EP0377807B1 - Highly alkaline phosphate-free liquid detergent - Google Patents

Highly alkaline phosphate-free liquid detergent Download PDF

Info

Publication number
EP0377807B1
EP0377807B1 EP89121135A EP89121135A EP0377807B1 EP 0377807 B1 EP0377807 B1 EP 0377807B1 EP 89121135 A EP89121135 A EP 89121135A EP 89121135 A EP89121135 A EP 89121135A EP 0377807 B1 EP0377807 B1 EP 0377807B1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
component
alkyl
sodium
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
EP89121135A
Other languages
German (de)
French (fr)
Other versions
EP0377807A1 (en
Inventor
Uwe Dr. Trabitzsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE3841129A external-priority patent/DE3841129A1/en
Priority claimed from DE19893906766 external-priority patent/DE3906766A1/en
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT89121135T priority Critical patent/ATE101412T1/en
Publication of EP0377807A1 publication Critical patent/EP0377807A1/en
Application granted granted Critical
Publication of EP0377807B1 publication Critical patent/EP0377807B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • Textile detergents to be used in commercial laundries differ considerably in their composition from those which are usually used in the household.
  • softened, ie Ca and Mg-free water is used regularly in commercial companies.
  • the commercially used agents often contain highly alkaline builder salts and alkalis, such as sodium metasilicate and sodium hydroxide, which can be handled safely by a person skilled in the art, but are unsuitable in the household for safety reasons.
  • These highly alkaline constituents can in turn interact with the surfactants usually present, in particular the nonionics from the class of the alkyl polyglycol ethers, and more or less decompose them if they are stored together for a long time.
  • surfactants which are made from natural, i.e. renewable raw materials are available and are characterized by their complete and rapid biodegradability in wastewater.
  • Highly alkaline cleaner concentrates for the industrial cleaning of metallic surfaces were known from EP-A-282 863. These agents contain 80 to 99.7 wt .-% of an aqueous solution of a builder mixture of alkali metal silicates and alkali metal hydroxides and 0.3 to 20 wt .-% of a surfactant combination of anionic surfactants, alkyl glucosides and other nonionic surfactants, with amounts of 0.1 to 10% by weight of alkyl glucosides and 0.1 to 5% by weight of nonionic surfactants in combination with 0.1 to 5% by weight of fatty acids or soaps are preferred.
  • EP-A-202 638 describes liquid cleaning agents for strongly alkaline cleaning formulations. These surfactant concentrates, which contain nonionic surfactants and alkyl glucosides, but no alkaline builder substances, are only mixed with alkaline builder substances during practical use.
  • WO-A-87/06949 further describes a liquid detergent which contains alkyl glucosides and builder substances which have a particular solubility. The solubility of relatively poorly soluble builder substances is supported by the use of alkyl glucosides.
  • R is preferably a C8 ⁇ 12 alkyl radical, in particular a C8 ⁇ 10 alkyl radical.
  • the alkyl glucosides can still contain small amounts of free fatty alcohol and glucose in their production. Those alkyl glucosides are preferably used whose content of fatty alcohols is less than 5% by weight, in particular less than 2% by weight (based on alkyl glucoside).
  • the agents can optionally also contain nonionic surfactants of the ethoxylated fatty alcohol and oxo alcohol type with 12 to 18 carbon atoms and 5 to 10 ethylene glycol ether groups (EO).
  • EO ethylene glycol ether groups
  • Suitable are e.g. Ethoxylates derived from coconut, tallow or palm kernel fatty alcohols with an HLB value of more than 12, for example from 13 to 18, and corresponding ethoxylates from oxo alcohols with 12 to 16 carbon atoms and 6 to 8 EO groups.
  • the builder component consists of sodium hydroxide (component B1), sodium silicate (component B2) and sequestering polyanionic salts derived from nitrilotriacetic acid (NTA) and possibly phosphonic acids (components B3 and B4).
  • the Na2O: SiO2 ratio can be 1: 1 (metasilicate) to 1: 3.4 (water glass).
  • metasilicate is preferably used in agents with a low proportion of sodium hydroxide, while in agents with a higher sodium hydroxide content the sodium silicate can consist predominantly or entirely of water glass.
  • the NTA is available as a trisodium salt and is also used in this form of quantity calculation. In particular, its proportion is 5 to 10% by weight.
  • the sodium salt of 1-hydroxyethane-1,1-diphosphonic acid is primarily suitable as the phosphonate.
  • the quantity calculation is based on the tetrasodium salt.
  • the sodium salts of aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs are also usable. unexplained function in wastewater less preferred.
  • Your quantity calculation is based on neutral reacting sodium salts (Na3 salt with ATMP, Na5 salt with EDTMP, Na6 salt with DTPMP).
  • the sum of components B3 + B4 is 3 to 12% by weight, preferably 6 to 11% by weight.
  • the detergents can also contain conventional detergent constituents which do not act as surfactants and builders. These include optical brighteners in proportions of up to 1% by weight, preferably 0.05 to 0.3% by weight. Examples of these are derivatives of bis (triazinylamino) stilbene disulfonic acid, for example the sodium salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid and the chlorinated diphenyldistyrylsulfonic acids.
  • optical brighteners in proportions of up to 1% by weight, preferably 0.05 to 0.3% by weight. Examples of these are derivatives of bis (triazinylamino) stilbene disulfonic acid, for example the sodium salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid and the
  • hydrotropes are e.g. Toluene sulfonate, xylene sulfonate and cumene sulfonate, each in the form of the sodium salts.
  • Usable solvents are, for example, ethanol, propanol, isopropanol and ether alcohols, such as diglycol and C1-C3 monoalkyl ethers of C2-C4 diols.
  • the hydrotropes can be present in proportions up to 6% by weight, the alcohols or ether alcohols in proportions up to 10% by weight.
  • the agents can also contain neutral salts, such as sodium sulfate and sodium chloride, as minor substances in the raw materials used. The difference of up to 100% by weight is water.
  • the agents are long-lasting, pourable liquids that are suitable for automatic dosing as well as for the preparation of stock solutions (base liquors).
  • the concentrates are still liquid down to temperatures of -10 ° C and are resistant to segregation.
  • Their application concentration is generally 2 to 10, preferably 3 to 7 g / l.
  • the amount of laundry was 7.5 kg, the water hardness 0 ° dH, normal program (without prewash), detergent concentration 4 g / l, 5 minutes at 40 ° C and 15 minutes at 90 ° C, three rinsing, low foaming.

