EP0971020B1 - Non-foaming detergent compositions for concentrated alkaline medium - Google Patents

Non-foaming detergent compositions for concentrated alkaline medium Download PDF

Info

Publication number
EP0971020B1
EP0971020B1 EP99401539A EP99401539A EP0971020B1 EP 0971020 B1 EP0971020 B1 EP 0971020B1 EP 99401539 A EP99401539 A EP 99401539A EP 99401539 A EP99401539 A EP 99401539A EP 0971020 B1 EP0971020 B1 EP 0971020B1
Authority
EP
European Patent Office
Prior art keywords
detergent
formula
foaming
anhydride
detergent composition
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
EP99401539A
Other languages
German (de)
French (fr)
Other versions
EP0971020A1 (en
Inventor
Philippe Gentilhomme
Bernard Mourrut
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.)
Carbonisation et Charbons Actifs CECA SA
Original Assignee
Carbonisation et Charbons Actifs CECA SA
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 Carbonisation et Charbons Actifs CECA SA filed Critical Carbonisation et Charbons Actifs CECA SA
Publication of EP0971020A1 publication Critical patent/EP0971020A1/en
Application granted granted Critical
Publication of EP0971020B1 publication Critical patent/EP0971020B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/362—Phosphates or phosphites
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the field of the present invention is that of detergency industrial or household.
  • alkaline aqueous solutions are commonly used containing non-foaming surfactants.
  • the surfactants selected for this purpose are very generally non-ionic surfactants, said to be capped.
  • compounds having the following structure a hydrophobic chain of the fatty alkyl or alkylaryl chain type, condensed with ethylene oxide forming a hydrophilic chain, itself capped with a hydrophobic group.
  • These compounds are well represented by alcohols with alkyl or alkylaryl chain with 8-20 carbon atoms, and preferably 8-12 carbons, condensed with 4-14, preferably 8-10 molecules of ethylene oxide, and terminated by a hydrophobic group, consisting of an alkyl chain 3-8 carbon atoms or alkylaryl or a halogen.
  • Such a surfactant is typically represented by the ⁇ -alkyl- ⁇ -halo-poly (oxy-1,2-ethanediyl), such as the compound ⁇ -decyl- ⁇ -chloronano (oxyethylene) of formula CH 3 - (CH 2 ) 9 - (O-CH 2 -CH 2 ) 9 -Cl
  • Stabilizers are well known those skilled in the art; among them, oxygenated solvents, toluene sulfonate sodium, xylene sulfonate or sodium cumene sulfonate, alkali salts phosphoric esters.
  • oxygenated solvents toluene sulfonate sodium, xylene sulfonate or sodium cumene sulfonate, alkali salts phosphoric esters.
  • These agents of stabilization do not participate in the detergency itself, and are cause of a unnecessary increase in chemical demand and biological demand in oxygen (COD - BOD) from releases of detergent compositions. They can even have the negative effect of imparting significant foaming power to the composition. How they no longer respond to the problem of jet cleaning under pressure.
  • the stabilizing agent is a phosphoric ester, of the monoester / diester type obtained by reaction of phosphoric anhydride with an aliphatic alcohol having from 4 to 12 carbon atoms;
  • Alkenylsuccinic acid is a compound of formula with n being from 4 to 12, and the anhydrides which are their immediate derivatives.
  • compositions combining ⁇ -decyl- ⁇ -chloro-nona (oxyethylene) H 3 C ⁇ (CH 2 ) 9 - (O ⁇ CH 2 ⁇ CH 2 ) 9 ⁇ C) or ⁇ -decyl- ⁇ -benzyloxy-trideca (oxyethylene) 2-ethylhexyl monoesterphosphoric acid and octenylsuccinic acid, of formula or its anhydride are preferred compositions of the invention.
  • compositions satisfy the stability / solubility criterion that is defined thus: they are liquid, limpid, stable at least 60 days on a domain of temperature of -15 ° C / + 40 ° C, and soluble in alkaline solutions.
  • detergents containing from 1 to 5 parts by weight in an aqueous solution of soda or potash, or mixtures of alkaline salts (phosphates, carbonates, sodium silicates and / or potassium), in which there is no need to introduce hydrotropes to ensure uniformity during storage.
  • alkaline salts phosphates, carbonates, sodium silicates and / or potassium
  • Such detergents are also objects of the invention. These detergents can be used for cleaning hard surfaces, after immediate dilution at room temperature in water, soft or hard.
  • the power has been determined detergent, foaming power and anti-foaming power according to the operating modes following.
  • Detergent detergent consists of an aqueous solution of sodium hydroxide 13%, containing 2.2% of the detergent composition to be tested.
  • the degreasing treatment is carried out in the Labomat device of the Mathis company, the stainless steel plate being immersed in the pot (capacity 500 ml) of the appliance in 400 ml of the previous detergent, and stirred for 15 minutes at the temperature of 70 ° C. The plate is then removed from the device, rinsed with water and dried.
  • the soiling mixture has so-called lubricating performance limits. Measuring the residual lubrication of the treated plate as defined above, is performed compared to a fat-free plate (100% detergent) and to a plate degreased with detergent as defined above but not containing the detergent agent (0% detergency). For this, we use a ball-disc tribometer which measures the coefficient of friction between a ball and the plate to be measured, the ball being subjected to an applied load of 2.6 kg and the plate rotating at a speed of 1.6 mm / s.
  • Anti-foaming power which assesses the ability of the composition to counteract the foaming effect developed by the soaps which are formed by reaction of alkaline detergents on the stains of the surfaces they evacuate, is measured as before from 900 ml of alkaline detergent solution but in the presence of 1 g / l of saponin. Antifoam power is measured by comparison at the values obtained, under the same conditions, by an alkaline solution detergency containing no saponin.
  • the detergent composition is as follows (parts by weight) ⁇ -decyl- ⁇ -chloro-nona (oxyethylene) 35 2-Ethylhexyl phosphate 19 Octenylsuccinic anhydride 46
  • the detergent power is 80%.
  • the antifoam power measured with 2 g / l of surfactant + 1 g / l of saponin is at T 0 of 130 ml, and at T 4 min of 40 ml; with 2 g / l of surfactant but without saponin, we measure at T 0 120 ml and at T 4 min 40 ml.
  • a composition (parts by weight): ⁇ -decyl- ⁇ -chloro-nona (oxyethylene) 65 2-ethylhexyl phosphoric monoester / diester 35 therefore free of octenylsuccinic derivative, leads to unstable detergents.
  • Alkaline detergent consisting of ⁇ -decyl- ⁇ -chloro-nona (oxyethylene) in 2.2% solution in 13% soda lye is not stable. It is moreover the immediate consequence of the known lack of solubility of the ⁇ -decyl- ⁇ -chloro-nona (oxyethylene). Despite this instability, we practiced foaming and anti-foaming controls. Foaming power of such detergent, compared to that of the test detergent of Example 1, is slightly lower, its anti-foaming power slightly higher, and its power 20% lower detergent. The appearance of the surface cleaned according to the test is also less good.
  • the detergent composition is as follows (parts by weight): Dehypon® LT 104 (Henkel) 35 2-ethylhexyl phosphate (Beycostat®) A081; CECA SA) 19 Octenylsuccinic anhydride 46
  • Dehypon® LT 104 is a mixture of compounds of formula H 3 C ⁇ (CH 2 ) m - (O ⁇ CH 2 ⁇ CH 2 ) 10 ⁇ O ⁇ (CH 2 ) 3 ⁇ CH 3 in which m is an integer varying from 9 to 17.
  • composition is prepared by simple mixing of its constituents. She is presented as a clear, yellow, stable solution with a viscosity of around 200 mPa.s at 25 ° C, and whose pH of its 10% aqueous dispersion is equal to 0.7.
  • the foaming power, evaluated under the conditions of Example 1 is zero (foam volume less than 50 ml).
  • the detergent power is comparable to that of Example 1.
  • the detergent composition is as follows (parts by weight): Plurafac® LF 221 (BASF) 35 2-Ethylhexyl phosphate (Beycostat® A081; CECA SA) 20 Octylsuccinic anhydride 45
  • Plurafac® LF 221 is a mixture of compounds of formula in which q is an integer varying from 8 to 9, the average value of n is equal to 8.3 and the average value of p is equal to 1.6.
  • composition is prepared by simple mixing of its constituents. She is presented as a clear, yellow, stable solution with a viscosity of around 200 mPa.s at 25 ° C, and whose pH of its 10% aqueous dispersion is equal to 0.7.
  • the foaming power, evaluated under the conditions of Example 1 is zero (foam volume less than 50 ml).
  • the detergent power is comparable to that of Example 1.
  • the detergent composition is as follows (parts by weight): Non-foaming detergent 35 2-Ethylhexyl phosphate (Beycostat® A081; CECA SA) 19 Octylsuccinic anhydride 46
  • the non-foaming detergent corresponds to the formula:
  • composition is prepared by simple mixing of its constituents. She is presented as a clear, yellow, stable solution with a viscosity of around 200 mPa.s at 25 ° C, and whose pH of its 10% aqueous dispersion is equal to 0.7.
  • the foaming power, evaluated under the conditions of Example 1 is zero (foam volume less than 50 ml).
  • the detergent power is comparable to that of Example 1.

