EP1966364B1 - Amélioration de la stabilité de détergents contenant de l'hypochlorite - Google Patents

Amélioration de la stabilité de détergents contenant de l'hypochlorite Download PDF

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Publication number
EP1966364B1
EP1966364B1 EP06829421.4A EP06829421A EP1966364B1 EP 1966364 B1 EP1966364 B1 EP 1966364B1 EP 06829421 A EP06829421 A EP 06829421A EP 1966364 B1 EP1966364 B1 EP 1966364B1
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EP
European Patent Office
Prior art keywords
hydrogen
alkali metal
hypochlorite
ammonium
tetra
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.)
Not-in-force
Application number
EP06829421.4A
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German (de)
English (en)
Other versions
EP1966364A1 (fr
Inventor
Carlos Malet
Miguel Osset
Mercedes Mendoza Cruz
Nuria Montaner
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
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL06829421T priority Critical patent/PL1966364T3/pl
Publication of EP1966364A1 publication Critical patent/EP1966364A1/fr
Application granted granted Critical
Publication of EP1966364B1 publication Critical patent/EP1966364B1/fr
Not-in-force 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
    • C11D3/395—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
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to the stabilization of hypochlorite-containing aqueous liquid detergents containing optical brighteners.
  • Sodium hypochlorite is known to be a highly effective bleaching agent and has been used for a long time, optionally with soaps and / or synthetic surfactants, to remove stains and all sorts of soils from laundry to textiles as well as hard surface cleaning. It is normally sold in concentrations of about 2% to 10% by weight in water for household use
  • Liquid detergent formulations or corresponding preparations of hard surface cleaners containing hypochlorite as a bleach component are susceptible to loss of activity upon prolonged storage, especially because of the then-degradation of the hypochlorite.
  • ingredients that are desirable from an application point of view or for aesthetic reasons in detergents and cleaners include, in addition to the performance of such agents crucial influencing agents, among which in particular the hypochlorite may be mentioned, also active ingredients, which rather the visual appearance of the so affect treated textiles.
  • active ingredients which rather the visual appearance of the so affect treated textiles.
  • optical brighteners to name, which raise during the washing process on the fibers of the textile material. These compounds are able to absorb light and emit light of shorter wavelength.
  • the present invention relates to the use of diethylenetriaminepentamethylenephosphonic acid and / or its alkali metal salt for stabilizing optical brighteners in aqueous liquid detergents which contain alkali metal hypochlorite.
  • hypochlorite-containing liquid agents With the addition of diethylenetriamine penta-methylenephosphonic acid and / or their alkali metal salts to hypochlorite-containing liquid agents, the stability of optical brighteners contained in these agents is increased and also the hypochlorite is degraded less rapidly during storage than without this addition of Case is.
  • Diethylenetriamine penta-methylenephosphonic acid is commercially available, for example, under the trade name Dequest® 2066.
  • the agent may contain any alkali salts of diethylenetriamine penta-methylenephosphonic acid. Preference is given to the use of the mono-, di-, tri-, tetra- or penta-sodium salt which can be used as such in the preparation of the compositions or in situ from the diethylenetriamine-penta-methylenephosphonic acid and alkali used instead forms.
  • optical brighteners which correspond to the formulas (I) or (II).
  • Optical brighteners are usually present only in small amounts, for example from 10 ppm to 0.5 wt .-%, in detergents or bleaches
  • the preparations are particularly suitable and very effective as a bleaching or bleaching detergent for white textiles.
  • Such an agent is effective against a variety of stains, including greasy soils such as sebum, makeup or lipstick, enzymatically removable stains such as blood, grass or cocoa, and bleachable soils such as wine, coffee or tea, even after aging of the composition, ie if it has been stored for a long time after its production.
  • a further advantage of using bleaches according to the present invention is that they are suitable for bleaching textiles of various materials, including those of natural fibers such as cotton or linen, but also those of synthetic material, such as synthetic polymer fibers, and also those of corresponding blended fabrics.
  • a liquid composition using the present invention is advantageously applied to the textiles to be cleaned in diluted form, for example, when it is used in manual or machine washing of textiles as a laundry detergent or alone as a detergent, but it can additionally or alternatively also undiluted on the Textile are applied, for example as a liquid pretreatment agent or stain remover.
  • a bleaching agent in the form of hypochlorite is an integral part of the invention.