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Description

In gewerblichen Wäschereien anzuwendende Textilwaschmittel unterscheiden sich in ihrer ihrer Zusammensetzung erheblich von solchen, die üblicherweise im Haushalt verwendet werden. Einerseits wird in gewerblichen Betrieben regelmäßig mit enthärtetem, d.h. Ca- und Mg-freiem Wasser gearbeitet. Zum anderen enthalten die gewerblich angewendeten Mittel vielfach hochalkalische Buildersalze und Alkalien, wie Natriummetasilikat und Natriumhydroxid, die zwar vom Fachmann gefahrlos gehandhabt werden können, im Haushalt jedoch aus Sicherheitsgründen unangebracht sind. Diese hochalkalischen Bestandteile können ihrerseits mit den üblicherweise anwesenden Tensiden, insbesondere den Nonionics aus der Klasse der Alkylpolyglykolether, in Wechselwirkung treten und sie bei längerer gemeinsamer Lagerung mehr oder weniger zersetzen. Diese Probleme existieren insbesondere bei flüssigen Konzentraten und Produkten, die zum Ansetzen konzentrierter Stammlaugen (Stock-solutions) bestimmt sind und bei denen mangels einer räumlich Trennung von Tensid- und Alakalikomponente der zersetzende Einfluß besonders intensiv ist. Hochalkalische Flüssigprodukte und Stammlaugen haben vor pulverförmigen, gleichartig zusammengesetzten Mitteln den Vorzug, daß sie staubfrei und insbesondere automatisch dosiert werden können und somit keine Bedienungsprobleme aufwerfen.Textile detergents to be used in commercial laundries differ considerably in their composition from those which are usually used in the household. On the one hand, softened, ie Ca and Mg-free water is used regularly in commercial companies. On the other hand, the commercially used agents often contain highly alkaline builder salts and alkalis, such as sodium metasilicate and sodium hydroxide, which can be handled safely by a person skilled in the art, but are unsuitable in the household for safety reasons. These highly alkaline constituents can in turn interact with the surfactants usually present, in particular the nonionics from the class of the alkyl polyglycol ethers, and more or less decompose them if they are stored together for a long time. These problems exist in particular in the case of liquid concentrates and products which are intended for the preparation of concentrated stock liquors (stock solutions) and in which, due to the lack of a spatial separation of the surfactant and alkali components, the decomposing influence is particularly intense. Highly alkaline liquid products and base liquors have the advantage over powdery, similar compositions that they can be dosed dust-free and in particular automatically and therefore do not pose any operating problems.