Description

Le domaine de la présente invention est celui de la détergence industrielle ou ménagère.The field of the present invention is that of detergency industrial or household.

Pour dégraisser les surfaces dures, et plus précisément pour nettoyer des surfaces métalliques, sols, parois, cuves, matériels divers, carrosseries, jantes ou moteurs en milieu industriel comme en milieu institutionnel (hôpitaux, cantines, restaurants, écoles), on utilise couramment des solutions aqueuses alcalines contenant des agents de surface non moussants.To degrease hard surfaces, and more specifically to clean metal surfaces, floors, walls, tanks, various materials, bodies, rims or engines in industrial and institutional environments (hospitals, canteens, restaurants, schools), alkaline aqueous solutions are commonly used containing non-foaming surfactants.

Les agents de surface retenus à cet effet sont très généralement des tensioactifs non ioniques dits chapeautés. On entend par-là des composés possédant la structure suivante: une chaíne hydrophobe du type chaíne grasse alkyle ou alkylaryle, condensée avec de l'oxyde d'éthylène formant une chaíne hydrophile, elle-même coiffée d'un groupement hydrophobe. Ces composés sont bien représentés par les alcools avec chaíne alkyle ou alkylaryle à 8-20 atomes de carbone, et de préférence 8-12 carbones, condensés avec 4-14, de préférence 8-10 molécules d'oxyde d'éthylène, et terminés par un groupe hydrophobe, constitué d'une chaíne alkyle 3-8 atomes de carbone ou alkylaryle ou un halogène. Un tel agent de surface est typiquement représenté par les α-alkyle-ω-halogéno-poly(oxy-1,2-éthanediyles), tel le composé α-décyl-ω-chloronano(oxyéthylène) de formule CH3-(CH2)9-(O-CH2-CH2)9-Cl The surfactants selected for this purpose are very generally non-ionic surfactants, said to be capped. By this is meant compounds having the following structure: a hydrophobic chain of the fatty alkyl or alkylaryl chain type, condensed with ethylene oxide forming a hydrophilic chain, itself capped with a hydrophobic group. These compounds are well represented by alcohols with alkyl or alkylaryl chain with 8-20 carbon atoms, and preferably 8-12 carbons, condensed with 4-14, preferably 8-10 molecules of ethylene oxide, and terminated by a hydrophobic group, consisting of an alkyl chain 3-8 carbon atoms or alkylaryl or a halogen. Such a surfactant is typically represented by the α-alkyl-ω-halo-poly (oxy-1,2-ethanediyl), such as the compound α-decyl-ω-chloronano (oxyethylene) of formula CH 3 - (CH 2 ) 9 - (O-CH 2 -CH 2 ) 9 -Cl