  • Bleaches per se are well-known components of detergent and cleaner compositions and, in particular, are also successful in controlling mildew and mildew and in disinfecting.
  • alkali metal hypochlorites such as potassium hypochlorite
  • sodium hypochlorite in stabilized compositions of this invention.
  • Commercially available aqueous sodium hypochlorite solutions often contain considerable amounts of chloride salts. These can be readily used to prepare such agents, so that one does not necessarily rely on the use of high purity NaOCl.
  • the compositions contain 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight, of alkali metal hypochlorite.
  • the stabilized agents are normally alkaline and may contain for this purpose from about 0.1% to 2%, more preferably from 0.1% to 1.1%, by weight, alkali metal hydroxide.
  • alkali hydroxide is sodium hydroxide, and also the alkali salts mentioned in connection with the other ingredients of the compositions are preferably the sodium salts.
  • the formulations may contain surfactants that are stable in the presence of the hypochlorite.
  • betaines in particular those of the general formula IX, wherein R 14 is an alkyl or alkenyl group having 6 to 22 carbon atoms or a group R 17 is CO-NH- (CH 2 ) n -, R 15 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 16 is hydrogen or an alkyl group with 1 to 4 carbon atoms, R 17 is an alkyl or alkenyl group having 6 to 22 carbon atoms, m is a number from 1 to 6 and, n is a number from 1 to 3.
  • surfactants examples include C 12-18 alkyl dimethyl betaine, commercially available as coconut betaine, and C 10-16 alkyl dimethyl betaine, commercially available as lauryl betaine.
  • Another class of particularly preferred surfactants are the alkyl ether sulfates obtainable by reacting alcohols (preferably having 6 to 22 carbon atoms) with alkylene oxides, especially ethylene oxide, followed by sulfation and neutralization, especially a C 12-14 fatty alcohol ether sulfate alkoxylated with 2 equivalents of ethylene oxide , In the ether sulfates, the corresponding cation is preferably sodium.
  • Surfactants are preferably included in the compositions in amounts of up to 20% by weight, in particular from 0.1% by weight to 15% by weight.
  • the preparations may optionally contain, in addition to the diethylenetriamine penta-methylenephosphonic acid and / or their alkali metal salt, further sequestering agents, preferably alkylphosphonic acids having at least one amine oxide substituent on the alkyl group, referred to herein as amine oxide phosphonic acids, polyacrylic acids and / or polyoxyacids containing phosphono groups, which are also known in the art may be in the form of their alkali metal salts.
  • amine oxide phosphonic acids having at least one amine oxide substituent on the alkyl group
  • polyacrylic acids and / or polyoxyacids containing phosphono groups which are also known in the art may be in the form of their alkali metal salts.
  • Amine oxide phosphonic acids are normally prepared by oxidation of aminoalkyl phosphonic acids.
  • amine oxide phosphonic acids are the amine oxide based on aminotrimethylene phosphonic acid.
  • R 18 is hydrogen, a group - (CH 2 ) x (CHCH 3 ) y -NH 2 -> O or an alkali metal
  • x is a number from 1 to 4
  • y is 0 or 1.
  • R 18 is hydrogen, a group - (CH 2 ) x (CHCH 3 ) y -NH 2 -> O or an alkali metal
  • x is a number from 1 to 4
  • y is 0 or 1.
  • the more preferred amine oxide phosphonic acids is the amine oxide based on aminotrimethylene phosphonic acid.
  • from 0.01% to 2% by weight of such additional sequestering agents are present.
  • the preparations may contain small amounts of pH-buffering substances and / or one or more pale-stable dyes or fragrances.
  • the optional perfume component is preferably of higher relative volatility than the ingredients optionally responsible for a bleaching odor.
  • the compositions contain from more than 0 wt% to about 0.01 wt%, more preferably from about 0.001 wt% to about 0.008 wt% of colored, especially blue and / or green, metal pigment.
  • complex compounds of nickel, cobalt, cuprous, iron and / or manganese are preferred; particularly preferred are copper phthalocyanine dyes.
  • alkali iodide in particular potassium iodide
  • Useful pH-buffering ingredients are preferably selected from the alkali carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, phosphates, stannates, aluminates, and mixtures thereof, the preferred alkali metals being sodium and Are potassium.
  • the starting materials for producing, for example, the hypohalite bleach may include by-products, for example, carbonate, which may result in levels of such by-products in the agents of optionally up to 0.4% by weight.
  • the aqueous compositions normally have viscosities in the range of about 25 mPa.s to 1500 mPa.s, in particular from 50 mPa.s to 1100 mPa.s.
  • a composition may be used, in dilute or undiluted form, to remove stains and stains on textiles by allowing the composition and the textile to contact one another for a time sufficient to bleach the fabric, and thereafter the fabric Water washes.
  • the textile may also be washed using such an agent by hand or in a machine washing process in which such agent is metered into a conventional washing machine.

