees

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61287990A (ja) * 1985-06-17 1986-12-18 花王株式会社 洗浄剤組成物

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Publication number Publication date
DE69808445T2 (de) 2003-01-23
DE69808445D1 (de) 2002-11-07
DK0973857T3 (da) 2003-02-03
ES2180160T3 (es) 2003-02-01
GB9706653D0 (en) 1997-05-21
WO1998044082A1 (fr) 1998-10-08
ATE225394T1 (de) 2002-10-15
CA2285907A1 (fr) 1998-10-08
CA2285907C (fr) 2005-10-25
EP0973857A1 (fr) 2000-01-26

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