Les agents de surface de ce type sont peu solubles, voire franchement insolubles dans les solutions alcalines, et les solutions alcalines de détergence qui les contiennent ont tendance à démixer. On remédie à ce phénomène par utilisation d'agents de stabilisation. Les agents de stabilisation sont bien connus de l'homme du métier; parmi eux, les solvants oxygénés, le toluène-sulfonate de sodium, le xylène-sulfonate ou le cumène-sulfonate de sodium, les sels alcalins d'esters phosphoriques. On en utilise des quantités considérables, pouvant aller jusqu'à dix parties par partie d'agent de détergence non moussant. Ces agents de stabilisation ne participent pas à la détergence elle-même, et sont cause d'une inutile augmentation de la demande chimique et de la demande biologique en oxygène (DCO - DBO) des rejets des compositions détergentes. Ils peuvent même avoir l'effet négatif de conférer un pouvoir moussant non négligeable à la composition. Ce en quoi elles ne répondent plus au problème du nettoyage par jet sous pression.Surfactants of this type are poorly soluble, or even frankly insoluble in alkaline solutions, and alkaline detergent solutions that contain them tend to demix. This phenomenon is remedied by use of stabilizers. Stabilizers are well known those skilled in the art; among them, oxygenated solvents, toluene sulfonate sodium, xylene sulfonate or sodium cumene sulfonate, alkali salts phosphoric esters. We use considerable quantities, ranging from up to ten parts per part of non-foaming detergent. These agents of stabilization do not participate in the detergency itself, and are cause of a unnecessary increase in chemical demand and biological demand in oxygen (COD - BOD) from releases of detergent compositions. They can even have the negative effect of imparting significant foaming power to the composition. How they no longer respond to the problem of jet cleaning under pressure.

On vient de trouver que des compositions du type détergent non moussant / agent de stabilisation / acide ou anhydride alkénylsuccinique constituaient des bases pour la réalisation de solutions alcalines de nettoyage tout à fait remarquables quant à leur efficacité détergente, leur DCO / DBO maintenues dans des limites raisonnables, leur stabilité au stockage, et leur absence de moussage, même dans des conditions d'utilisation au jet sous pression. Au sens de l'invention, l'agent détergent non moussant est un composé de formule R1-(O-CH2-CH2)n-R2 dans laquelle

  • R1 est une chaíne alkyle à 8-20 atomes de carbone, et de préférence 8-12 atomes de carbone, ou un radical octylphényle ou nonylphényle,
  • n vaut de 8 à 15,
  • R2 est un radical alkyloxy à 3-5 atomes de carbone, un radical poly(oxyalkylène) de formule :
    Figure 00020001
       dans laquelle
  • R' est un radical alkyle à 1-2 atomes de carbone
  • p vaut de 1 à 10,
  • un radical benzyloxy, ou le chlore.
    • It has just been found that compositions of the non-foaming detergent / stabilizing agent / alkenylsuccinic acid or anhydride type constituted bases for the production of alkaline cleaning solutions quite remarkable as regards their detergent efficiency, their COD / BOD kept within limits. reasonable, their stability in storage, and their absence of foaming, even under conditions of use with a pressure jet. Within the meaning of the invention, the non-foaming detergent agent is a compound of formula R 1 - (O-CH 2 -CH 2 ) n -R 2 in which
  • R 1 is an alkyl chain with 8-20 carbon atoms, and preferably 8-12 carbon atoms, or an octylphenyl or nonylphenyl radical,
  • n is 8 to 15,
  • R 2 is an alkyloxy radical with 3-5 carbon atoms, a poly (oxyalkylene) radical of formula:
    Figure 00020001
    in which
  • R 'is an alkyl radical with 1-2 carbon atoms
  • p is from 1 to 10,
  • a benzyloxy radical, or chlorine.

    • Ces compositions sont formées de

  • 25 à 45 parties en poids de l'agent détergent non moussant,
  • 15 à 25 parties en poids d'un agent de stabilisation,
  • 30 à 60 parties en poids d'acide ou d'anhydride alkénylsuccinique.
    • These compositions are formed from
  • 25 to 45 parts by weight of the non-foaming detergent agent,
  • 15 to 25 parts by weight of a stabilizing agent,
  • 30 to 60 parts by weight of alkenyl succinic acid or anhydride.

    • L'agent de stabilisation est un ester phosphorique, du type monoester /diester obtenu par réaction d'anhydride phosphorique avec un alcool aliphatique comportant de 4 à 12 atomes de carbone ;The stabilizing agent is a phosphoric ester, of the monoester / diester type obtained by reaction of phosphoric anhydride with an aliphatic alcohol having from 4 to 12 carbon atoms;

    L'acide alkénylsuccinique est un composé de formule

    Figure 00030001
    avec n valant de 4 à 12, et les anhydrides qui en sont leurs dérivés immédiats.Alkenylsuccinic acid is a compound of formula
    Figure 00030001
    with n being from 4 to 12, and the anhydrides which are their immediate derivatives.

    Les compositions associants l'α-décyl-ω-chloro-nona(oxyéthylène) H3C―(CH2)9―(O―CH2―CH2)9―C) ou l'α-décyl-ω-benzyloxy-tridéca(oxyéthylène)

    Figure 00030002
    le monoesterphosphorique de 2-éthylhexyle et l'acide octénylsuccinique, de formule
    Figure 00030003
    ou son anhydride sont des compositions préférées de l'invention.The compositions combining α-decyl-ω-chloro-nona (oxyethylene) H 3 C― (CH 2 ) 9 - (O ― CH 2 ―CH 2 ) 9 ―C) or α-decyl-ω-benzyloxy-trideca (oxyethylene)
    Figure 00030002
    2-ethylhexyl monoesterphosphoric acid and octenylsuccinic acid, of formula
    Figure 00030003
    or its anhydride are preferred compositions of the invention.