Ein weiterer Aspekt ist eine möglichst weitgehende Verwendung von Tensiden, die aus natürlichen, d.h. nachwachsenden Rohstoffen erhältlich sind und sich durch eine vollständige und schnelle biologische Abbaufähigkeit im Abwasser auszeichnen.Another aspect is the greatest possible use of surfactants, which are made from natural, i.e. renewable raw materials are available and are characterized by their complete and rapid biodegradability in wastewater.

Weiterhin sollen derartige Mittel im Hauptwaschgang und während des Nachspülens keine störende Schaummengen entwickeln. Da übliche Entschäumer, wie Polysiloxane und Paraffinkohlenwasserstoffe beim Dispergieren in Flüssigwaschmitteln Wirkungsverluste erleiden bzw. im Falle der Polysiloxane durch Alkali zersetzt werden, muß die Tensidkomponente von sich aus schwach schäumend sein.Furthermore, such agents should not develop any troublesome amounts of foam in the main wash and during the rinsing. Since conventional defoamers, such as polysiloxanes and paraffin hydrocarbons, lose their effectiveness when dispersed in liquid detergents or, in the case of the polysiloxanes, are decomposed by alkali, the surfactant component must be inherently low-foaming.

Aus der EP-A-282 863 waren hochalkalische Reinigerkonzentrate für die industrielle Reinigung von metallischen Oberflächen bekannt. Diese Mittel enthalten 80 bis 99,7 Gew.-% einer wäßrigen Lösung eines Buildergemisches von Alkalimetallsilikaten und Alkalimetallhydroxiden und 0,3 bis 20 Gew.-% einer Tensidkombination aus anionischen Tensiden, Alkylglucosiden und anderen nichtionischen Tensiden, wobei Mengen von 0,1 bis 10 Gew.-% Alkylglucosiden und 0,1 bis 5 Gew.-% nichtionischen Tensiden in Kombination mit 0,1 bis 5 Gew.-% Fettsäuren bzw. Seifen bevorzugt sind. Zusätzliche Builder wie Nitrilotriessigsäure und Phosphonate können in Mengen von 0,1 bis 10 Gew.-% zugesetzt werden. EP-A-202 638 beschreibt flüssige Reinigungsmittel für stark alkalische Reinigungsformulierungen. Diese Tensidkonzentrate, die nichtionische Tenside und Alkylglucoside, aber keine alkalischen Buildersubstanzen enthalten, werden erst bei der praktischen Anwendung mit alkalischen Buildersubstanzen versetzt. WO-A-87/06949 beschreibt weiterhin ein Flüssigwaschmittel, das Alkylglucoside und Buildersubstanzen enthält, die eine spezielle Löslichkeit aufweisen. Dabei wird die Löslichkeit relativ schwerlöslicher Buildersubstanzen durch den Einsatz von Alkylglucosiden unterstützt.Highly alkaline cleaner concentrates for the industrial cleaning of metallic surfaces were known from EP-A-282 863. These agents contain 80 to 99.7 wt .-% of an aqueous solution of a builder mixture of alkali metal silicates and alkali metal hydroxides and 0.3 to 20 wt .-% of a surfactant combination of anionic surfactants, alkyl glucosides and other nonionic surfactants, with amounts of 0.1 to 10% by weight of alkyl glucosides and 0.1 to 5% by weight of nonionic surfactants in combination with 0.1 to 5% by weight of fatty acids or soaps are preferred. Additional builders such as nitrilotriacetic acid and phosphonates can be added in amounts of 0.1 to 10% by weight. EP-A-202 638 describes liquid cleaning agents for strongly alkaline cleaning formulations. These surfactant concentrates, which contain nonionic surfactants and alkyl glucosides, but no alkaline builder substances, are only mixed with alkaline builder substances during practical use. WO-A-87/06949 further describes a liquid detergent which contains alkyl glucosides and builder substances which have a particular solubility. The solubility of relatively poorly soluble builder substances is supported by the use of alkyl glucosides.

