EP0265979B1 - Compositions détergentes aqueuses épaissies - Google Patents

Compositions détergentes aqueuses épaissies Download PDF

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Publication number
EP0265979B1
EP0265979B1 EP87201850A EP87201850A EP0265979B1 EP 0265979 B1 EP0265979 B1 EP 0265979B1 EP 87201850 A EP87201850 A EP 87201850A EP 87201850 A EP87201850 A EP 87201850A EP 0265979 B1 EP0265979 B1 EP 0265979B1
Authority
EP
European Patent Office
Prior art keywords
sulphonate
carbon atoms
contain
weight
acid
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
EP87201850A
Other languages
German (de)
English (en)
Other versions
EP0265979A2 (fr
EP0265979A3 (en
EP0265979B2 (fr
Inventor
Hans Rörig
Norbert Porta
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.)
Akzo Nobel NV
Original Assignee
Akzo NV
Akzo Nobel NV
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
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Application filed by Akzo NV, Akzo Nobel NV filed Critical Akzo NV
Priority to EP87201850A priority Critical patent/EP0265979B2/fr
Priority to AT87201850T priority patent/ATE103970T1/de
Publication of EP0265979A2 publication Critical patent/EP0265979A2/fr
Publication of EP0265979A3 publication Critical patent/EP0265979A3/en
Publication of EP0265979B1 publication Critical patent/EP0265979B1/fr
Application granted granted Critical
Publication of EP0265979B2 publication Critical patent/EP0265979B2/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • the invention relates to aqueous cleaning compositions incorporating low levels of quaternary ammonium salt or amine oxide surfactant and displaying pronounced shear thinning behaviour, i.e. exhibiting high viscosities at low rates of shear.
  • This type of behaviour is of particular advantage in cleaning compositions intended to be applied to non-horizontal structural surfaces such as walls and windows and sanitary fittings such as sinks, baths, showers, wash basins and lavatories.
  • the invention is especially concerned with aqueous acid-containing cleaning compositions which are commonly applied to the surfaces of sanitary fittings.
  • GB 1 240 469 discloses compositions, suitable for cleaning metal, glass and painted surfaces, which compositions have a pH not higher than 7,0 and comprise (a) an inorganic acid, an organic acid or an acidic salt (b) a cationic detergent and (c) a water insoluble or partially water soluble covalent compound other than the compounds under (b) and which contains oxygen or halogen and at least one hydrocarbon chain of at least four carbon atoms.
  • component (c) can more particularly be used an ester of an inorganic acid, a fatty acid or an ester of a fatty acid, a carboxylic acid ester in which the hydrocarbon chain derived from the alcohol has at least four carbon atoms, an alkyl chloride, a hydroxyl compound or substituted hydroxy compound, and the hydroxy compound is preferably water insoluble, such as a fatty alcohol, containing from 4-30 carbon atoms in at least one alkyl chain.
  • cationic detergent only an amine oxide of a special structure is mentioned, which is exemplified by a large number of representatives, the actual application of quaternary ammonium salts being neither disclosed in general terms, nor in specifically exemplified representatives.
  • US Patent Specification 3 997 453 discloses a stable, cold water dispersible fabric softening composition
  • a stable, cold water dispersible fabric softening composition comprising from about 60 to 20% by weight of a cationic quaternary ammonium softener, an organic anionic sulfonate, the weight ratio of the cationic softener to the anionic detergent being from about 40:1 to 5:1 and wherein the anionic sulphonate being selected from amongst benzene or naphthalene sulphonate or a polyalkyl substituted aromatic sulphonate with one of the alkyl groups having not more than 18 C-atoms and each of the remaining alkyl group having not more than 2 carbon atoms.