    Ces compositions satisfont au critère de stabilité/solubilité qu'on définit ainsi : elles sont liquides, limpides, stables au moins 60 jours sur un domaine de température de -15°C/+40°C, et solubles dans les solutions alcalines.These compositions satisfy the stability / solubility criterion that is defined thus: they are liquid, limpid, stable at least 60 days on a domain of temperature of -15 ° C / + 40 ° C, and soluble in alkaline solutions.

    On peut s'en servir pour composer des lessives de détergence contenant de 1 à 5 parties en poids dans une solution aqueuse de soude ou de potasse, ou de mélanges de sels alcalins (phosphates, carbonates, silicates de sodium et/ou de potassium), dans lesquelles il n'est nul besoin d'introduire des hydrotropes pour en assurer l'homogénéité au stockage. De telles lessives sont également des objets de l'invention. Ces lessives sont utilisables pour le nettoyage des surfaces dures, après dilution immédiate à la température ambiante dans l'eau, douce ou dure.It can be used to compose detergents containing from 1 to 5 parts by weight in an aqueous solution of soda or potash, or mixtures of alkaline salts (phosphates, carbonates, sodium silicates and / or potassium), in which there is no need to introduce hydrotropes to ensure uniformity during storage. Such detergents are also objects of the invention. These detergents can be used for cleaning hard surfaces, after immediate dilution at room temperature in water, soft or hard.

    EXEMPLESEXAMPLES

    Dans les exemples, non limitatifs de l'invention, on a déterminé le pouvoir détergent, le pouvoir moussant et le pouvoir anti-mousse selon les modes opératoires suivants.In the nonlimiting examples of the invention, the power has been determined detergent, foaming power and anti-foaming power according to the operating modes following.

    Pouvoir détergent.Detergent power.

    Le pouvoir détergent est évalué par dégraissage d'une plaque en inox dont la salissure est obtenue par trempage dans le mélange fondu de (parties en poids)

  • 15 parties d'acide stéarique,
  • 15 parties d'acide oléique
  • 30 parties d'huile de colza
  • 25 parties d'une huile minérale (Elf 15W40)
  • 8 parties d'alcool cétostéarylique.
    • The detergent power is evaluated by degreasing a stainless steel plate, the soiling of which is obtained by soaking in the molten mixture of (parts by weight)
  • 15 parts of stearic acid,
  • 15 parts of oleic acid
  • 30 parts of rapeseed oil
  • 25 parts of mineral oil (Elf 15W40)
  • 8 parts of cetostearyl alcohol.

    • La lessive détergente est constituée d'une solution aqueuse de soude à 13 %, contenant 2,2 % de la composition détergente à tester.Detergent detergent consists of an aqueous solution of sodium hydroxide 13%, containing 2.2% of the detergent composition to be tested.

    Le traitement de dégraissage est réalisé dans l'appareil Labomat de la société Mathis, la plaque d'inox étant immergée dans le pot (contenance 500 ml) de l'appareil dans 400 ml de la lessive précédente, et agitée durant 15 minutes à la température de 70°C. La plaque est alors extraite de l'appareil, rincée à l'eau et séchée.The degreasing treatment is carried out in the Labomat device of the Mathis company, the stainless steel plate being immersed in the pot (capacity 500 ml) of the appliance in 400 ml of the previous detergent, and stirred for 15 minutes at the temperature of 70 ° C. The plate is then removed from the device, rinsed with water and dried.

    Le mélange de salissures possède des performances lubrifiantes dites limites. La mesure de la lubrification résiduelle de la plaque traitée comme défini plus haut, est effectuée comparativement à une plaque exempte de gras (100 % de détergence) et à une plaque dégraissée à l'aide de la lessive détergente comme définie plus haut mais ne contenant pas l'agent détergent (0 % de détergence). Pour cela, on utilise un tribomètre bille-disque qui permet de mesurer le coefficient de frottement entre une bille et la plaque à mesurer, la bille étant soumise à une charge appliquée de 2,6 kg et la plaque tournant à une vitesse de 1,6 mm/s.The soiling mixture has so-called lubricating performance limits. Measuring the residual lubrication of the treated plate as defined above, is performed compared to a fat-free plate (100% detergent) and to a plate degreased with detergent as defined above but not containing the detergent agent (0% detergency). For this, we use a ball-disc tribometer which measures the coefficient of friction between a ball and the plate to be measured, the ball being subjected to an applied load of 2.6 kg and the plate rotating at a speed of 1.6 mm / s.

    Pouvoir moussantFoaming power

    Une prise de 900 ml de la lessive alcaline de détergence, telle que définie ci-dessus, est soumise à une agitation violente pendant 5 minutes, sous l'effet d'une turbine tournant à 2000 tr/min. Dans une éprouvette de deux litres, on mesure, après agitation, la hauteur de mousse en fonction du temps. On admet que le produit est suffisamment dénué de pouvoir moussant si le volume de mousse, après agitation, est inférieur à 50 ml.One intake of 900 ml of alkaline detergent, as defined above, is subjected to violent agitation for 5 minutes, under the effect of a turbine rotating at 2000 rpm. In a two-liter test tube, we measures, after stirring, the height of foam as a function of time. We admit that the product is sufficiently devoid of foaming power if the volume of foam, after stirring, is less than 50 ml.