Gegenstand der Erfindung, mit der die oben erwähnten Probleme gelöst werden, ist ein flüssiges, wäßriges, phosphatfreies Waschmittelkonzentrat, enthaltend 5 bis 20 Gew.-% einer nichtionischen Tensidkomponente (A), 15 bis 40 Gew.-% einer Builderkomponente (B), 0 bis 1 Gew.-% optische Aufheller, 0 bis 6 Gew.-% Hydrotrope, 0 bis 10 Gew.-% mit Wasser mischbare Alkohole bzw. Etheralkohole und sonstige fakultative nicht tensidische und nicht builderhaltige Waschmittelbestandteile sowie Wasser (Differenz bis 100 Gew.-%), wobei die Komponenten, bezogen auf das Waschmittel wie folgt zusammengesetzt sind:

  • A1) 4 bis 20 Gew.-% eines Alkylglucosids der Formel I



            R-O-Gx   (I)



    mit R = C₈-C₁₄-Alkylrest, G = Glucoserest und x = Zahlen von 1,2 bis 5,
  • A2) 0 bis 2 Gew.-% mindestens eines nichtionischen Tensids aus der Klasse der Alkylpolyglykolether mit C₁₂-C₁₈-Alkylgruppen und 5 bis 10 Ethylenglykolethergruppen,
  • B1) 4 bis 20 Gew.-% Natriumhydroxid,
  • B2) 0,5 is 12 Gew.-% Natriumsilikat der Zusammensetzung Na₂O : SiO₂ = 1:1 bis 1:3,4
  • B3) 2 bis 12 Gew.-% Natrium-nitrilotriacetat,
  • B4) 0 bis 3,5 Gew.-% Natriumsalz mindestens einer Phosphonsäure, mit der Maßgabe, daß der Anteil der Bestandteile (B3 + B4) 3 bis 12 Gew.-% beträgt.
The invention, with which the above-mentioned problems are solved, is a liquid, aqueous, phosphate-free detergent concentrate containing 5 to 20% by weight of a nonionic surfactant component (A), 15 to 40% by weight of a builder component (B), 0 to 1% by weight of optical brighteners, 0 to 6% by weight of hydrotropes, 0 to 10% by weight of water-miscible alcohols or ether alcohols and other optional non-surfactant and non-builder-containing detergent components and water (difference up to 100% by weight). -%), whereby the components, based on the detergent, are composed as follows:
  • A1) 4 to 20% by weight of an alkyl glucoside of the formula I.



    ROG x (I)



    with R = C₈-C₁₄ alkyl radical, G = glucose radical and x = numbers from 1.2 to 5,
  • A2) 0 to 2% by weight of at least one nonionic surfactant from the class of the alkyl polyglycol ethers with C₁₂-C₁₈ alkyl groups and 5 to 10 ethylene glycol ether groups,
  • B1) 4 to 20% by weight of sodium hydroxide,
  • B2) 0.5 to 12% by weight sodium silicate of the composition Na₂O: SiO₂ = 1: 1 to 1: 3.4
  • B3) 2 to 12% by weight of sodium nitrilotriacetate,
  • B4) 0 to 3.5% by weight of sodium salt of at least one phosphonic acid, with the proviso that the proportion of constituents (B3 + B4) is 3 to 12% by weight.