  • FR-A-2 409 303 example 98, describes a composition containing a coco dimethyl amine oxide, an amine oxide wherein R 1 is a group with 12 carbon atoms. Thickening is achieved by combining a soap and an amine oxide.
  • US-A-3 892 669 discloses fabric-softening compositions which are thickened by the addition of thickeners as hydroxyethylcellulose.
  • GB-A-948 396 discloses an aqueous cleaning composition which is opaque and viscous at room temperature and which contains an alkali borate, a tertiary amine oxide, one or more detergent salts of anionic organic sulfuric reaction products, a salt of a non-detergent aryl sulfonic acid hydrotrope anion, and a pyrophosphate salt.
  • cleaning, desinfecting and/or odorizing agents are auxiliary detergents, acids, detergent builder salts, perfumes, antibiotics or active chlorine providing means.
  • a preferred embodiment of the present invention is formed by thickened aqueous cleaning compositions having a pH of not more than 7 and preferably between 0 and 6 and more preferably between 0-4, and containing 1-15% by weight of an acid, normally occurring in cleaning compositions.
  • quaternary ammonium compounds referred to under (a) are:
  • a preferred group of the cationic ammonium compounds are:
  • Typical examples of tertiary amine oxides referred to under (a) are:
  • a preferred group of the amine oxides are:
  • the amine oxide and/or quaternary ammonium compound may preferably be used in amounts from 0.1% to 5% by weight based on the total weight of the composition dependent on the viscosity and the type of the agent desired.
  • a preferred embodiment of the present invention is formed by thickened compositions containing one or more salts of the specified sulphonates.
  • Typical salts of the sulphonates specified under (b) are the sodium, potassium, ammonium, lower amine and alkanolamine salts, of which the sodium salts are preferred.
  • Typical acids which may be applied in the compositions of the present invention are sulphuric acid, phosphoric acid, sulphamic acid, hydrochloric acid, citric acid, acetic acid, formic acid or an acidic salt of the type conventionally used in cleaning compositions, or combinations thereof in an amount of from 1-15%.
  • the ratio of the weights of the quaternary ammonium compound or tertiary amine oxide to the sulphonate is in the range from 0.1-6 and preferably from 1.5-2.5 and more preferably around about 2.0.
  • a preferred embodiment of the invention is formed by the thickened cleaning composition which comprises: which showed the following viscosity values at different shear rates, using a Haake Rotovisco (trade name of Haake MeBtechnik GmbH and Co, Düsseldorf, Germany) RV 100 viscosimeter.
  • the thickening systems described above display a viscosity temperature relationship that has a parabolic profile with the maximum viscosity being exhibited at a temperature in the range from 0 ° C to 30 °C.
  • An increase in chain length of higher alkyl chain in the quaternary ammonium ion or amine oxide in general increases the temperature at which this peak occurs while a reduction in this higher alkyl chain length and/or branching in this alkyl group, reduces the temperature at which the maximum viscosity is produced by the system.
  • compositions of the present invention will be governed by the specific kind of surfactant (quaternary ammonium ion or amine oxide), kind of sulphonate, kind of acid in the composition, amount of acid electrolyte concentration in total composition, ratio of weights of the surfactant-sulphonate combinations, and counter ion of the sulphonates.