    Pouvoir anti-mousseAnti-foaming power

    Le pouvoir anti-mousse, qui évalue l'aptitude de la composition à contrarier l'effet moussant développé par les savons qui se forment par réaction des lessives alcalines sur les souillures des surfaces qu'elles évacuent, se mesure comme précédemment à partir de 900 ml de solution alcaline de détergence mais en présence de 1 g/l de saponine. Le pouvoir antimousse est mesuré par comparaison aux valeurs obtenues, suivant les mêmes conditions, par une solution alcaline de détergence ne contenant pas de saponine.Anti-foaming power, which assesses the ability of the composition to counteract the foaming effect developed by the soaps which are formed by reaction of alkaline detergents on the stains of the surfaces they evacuate, is measured as before from 900 ml of alkaline detergent solution but in the presence of 1 g / l of saponin. Antifoam power is measured by comparison at the values obtained, under the same conditions, by an alkaline solution detergency containing no saponin.

    EXEMPLE 1EXAMPLE 1

    La composition détergente est la suivante (parties en poids) α-décyle-ω-chloro-nona(oxyéthylène) 35 Phosphate de 2-éthylhexyle 19 Anhydride octénylsuccinique 46 The detergent composition is as follows (parts by weight) α-decyl-ω-chloro-nona (oxyethylene) 35 2-Ethylhexyl phosphate 19 Octenylsuccinic anhydride 46

    Elle se prépare par simple mélange de ses constituants. On a pris ici pour l'α-décyle-ω-chloro-nona(oxyéthylène) le Déterflo®A210 et pour le phosphate de 2-éthylhexyle, le Beycostat®A081 de CECA S.A. La composition se présente comme une solution limpide, jaune, stable, de viscosité d'environ 180 mPa.s à 25°C, dont le pH de sa dispersion aqueuse à 10 % est de 0,7. Une lessive détergente constituée d'une solution aqueuse de soude à 13 %, contenant 2,2 % de cette composition est stable. It is prepared by simple mixing of its constituents. We took it here α-decyl-ω-chloro-nona (oxyethylene) Deterflo®A210 and for phosphate 2-ethylhexyl, Beycostat®A081 from CECA S.A. The composition is presented as a clear, yellow, stable solution with a viscosity of around 180 mPa.s at 25 ° C, the pH of its 10% aqueous dispersion is 0.7. Detergent detergent consisting of a 13% aqueous sodium hydroxide solution, containing 2.2% of this composition is stable.

    Le pouvoir moussant évalué comme indiqué plus haut, dans une eau à 25°TH, à la concentration de 5,3 % de soude, en présence de 0,5, 1, 2 et 4 g/l de composition détergente et à la température de 50°C, après 5 minutes d'agitation et 15 minutes de repos, est nul.The foaming power evaluated as indicated above, in water with 25 ° TH, at a concentration of 5.3% soda, in the presence of 0.5, 1, 2 and 4 g / l of detergent composition and at a temperature of 50 ° C., after 5 minutes of stirring and 15 minutes of rest, sucks.

    Le pouvoir détergent est de 80 %.The detergent power is 80%.

    Le pouvoir anti-mousse mesuré avec 2 g/l d'agent de surface + 1 g/l de saponine est à T0 de 130 ml, et à T4min de 40 ml ; avec 2 g/l d'agent de surface mais sans saponine, on mesure à T0 120 ml et à T4min 40 ml.The antifoam power measured with 2 g / l of surfactant + 1 g / l of saponin is at T 0 of 130 ml, and at T 4 min of 40 ml; with 2 g / l of surfactant but without saponin, we measure at T 0 120 ml and at T 4 min 40 ml.

    EXEMPLE 2 (contre-exemple) EXAMPLE 2 (counterexample)

    Une composition (parties en poids) : α-décyle-ω-chloro-nona(oxyéthylène) 65 monoester/diester phosphorique de 2-éthylhexyle 35 donc exempte de dérivé octénylsuccinique, conduit à des lessives instables.A composition (parts by weight): α-decyl-ω-chloro-nona (oxyethylene) 65 2-ethylhexyl phosphoric monoester / diester 35 therefore free of octenylsuccinic derivative, leads to unstable detergents.

    EXEMPLE 3 (contre-exemple) EXAMPLE 3 (counterexample)

    Une composition (parties en poids) α-décyle-ω-chloro-nona(oxyéthylène) 43 anhydride octénylsuccinique 57 donc exempte d'ester phosphorique conduit à des lessives instables.A composition (parts by weight) α-decyl-ω-chloro-nona (oxyethylene) 43 octenylsuccinic anhydride 57 therefore free of phosphoric ester leads to unstable detergents.

    EXEMPLE 4 (comparatif) EXAMPLE 4 (comparative)

    La lessive alcaline constituée d'α-décyle-ω-chloro-nona(oxyéthylène) en solution à 2,2% dans une lessive de soude à 13 % n'est pas stable. C'est d'ailleurs la conséquence immédiate du manque de solubilité connu de l'α-décyle-ω-chloro-nona(oxyéthylène). Malgré cette instabilité, on a pratiqué les contrôles de pouvoir moussant et de pouvoir anti-mousse. Le pouvoir moussant d'une telle lessive, comparé à celui de la lessive test de l'exemple 1, est légèrement inférieur, son pouvoir anti-mousse légèrement supérieur, et son pouvoir détergent inférieur de 20 %. L'aspect de la surface nettoyée selon le test est aussi moins bon. Alkaline detergent consisting of α-decyl-ω-chloro-nona (oxyethylene) in 2.2% solution in 13% soda lye is not stable. It is moreover the immediate consequence of the known lack of solubility of the α-decyl-ω-chloro-nona (oxyethylene). Despite this instability, we practiced foaming and anti-foaming controls. Foaming power of such detergent, compared to that of the test detergent of Example 1, is slightly lower, its anti-foaming power slightly higher, and its power 20% lower detergent. The appearance of the surface cleaned according to the test is also less good.