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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 (6)

  1. Utilisation de l'acide diéthylènetriaminepentaméthylènephosphonique et/ou de son sel de métal alcalin pour la stabilisation d'azurants optiques dans des agents de lavage liquides aqueux qui contiennent de l'hypochlorite de métal alcalin.
  2. Utilisation selon la revendication 1, caractérisée en ce que le sel de métal alcalin est un sel de sodium.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que la composition contient de plus de 0 % en poids à 0,5 % en poids, en particulier de 0,01 % en poids à 0,1 % en poids de l'acide diéthylènetriaminepentaméthylènephosphonique et/ou de son sel de métal alcalin.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que l'azurant optique est choisi parmi un composé répondant à l'une quelconque des formes suivantes (I) à (VIII) ou leurs mélanges :
    Figure imgb0027
    Figure imgb0028
    Figure imgb0029
    Figure imgb0030
    Figure imgb0031
    Figure imgb0032
    Figure imgb0033
    Figure imgb0034
     dans lesquelles
    R1 représente un atome d'hydrogène, un groupe -SO3M, un groupe -OR13, un groupe -CN, un atome de chlore, un groupe -COOR13, un groupe -CON(R13)2 ;
    R2 et R3 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe -R13 ou un groupe -Ar ;
    R4 et R5 représentent, indépendamment l'un de l'autre, un groupe -OH, un atome de chlore, un groupe -NH2, un groupe -OR13, un groupe -O-Ar, un groupe -NHR13, un groupe -N(R13)2, un groupe -NR13R14, un groupe -N(R14)2, un groupe -NH-Ar, un groupe morpholino, un groupe -S-R13 ou un groupe -S-Ar ;
    R6 représente un atome d'hydrogène, un atome de chlore ou un groupe -SO3M ;
    R7 représente un groupe -CN, un groupe -SO3M, un groupe -S-R13 ou un groupe -S-Ar ;
    R8 représente un atome d'hydrogène, un groupe -R13, un atome de chlore ou un groupe -SO3M ;
    R9 et R10 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe -R13, un atome de chlore, un groupe -SO3M ou un groupe -OR13 ;
    R11 représente un atome d'hydrogène ou un groupe -R13 ;
    R12 représente un atome d'hydrogène, un groupe -R13, un groupe -CN, un atome de chlore, un groupe -COOR13, un groupe -CON(R13)2, un groupe -Ar ou un groupe -O-Ar ;
    R13 représente un groupe alkyle en C1-C4 ramifié ou non ramifié ;
    R14 représente un groupe hydroxyalkyle en C1-C4 ramifié ou non ramifié ;
    Ar représente un groupe phényle, un groupe naphtyle, un groupe pyridinyle, un groupe pyridazinyle, un groupe pyrimidinyle, un groupe pyrazinyle, un groupe triazinyle, un groupe indolyle, un groupe anthracényle, un groupe phénanthrényle ou un groupe benzonaphtyle substitué de manière facultative avec un groupe -R13, un atome de chlore, un groupe -SO3M ou un groupe -OR13 ;
    M représente un atome d'hydrogène, un atome de sodium, un atome de potassium, un atome de calcium, un atome de magnésium, un groupe d'ammonium, un groupe d'ammonium monosubstitué, disubstitué, trisubstitué ou tétrasubstitué avec un groupe -R13 ou un groupe d'ammonium monosubstitué, disubstitué, trisubstitué ou tétrasubstitué avec un groupe -R14 ou un groupe d'ammonium monosubstitué, disubstitué, trisubstitué ou tétrasubstitué avec un mélange d'un groupe R13 et d'un groupe R14.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la composition contient de 0,5 % en poids à 5 % en poids d'un hypochlorite de métal alcalin, en particulier d'hypochlorite de sodium.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que la composition contient jusqu'à 20 % en poids d'un agent tensioactif stable au blanchiment, en particulier de la bétaïne et/ou un alkyléthersulfate.
EP06829421.4A 2005-12-30 2006-12-08 Amélioration de la stabilité de détergents contenant de l'hypochlorite Not-in-force EP1966364B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06829421T PL1966364T3 (pl) 2005-12-30 2006-12-08 Podwyższenie stabilności podchlorynonośnych środków piorących

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005063177A DE102005063177A1 (de) 2005-12-30 2005-12-30 Erhöhung der Stabilität hypochlorihaltiger Waschmittel
PCT/EP2006/011814 WO2007079856A1 (fr) 2005-12-30 2006-12-08 Amélioration de la stabilité de détergents contenant de l'hypochlorite

Publications (2)

Publication Number Publication Date
EP1966364A1 EP1966364A1 (fr) 2008-09-10
EP1966364B1 true EP1966364B1 (fr) 2014-03-19

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US (1) US7786066B2 (fr)
EP (1) EP1966364B1 (fr)
DE (1) DE102005063177A1 (fr)
ES (1) ES2455145T3 (fr)
PL (1) PL1966364T3 (fr)
WO (1) WO2007079856A1 (fr)

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US20130096045A1 (en) 2011-10-12 2013-04-18 Ecolab Usa Inc. Moderately alkaline cleaning compositions for proteinaceous and fatty soil removal at low temperatures

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Publication number Publication date
US20080305980A1 (en) 2008-12-11
US7786066B2 (en) 2010-08-31
DE102005063177A1 (de) 2007-07-05
ES2455145T3 (es) 2014-04-14
EP1966364A1 (fr) 2008-09-10
WO2007079856A1 (fr) 2007-07-19
PL1966364T3 (pl) 2014-08-29

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