  • the thickening compositions according to the present invention have however appeared to be rather insensitive to other types of ingredients occurring in the complete aqueous cleaning composition, such as perfume.
  • the weight ratio of tallow trimethyl ammonium chloride and sodium xylene sulphonate in citric acid solution of 4.5% by weight (100%), i.e., 5% of hydrated citric acid, may vary from 2.0-2.5, and more preferably 2.15-2.25, while acceptable compositions for practical purposes may show ratios from 0.5-4.0 (based on 100% ingredients).
  • a thickening premix composition which comprises at least:
  • thickening premix compositions have appeared to be rather insensitive to the presence of other ingredients in the final cleaning composition, e.g., perfume.
  • Such thickening premix compositions have been found to consist of homogeneous mixtures of components (a) and (b) and to exhibit a long storage stability. When mixed with water or an aqueous solution they display a surprising thickening effect.
  • Another feature of the present invention is formed by the application of the thickened aqueous single phase compositions according to the usual methods of this specific art of cleaning non-horizontal surfaces such as walls, windows and sanitary fittings.
  • Citric acid monohydrate (5.0 g) is dissolved in about 85.0 ml of demineralized water, with stirring, at 20 ° C, whereafter 2.2 g of tallow trimethyl ammonium chloride (as 50% solution Arquad T 50@) are added, followed by the addition of 1.25 g of sodium xylene sulphonate (as 40% solution), with continued stirring. The viscosity increases immediately during the addition of the sulphonate.
  • the perfume may be mixed with the tallow trimethyl ammonium chloride.
  • the obtained composition comprises:
  • composition shows a good viscosity and is completely clear and stable at elevated temperature (40 °C). The colour does not change during storage.
  • the viscosity was measured by Brookfield LVT, 60 rev/min, 230 m Pa.s (20°C). The composition did not show any cloud point on cooling down to 0 °C, and on heating up to 95 °C.
  • the viscosities were measured by using a Brookfield LVT 60 rpm.
  • compositions were prepared containing respectively:
  • composition I was reported as becoming cloudy and thin, while composition II remained clear and had a viscosity of 190 m Pa.s. at 20 °C.
  • composition II remained clear and had a viscosity of 190 m Pa.s. at 20 °C.
  • the same behaviour could be observed in the case of similar compositions containing sodium cumene sulphonate or sodium toluene sulphonate, showing a rather small perfume susceptibility which permits the use of premix compositions derived from sulphonate-quaternary ammonium derivatives.
  • composition II could be applied in all acids specified in Example 2.
  • compositions were prepared along the lines of the process described in Example 1, starting from bis(2-hydroxy ethyl) tallowamine oxide (Aromox T12@) in amounts from 3 to 7% by weight, sodium xylene sulphonate, sodium toluene sulphonate, sodium cumene sulphonate, or secondary n-alkane sulphonates of the formulae and wherein R and R 1 represent an alkane residue of from 13-18 carbon atoms (Hostapur@ SAS wherein C 13 -n-alkanesulphonate represents 3% of the composition, C14-n-alkanesulphonate 25%, C15-n-alkanesulphonate 30%, C 16 -n-alkanesulphonate 25, C 17 -n-alkanesulphonate 15% and C 18 -n-alkanesulphonate 2%, being an example of a composition according to EP-0 137 871) in amounts of from 0-2% by weight, and hydrated citric
  • compositions containing amine oxide and olefin sulphonates e.g. ELFAN OS46@ III showed inferior thickening properties as compared with combination I and moreover had an intensive yellow colour.