    EXEMPLES 5 (hors du domaine des revendications) EXAMPLES 5 (outside the scope of the claims)

    La composition détergente est la suivante (parties en poids) : Dehypon® LT 104 (Henkel) 35 Phosphate de 2-éthylhexyle (Beycostat®) A081 ; CECA S.A.) 19 Anhydride octénylsuccinique 46 The detergent composition is as follows (parts by weight): Dehypon® LT 104 (Henkel) 35 2-ethylhexyl phosphate (Beycostat®) A081; CECA SA) 19 Octenylsuccinic anhydride 46

    Le Dehypon® LT 104 est un mélange de composés de formule H3C―(CH2)m―(O―CH2―CH2)10―O―(CH2)3―CH3 dans laquelle m est un entier variant de 9 à 17.Dehypon® LT 104 is a mixture of compounds of formula H 3 C― (CH 2 ) m - (O ― CH 2 ―CH 2 ) 10 ―O― (CH 2 ) 3 ―CH 3 in which m is an integer varying from 9 to 17.

    La composition se prépare par simple mélange de ses constituants. Elle se présente comme une solution limpide, jaune, stable, ayant une viscosité de l'ordre de 200 mPa.s à 25°C, et dont le pH de sa dispersion aqueuse à 10 % est égal à 0,7.The composition is prepared by simple mixing of its constituents. She is presented as a clear, yellow, stable solution with a viscosity of around 200 mPa.s at 25 ° C, and whose pH of its 10% aqueous dispersion is equal to 0.7.

    Une lessive détergente comprenant (% en poids) :

    • 17 % de pyrophosphate tétrapotassique,
    • 14 % de potasse pure,
    • 15 % de silicate de sodium (densité : 1,33),
    • et 2 % de la composition détergente,
    est stable.A detergent detergent comprising (% by weight):
    • 17% tetrapotassium pyrophosphate,
    • 14% pure potash,
    • 15% sodium silicate (density: 1.33),
    • and 2% of the detergent composition,
    is stable.

    Le pouvoir moussant, évalué dans les conditions de l'Exemple 1 est nul (volume de mousse inférieur à 50 ml).The foaming power, evaluated under the conditions of Example 1 is zero (foam volume less than 50 ml).

    Le pouvoir détergent est comparable à celui de l'Exemple 1.The detergent power is comparable to that of Example 1.

    EXEMPLE 6 (hors du domaine des revendications) EXAMPLE 6 (outside the scope of the claims)

    La composition détergente est la suivante (parties en poids) : Plurafac® LF 221 (BASF) 35 Phosphate de 2-éthylhexyle (Beycostat® A081 ; CECA S.A.) 20 Anhydride octylsuccinique 45 The detergent composition is as follows (parts by weight): Plurafac® LF 221 (BASF) 35 2-Ethylhexyl phosphate (Beycostat® A081; CECA SA) 20 Octylsuccinic anhydride 45

    Le Plurafac® LF 221 est un mélange de composés de formule

    Figure 00080001
       dans laquelle q est un entier variant de 8 à 9, la valeur moyenne de n est égale à 8,3 et la valeur moyenne de p est égale à 1,6.Plurafac® LF 221 is a mixture of compounds of formula
    Figure 00080001
    in which q is an integer varying from 8 to 9, the average value of n is equal to 8.3 and the average value of p is equal to 1.6.

    La composition se prépare par simple mélange de ses constituants. Elle se présente comme une solution limpide, jaune, stable, ayant une viscosité de l'ordre de 200 mPa.s à 25°C, et dont le pH de sa dispersion aqueuse à 10 % est égal à 0,7.The composition is prepared by simple mixing of its constituents. She is presented as a clear, yellow, stable solution with a viscosity of around 200 mPa.s at 25 ° C, and whose pH of its 10% aqueous dispersion is equal to 0.7.

    Une lessive détergente comprenant (% en poids) :

    • 17 % de pyrophosphate tétrapotassique,
    • 14 % de potasse pure,
    • 15 % de silicate de sodium (densité : 1,33),
    • et 2,5 % de la composition détergente,
    est stable.A detergent detergent comprising (% by weight):
    • 17% tetrapotassium pyrophosphate,
    • 14% pure potash,
    • 15% sodium silicate (density: 1.33),
    • and 2.5% of the detergent composition,
    is stable.

    Le pouvoir moussant, évalué dans les conditions de l'Exemple 1 est nul (volume de mousse inférieur à 50 ml).The foaming power, evaluated under the conditions of Example 1 is zero (foam volume less than 50 ml).

    Le pouvoir détergent est comparable à celui de l'Exemple 1.The detergent power is comparable to that of Example 1.

    EXEMPLE 7 (hors du domaine des revendications) EXAMPLE 7 (outside the scope of the claims)

    La composition détergente est la suivante (parties en poids) : Détergent non moussant 35 Phosphate de 2-éthylhexyle (Beycostat® A081 ; CECA S.A.) 19 Anhydride octylsuccinique 46 The detergent composition is as follows (parts by weight): Non-foaming detergent 35 2-Ethylhexyl phosphate (Beycostat® A081; CECA SA) 19 Octylsuccinic anhydride 46

    Le détergent non moussant répond à la formule :

    Figure 00090001
    The non-foaming detergent corresponds to the formula:
    Figure 00090001

    Il est obtenu par réaction de l'alcool gras éthoxylé correspondant et de chlorure de benzyle.It is obtained by reaction of the corresponding ethoxylated fatty alcohol and benzyl chloride.

    La composition se prépare par simple mélange de ses constituants. Elle se présente comme une solution limpide, jaune, stable, ayant une viscosité de l'ordre de 200 mPa.s à 25°C, et dont le pH de sa dispersion aqueuse à 10 % est égal à 0,7.The composition is prepared by simple mixing of its constituents. She is presented as a clear, yellow, stable solution with a viscosity of around 200 mPa.s at 25 ° C, and whose pH of its 10% aqueous dispersion is equal to 0.7.

    Une lessive comprenant (% en poids)

    • 17 % de pyrophosphate tétrapotassique,
    • 14 % de potasse pure,
    • 15 % de silicate de sodium (densité : 1,33),
    • et 2,2 % de la composition détergente,
    est stable.One detergent including (% by weight)
    • 17% tetrapotassium pyrophosphate,
    • 14% pure potash,
    • 15% sodium silicate (density: 1.33),
    • and 2.2% of the detergent composition,
    is stable.