Vorzugsweise beträgt der Gehalt der Mittel an den Einzelkomponenten

  • A1) 5 bis 12 Gew.-%
  • A2) 0,5 bis 1,5 Gew.-%
  • B1) 6 bis 15 Gew.-%
  • B2) 0,5 bis 3 Gew.%
  • B3) 3 bis 10 Gew.-%
  • B4) 0,2 bis 2 Gew.
Die Komponente (A1) besteht aus Alkylglucosiden bzw. Alkyloligoglucosiden, wie sie beispielsweise aus den US-Patentschriften 35 47 828, 37 72 269 und 38 39 318 bekannt sind. Sie sind durch Umsetzung von Glucose oder depolymeriserter Stärke und Alkoholen mit C₈₋₁₄-Alkylresten, ohne oder in Gegenwart von niederen Alkoholen oder Glykolen, wie Butanol der Propylenglykol, sowie von sauren Acetalisierungs-Katalysatoren erhältlich. Als Fettalkohole werden bevorzugt aus nativen Fetten, wie Kokos- oder Palmkernfett, gewonnene Alkohole oder Alkoholgemische eingesetzt. Beispeile sind Octyl-, Decyl-, Lauryl- und Myristylalkohol sowie deren Gemische. Alternativ hierzu können auch Alkylglucoside eingesetzt werden, die sich von Oxoalkoholen ableiten und neben linearen Alkoholen auch in 2-Stellung methylverzweigte Alkohole im Gemisch enthalten bzw. eine gerade und/oder ungerade Anzahl von C-Atomen in der Alkylkette aufweisen.The content of the detergents in the individual components is preferably
  • A1) 5 to 12% by weight
  • A2) 0.5 to 1.5% by weight
  • B1) 6 to 15% by weight
  • B2) 0.5 to 3% by weight
  • B3) 3 to 10% by weight
  • B4) 0.2 to 2 wt.
Component (A1) consists of alkyl glucosides or alkyl oligoglucosides, as are known, for example, from US Pat. Nos. 35 47 828, 37 72 269 and 38 39 318. They can be obtained by reacting glucose or depolymerized starch and alcohols with C₈₋₁₄ alkyl radicals, without or in the presence of lower alcohols or glycols, such as butanol or propylene glycol, as well as acidic acetalization catalysts. Alcohols or alcohol mixtures obtained from native fats, such as coconut or palm kernel fat, are preferably used as fatty alcohols. Examples are octyl, decyl, lauryl and myristyl alcohol and their mixtures. Alternatively, it is also possible to use alkyl glucosides which are derived from oxo alcohols and, in addition to linear alcohols, also contain methyl-branched alcohols in the mixture in the 2-position or have an even and / or odd number of carbon atoms in the alkyl chain.

Beispiele hierfür sind Octyl-, Nonyl-, Decyl-, Undecyl-, Dodecyl-und Tridecylalkohol sowie deren Gemische untereinander. Vozugsweise steht R für einen C₈₋₁₂-Alkylrest, insbesondere für einen C₈₋₁₀-Alkylrest. Bei der Umsetzung der Glucose oder glucosehaltigen Stärkeabbauprodukte mit den Alkoholen kommt es in Gegenwart saurer Acetalisierungs-Katalysatoren zu einer teilweisen Oligomerisierung der Glucose, wobei sich Gemische aus Alkylmonoglucosiden und Alkyloligogucosiden bilden. Der Parameter x gemäß Formel I bezeichnet somit einen mittleren Oligomerisierungsgrad. Dieser soll vorzugsweise 1,3 bis 3 betragen. Derartige Gemische sind gemeint, wenn im Zusammenhang mit der Erfindung allgemein von Alkylglucosiden die Rede ist.Examples include octyl, nonyl, decyl, undecyl, dodecyl and tridecyl alcohol and their mixtures with one another. R is preferably a C₈₋₁₂ alkyl radical, in particular a C₈₋₁₀ alkyl radical. When the glucose or starch degradation products containing glucose are reacted with the alcohols, partial glucose oligomerization occurs in the presence of acidic acetalization catalysts, with mixtures of alkyl monoglucosides and alkyl oligogucosides being formed. The parameter x according to formula I thus denotes an average degree of oligomerization. This should preferably be 1.3 to 3. Such mixtures are meant when the context of the invention generally refers to alkyl glucosides.