Claims (11)

1. Compositions aqueuses épaissies de nettoyage à une seule phase qui comprennent : a. de 0,1 à 10 % en poids d'un tensioactif choisi dans le groupe constitué de : (1) composés d'ammonium quaternaire dans lesquels au moins l'un des groupements hydrocarbure liés à l'azote est un groupement hydrocarbure alkylique ou insaturé, linéaire ou ramifié, contenant au moins 12 atomes de carbone et, de préférence, 16 à 20 atomes de carbone et dans lesquels deux ou trois des groupements liés à l'atome d'azote sont indépendamment des groupements alkyle éventuellement substitués qui contiennent de 1 à 6 atomes de carbone et dans lesquels un ou plusieurs des groupements alkyle peuvent contenir un substituant aryle ou peuvent être remplacés par un groupement aryle et dans lesquels un anion est présent, par exemple, un halogénure, un acétate, un méthosulfate et analogue, et (2) oxydes d'amines tertiaires dans lesquels au moins l'un des groupements hydrocarbure liés à l'atome d'azote est un groupement hydrocarbure alkyle ou insaturé, linéaire ou ramifié, contenant au moins 16 atomes de carbone et de préférence 16 à 20 atomes de carbone et, dans lesquels deux des groupements liés à l'atome d'azote sont indépendamment des groupements alkyle éventuellement substitués qui contiennent de 1 à 6 atomes de carbone et dans lesquels l'un ou plusieurs des groupements alkyle peuvent contenir un substituant aryle ou peuvent être remplacés par un groupement aryle. b. De 0,01 % jusqu'à 3% en poids d'un sulfonate organique anionique choisi dans le groupe constitué de cumènesulfonate, xylènesulfonate et toluènesulfonate sous leur forme d'acide ou de sel et de mélanges de ceux-ci, et c. de l'eau dans laquelle sont éventuellement dissous ou dispersés un ou plusieurs agents nettoyants, désinfectants et odorants, le pourcentage en poids étant calculé par rapport au poids total de la composition aqueuse.
2. Compositions de nettoyage aqueuses épaissies selon la revendication 1, caractérisées en ce que le pH est compris entre 0 et 6 et, de préférence entre 0 et 4.
3. Compositions aqueuses épaissies selon la revendication 1 ou 2, caractérisées en ce qu'elles contiennent au moins du chlorure de suif-triméthylammonium.
4. Compositions épaissies selon l'une quelconque des revendications précédentes, caractérisées en ce qu'elles contiennent un composé d'ammonium quaternaire en une quantité comprise entre 0,1 et 5,0 % en poids par rapport au poids total de la composition.
5. Compositions épaissies selon l'une quelconque des revendications précédentes, caractérisées en ce qu'elles contiennent le sel sodique de sulfonates.
6. Compositions épaissies selon la revendication 5, caractérisées en ce qu'elles contiennent le sel sodique de xylènesulfonate.
7. Compositions épaissies selon l'une quelconque des revendications précédentes, caractérisées en ce qu'elles contiennent un acide en une quantité comprise entre 1 et 15 % en poids par rapport au poids total de la composition.
8. Utilisation de compositions de mélange préalable épaississantes pour la préparation des compositions selon l'une quelconque des revendications précédentes, le mélange préalable comprenant :
a. un tensioactif choisi dans le groupe constitué de : (1) composés d'ammonium quaternaire dans lesquels au moins l'un des groupements hydrocarbure liés à l'atome d'azote est un groupement hydrocarbure alkylique ou insaturé, linéaire ou ramifié, contenant au moins 12 atomes de carbone et, de préférence, 16 à 20 atomes de carbone, et dans lesquels deux ou trois des groupements liés à l'atome d'azote sont indépendamment des groupements alkyle éventuellement substitués qui contiennent de 1 à 6 atomes de carbone et dans lesquels un ou plusieurs des groupements alkyle peuvent contenir un substituant aryle ou peuvent être remplacés par un groupement aryle et dans lesquels il peut y avoir un anion tel qu'un halogénure, un acétate, un méthosulfate ou analogue, et (2) oxydes d'amines tertiaires, dans lesquels au moins l'un des groupement hydrocarbure liés à l'atome d'azote est un groupement hydrocarbure alkylique ou insaturé, linéaire ou ramifié, contenant au moins 16 atomes de carbone et de préférence 16 à 20 atomes de carbone et dans lesquels deux des groupements liés à l'atome d'azote sont indépendamment des groupements alkyle éventuellement substitués qui contiennent de 1 à 6 atomes de carbone et dans lesquels un ou plusieurs des groupements alkyle peuvent contenir un substituant aryle ou peuvent être remplacés par un groupement aryle.
b. un sulfonate organique anionique choisi dans le groupe constitué de cumènesulfonate, xylènesulfonate et toluènesulfonate sous leur forme d'acide ou de sel, et des mélanges de ceux-ci.
9. Utilisation selon la revendication 8, caractérisée en ce que le rapport en poids du composé d'ammonium quaternaire au sulfonate est dans l'intervalle de 1,5 à 2,5.
10. Utilisation selon la revendication 8 ou 9, caractérisée en ce que le mélange préalable contient au moins un chlorure de suif-triméthylammonium.
11. Procédé de nettoyage de surfaces non horizontales comme des murs, des fenêtres et des installations sanitaires par l'application de la composition aqueuse épaissie de nettoyage à phase unique selon l'une quelconque des revendications 1 à 7 par des procédés habituels dans la technique.
EP87201850A 1986-09-29 1987-09-26 Compositions détergentes aqueuses épaissies Expired - Lifetime EP0265979B2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP87201850A EP0265979B2 (fr) 1986-09-29 1987-09-26 Compositions détergentes aqueuses épaissies
AT87201850T ATE103970T1 (de) 1986-09-29 1987-09-26 Verdickte, waesserige reinigungsmittel.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP86201667 1986-09-29
EP86201667 1986-09-29
EP87201850A EP0265979B2 (fr) 1986-09-29 1987-09-26 Compositions détergentes aqueuses épaissies