    Le pouvoir moussant, évalué dans les conditions de l'Exemple 1 est nul (volume de mousse inférieur à 50 ml).The foaming power, evaluated under the conditions of Example 1 is zero (foam volume less than 50 ml).

    Le pouvoir détergent est comparable à celui de l'Exemple 1.The detergent power is comparable to that of Example 1.

    Claims (5)

    1. Use of a detergent composition for industrial or household cleaning, which is non-foaming and stable in a highly alkaline medium, in detergent washing products consisting of a solution containing 1-5% by weight of the detergent composition in an aqueous solution containing 13% sodium hydroxide, the said detergent composition comprising
      25 to 45 parts by weight of a non-foaming detergent agent,
      15 to 25 parts by weight of a stabilizer,
      30 to 60 parts by weight of alkenylsuccinic acid or anhydride,
      the non-foaming detergent agent being a compound of formula R1-(O-CH2-CH2)n-R2 in which
      R1 is an alkyl chain of 8-20 carbon atoms, and preferably 8-12 carbons, or an octylphenyl or nonylphenyl radical,
      n is from 8 to 15,
      R2 is an alkoxy radical of 3-5 carbon atoms, a poly(oxyalkylene) radical of formula:
      Figure 00160001
         in which
      R' is an alkyl radical containing 1 or 2 carbon atoms,
      p is from 1 to 10,
      a benzyloxy radical, or chlorine;
      the stabilizer being a phosphoric ester of monoester/diester type, obtained by reaction of phosphorus pentoxide with an aliphatic alcohol containing from 4 to 12 carbon atoms;
      the alkenylsuccinic acid being a compound of formula
      Figure 00160002
      where n is from 4 to 12,
      and the anhydride which is the immediate derivative thereof.
    2. Use of a detergent composition according to Claim 1, characterized in that the non-foaming detergent agent is α-decyl-ω-chloronona(oxyethylene), of formula CH3-(CH2)9-(O-CH2-CH2)9-Cl or α-decyl-ω-benzyloxytrideca(oxyethylene), of formula
      Figure 00170001
    3. Use of a detergent composition according to Claim 1, characterized in that the stabilizer is the phosphoric monoester/diester of 2-ethylhexyl.
    4. Use of a detergent composition according to Claim 1, characterized in that the alkenylsuccinic acid or anhydride is octenylsuccinic acid or anhydride.
    5. Use of a detergent composition according to Claim 1, characterized in that the non-foaming detergent agent is α-decyl-ω-chloronona(oxyethylene), of formula CH3-(CH2)9-(O-CH2-CH2)9-Cl, or α-decyl-ω-benzyloxytrideca(oxyethylene), of formula
      Figure 00170002
      the stabilizer is the phosphoric monoester/diester of 2-ethylhexyl, and the alkenylsuccinic acid or anhydride is octenylsuccinic acid or anhydride.
    EP99401539A 1998-07-06 1999-06-21 Non-foaming detergent compositions for concentrated alkaline medium Expired - Lifetime EP0971020B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    FR9808608 1998-07-06
    FR9808608A FR2780732B1 (en) 1998-07-06 1998-07-06 NON-FOAMING DETERGENT COMPOSITIONS FOR CONCENTRATED ALKALINE MEDIA

    Publications (2)

    Publication Number Publication Date
    EP0971020A1 EP0971020A1 (en) 2000-01-12
    EP0971020B1 true EP0971020B1 (en) 2004-03-10

    Family

    ID=9528291

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP99401539A Expired - Lifetime EP0971020B1 (en) 1998-07-06 1999-06-21 Non-foaming detergent compositions for concentrated alkaline medium

    Country Status (10)

    Country Link
    US (1) US6693065B2 (en)
    EP (1) EP0971020B1 (en)
    JP (1) JP2000178582A (en)
    AR (1) AR019888A1 (en)
    AT (1) ATE261488T1 (en)
    BR (1) BR9902540A (en)
    CA (1) CA2276906C (en)
    DE (1) DE69915414T2 (en)
    FR (1) FR2780732B1 (en)
    NO (1) NO993319L (en)

    Families Citing this family (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US20050227907A1 (en) * 2004-04-13 2005-10-13 Kaiping Lee Stable fragrance microcapsule suspension and process for using same
    US20050226900A1 (en) * 2004-04-13 2005-10-13 Winton Brooks Clint D Skin and hair treatment composition and process for using same resulting in controllably-releasable fragrance and/or malodour counteractant evolution
    US7594594B2 (en) * 2004-11-17 2009-09-29 International Flavors & Fragrances Inc. Multi-compartment storage and delivery containers and delivery system for microencapsulated fragrances
    US20070207174A1 (en) * 2005-05-06 2007-09-06 Pluyter Johan G L Encapsulated fragrance materials and methods for making same
    DE102007006628A1 (en) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa cleaning supplies
    US8334323B2 (en) * 2008-01-11 2012-12-18 Dow Global Technologies Llc Alkylene oxide-capped secondary alcohol alkoxylates useful as surfactants
    EP2346925B1 (en) * 2008-09-24 2016-08-10 Dow Global Technologies LLC Alkylene oxide capped secondary alcohol ethoxylates as fermentation foam control agents
    CN108137459B (en) 2015-10-07 2021-06-18 海名斯精细化工公司 Wetting and antifoam agents

    Family Cites Families (16)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3579453A (en) * 1968-11-12 1971-05-18 Rohm & Haas Alkali-soluble surfactant consisting of substituted succinic acid-nonionic ethoxylate blends
    SE408714B (en) * 1974-11-25 1979-07-02 Berol Kemi Ab LIQUID AQUATIZED DETERGENT CONTAINING A SURFACTIVE PART AND COMPLEX MOLDERS
    GB1528171A (en) * 1975-01-06 1978-10-11 Diamond Shamrock Europ Foaming hard surface cleaner formulations
    SE7601749L (en) * 1975-02-18 1976-08-19 Hart Chemical Ltd WATER DISPERGABLE ANTI-FOAM COMPOSITION
    US4137190A (en) * 1977-04-04 1979-01-30 Gaf Corporation Detergent composition comprising synergistic hydrotrope mixture of two classes of organic phosphate esters
    JPS59196398A (en) * 1983-04-22 1984-11-07 花王株式会社 Liquid detergent composition
    US4786431A (en) * 1984-12-31 1988-11-22 Colgate-Palmolive Company Liquid laundry detergent-bleach composition and method of use
    US4597888A (en) * 1985-06-19 1986-07-01 Parker Chemical Company Cleaner for steel cans
    US4744916A (en) * 1985-07-18 1988-05-17 Colgate-Palmolive Company Non-gelling non-aqueous liquid detergent composition containing higher fatty dicarboxylic acid and method of use
    GB8528521D0 (en) * 1985-11-20 1985-12-24 Procter & Gamble Liquid detergent compositions
    US4721580A (en) * 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
    US4793942A (en) * 1987-01-08 1988-12-27 Ecolab Inc. Detersive systems with a dispersed aqueous-organic softening agent for hardness removal
    EP0482275B1 (en) * 1990-10-22 1996-07-10 The Procter & Gamble Company Stable liquid detergent compositions containing bleach
    WO1995034694A1 (en) * 1994-06-13 1995-12-21 E.I. Du Pont De Nemours And Company Corrosion inhibitor composition for steel
    US5634979A (en) * 1994-12-22 1997-06-03 Henkel Corporation Composition and method for degreasing metal surfaces
    US5555756A (en) * 1995-01-24 1996-09-17 Inland Steel Company Method of lubricating steel strip for cold rolling, particularly temper rolling

    Also Published As

    Publication number Publication date
    BR9902540A (en) 2000-01-18
    US20030078175A1 (en) 2003-04-24
    EP0971020A1 (en) 2000-01-12
    DE69915414D1 (en) 2004-04-15
    FR2780732A1 (en) 2000-01-07
    CA2276906A1 (en) 2000-01-06
    CA2276906C (en) 2003-09-23
    DE69915414T2 (en) 2005-03-03
    FR2780732B1 (en) 2000-09-08
    AR019888A1 (en) 2002-03-20
    JP2000178582A (en) 2000-06-27
    NO993319L (en) 2000-01-07
    NO993319D0 (en) 1999-07-05
    US6693065B2 (en) 2004-02-17
    ATE261488T1 (en) 2004-03-15

    Similar Documents

    Publication Publication Date Title
    EP0293040B2 (en) Liquid detergent containing solid peroxygen bleach
    US4878951A (en) Low-foaming alkaline, hypochlorite cleaner
    JPH01156399A (en) Aqueous detergent composition containing diethylene glycol monohexyl ether solvent
    FR2613378A1 (en) DETERGENT COMPOSITIONS FOR DISHWASHER
    EP0971020B1 (en) Non-foaming detergent compositions for concentrated alkaline medium
    FR2580664A1 (en) BIODEGRADABLE LIQUID SURFACTANT AGENT AND USE THEREOF
    JP5284609B2 (en) Non-electrolytically cleaned cold-rolled steel sheet detergent composition
    EP0598693B1 (en) Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
    FR2550959A1 (en) POLYOXYALKYL ALCOHOLIC ACTIVE ALCOHOL AGENTS, DETERGENT COMPOSITIONS AND RINSING AGENTS CONTAINING SAME
    EP0634476A1 (en) Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
    US4954283A (en) Polyethylene glycol ether low temperature foam suppressing agents in low-foam cleaning agents
    EP0165885B1 (en) Liquid composition for the cleaning of hard surfaces
    US4212760A (en) Solubilized alkaline, aqueous solutions of nonionic surfactants
    JPH10504584A (en) Bleaching composition
    JP3898109B2 (en) Alkaline detergent composition for steel sheet
    US4855075A (en) Ethoxylates of alkyl and alkenyl catechols
    BE898436A (en) Liquid detergent composition containing a mixture of enzymes and method of washing the laundry using it.
    JPH08176590A (en) Powder cleaner composition
    JP2007231133A (en) Nonionic surfactant
    JP3248783B2 (en) Alkaline liquid detergent composition for metals
    JPS631359B2 (en)
    JP4694056B2 (en) Two-part bleach
    JP2001107094A (en) Liquid detergent composition
    FR2617862A1 (en) DETERGENT COMPOSITIONS EXEMPT FROM BUILDERS
    JPH0711294A (en) Detergent composition

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 19990706

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    AKX Designation fees paid

    Free format text: AT BE CH CY DE DK ES FR GB GR IE IT LI NL

    RBV Designated contracting states (corrected)

    Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL SE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    17Q First examination report despatched

    Effective date: 20030311

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL SE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

    Effective date: 20040310

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040310

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040310

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040310

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 69915414

    Country of ref document: DE

    Date of ref document: 20040415

    Kind code of ref document: P

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20040604

    Year of fee payment: 6

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040610

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040610

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040610

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IE

    Payment date: 20040611

    Year of fee payment: 6

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DK

    Payment date: 20040615

    Year of fee payment: 6

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20040616

    Year of fee payment: 6

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040621

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: CH

    Payment date: 20040629

    Year of fee payment: 6

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20040813

    Year of fee payment: 6

    GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

    Effective date: 20040310

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20041213

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: CA

    BERE Be: lapsed

    Owner name: S.A. *CECA

    Effective date: 20050630

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20090603

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20090619

    Year of fee payment: 11

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: V1

    Effective date: 20110101

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20110228

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110101

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20100630

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110101

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20090611

    Year of fee payment: 11