Publications (4)

Publication Number Publication Date
EP0265979A2 EP0265979A2 (fr) 1988-05-04
EP0265979A3 EP0265979A3 (en) 1989-08-16
EP0265979B1 true EP0265979B1 (fr) 1994-04-06
EP0265979B2 EP0265979B2 (fr) 1998-06-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201850A Expired - Lifetime EP0265979B2 (fr) 1986-09-29 1987-09-26 Compositions détergentes aqueuses épaissies

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EP (1) EP0265979B2 (fr)
AT (1) ATE103970T1 (fr)

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US5055219A (en) * 1987-11-17 1991-10-08 The Clorox Company Viscoelastic cleaning compositions and methods of use therefor
TR27379A (tr) * 1992-07-29 1995-02-01 Clorox Co Faz dengeli viskoelastik temizleme bilesimleri.
US5399285A (en) * 1992-10-30 1995-03-21 Diversey Corporation Non-chlorinated low alkalinity high retention cleaners
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CA2107939C (fr) * 1993-01-13 2001-01-30 Stephen B. Kong Compositions acides de nettoyage en solution aqueuse
US5977054A (en) * 1993-09-01 1999-11-02 The Procter & Gamble Company Mildly acidic hard surface cleaning compositions containing amine oxide detergent surfactants
DK0716679T3 (da) * 1993-09-01 1999-06-28 Procter & Gamble Fremgangsmåde til rensning af vinyloverflader ved hjælp af let sure rensesammensætninger til hårde overflader indeholdende
EP0790296B1 (fr) * 1993-11-29 2000-09-06 The Procter & Gamble Company Des compositions pour enlever le tartre
MX9605996A (es) * 1994-05-31 1997-12-31 Procter & Gamble Composiciones limpiadoras.
DE69529533T2 (de) * 1994-11-25 2003-12-04 Procter & Gamble Verdickte bleichmittelzusammensetzungen, gebrauchsverfahren und verfahren zu deren herstellung
EP0726309B1 (fr) * 1995-02-08 2001-12-12 The Procter & Gamble Company Des compositions pour enlever le tartre
ES2164740T3 (es) * 1995-02-08 2002-03-01 Procter & Gamble Composiciones para la eliminacion de incrustaciones de cal.
DE19504192A1 (de) * 1995-02-09 1996-08-14 Henkel Ecolab Gmbh & Co Ohg Verdickende wäßrige Reinigungsmittel für harte Oberflächen
NL1000065C2 (nl) * 1995-04-05 1996-10-08 Dija Zeist B V Werkwijze en middel voor het reinigen van oppervlakken.
EP0745663A1 (fr) 1995-05-31 1996-12-04 The Procter & Gamble Company Compositions liquides colorées, acides, aqueuses contenant un agent de blanchiment peroxydant
DE19731398A1 (de) 1997-07-22 1999-01-28 Henkel Ecolab Gmbh & Co Ohg Verwendung enzymhaltiger Lösungen zum Reinigen von Gär- und Lagertanks
DE19918188A1 (de) 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918183A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
GB2375356A (en) * 2001-05-11 2002-11-13 Reckitt Benckiser Nv Cationic fabric softening compositions
WO2014198547A2 (fr) 2013-06-12 2014-12-18 Unilever N.V. Composition de détergent versable contenant des particules en suspension

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GB1294642A (en) * 1969-05-29 1972-11-01 Colgate Palmolive Co Fabric softening composition and process
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Also Published As

Publication number Publication date
EP0265979A2 (fr) 1988-05-04
ATE103970T1 (de) 1994-04-15
EP0265979A3 (en) 1989-08-16
EP0265979B2 (fr) 1998-06-03

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