Von ihrer Herstellung her können die Alkylglucoside noch geringe Mengen an freiem Fettalkohol und Glucose enthalten. Vorzugsweise werden solche Alkylglucoside eingesetzt, deren Gehalt an Fettalkoholen weniger als 5 Gew.-%, insbesondere weniger als 2 Gew.-% (bezogen auf Alkylglucosid) beträgt.The alkyl glucosides can still contain small amounts of free fatty alcohol and glucose in their production. Those alkyl glucosides are preferably used whose content of fatty alcohols is less than 5% by weight, in particular less than 2% by weight (based on alkyl glucoside).

Fakultativ können die Mittel außer den Alkylglucosiden als Komponente (A2) noch nichtionische Tenside vom Typ der ethoxylierten Fettalkohole und Oxoalkohole mit 12 bis 18 C-Atomen und 5 bis 10 Ethylenglykolethergruppen (EO) enthalten. Geeignet sind z.B. von Kokos-, Talg- oder Palmkernfettalkoholen abgeleitete Ethoxylate mit einem HLB-Wert von mehr als 12, beispielsweise von 13 bis 18, sowie entsprechende Ethoxylate von Oxoalkoholen mit 12 bis 16 C-Atomen und 6 bis 8 EO-Gruppen.In addition to the alkyl glucosides as component (A2), the agents can optionally also contain nonionic surfactants of the ethoxylated fatty alcohol and oxo alcohol type with 12 to 18 carbon atoms and 5 to 10 ethylene glycol ether groups (EO). Suitable are e.g. Ethoxylates derived from coconut, tallow or palm kernel fatty alcohols with an HLB value of more than 12, for example from 13 to 18, and corresponding ethoxylates from oxo alcohols with 12 to 16 carbon atoms and 6 to 8 EO groups.

Die Builderkomponente besteht aus Natriumhydroxid (Bestandteil B1), Natriumsilikat (Bestandteil B2) und sequestrierend wirkenden polyanionischen Salzen, abgeleitet von Nitrilotriessigsäure (NTA) und ggf. Phosphonsäuren (Bestandteil B3 und B4).The builder component consists of sodium hydroxide (component B1), sodium silicate (component B2) and sequestering polyanionic salts derived from nitrilotriacetic acid (NTA) and possibly phosphonic acids (components B3 and B4).

Im Natriumsilikat kann das Na₂O : SiO₂-Verhältnis 1:1 (Metasilikat) bis 1:3,4 (Wasserglas) betragen. In Mitteln mit geringeren Anteilen an Natriumhydroxid wird im Interesse einer hohen Alkalität bevorzugt Metasilikat eingesetzt, während in Mitteln mit höheren Natriumhydroxid-Gehalten das Natriumsilikat überwiegend oder vollständig aus Wasserglas bestehen kann.In sodium silicate, the Na₂O: SiO₂ ratio can be 1: 1 (metasilicate) to 1: 3.4 (water glass). In the interest of a high alkalinity, metasilicate is preferably used in agents with a low proportion of sodium hydroxide, while in agents with a higher sodium hydroxide content the sodium silicate can consist predominantly or entirely of water glass.

Das NTA liegt als Trinatriumsalz vor und wird auch in dieser Form der Mengenberechnung zugrunde gelegt. Insbesondere beträgt sein Anteil 5 bis 10 Gew.-%.The NTA is available as a trisodium salt and is also used in this form of quantity calculation. In particular, its proportion is 5 to 10% by weight.

Als Phosphonat kommt in erster Linie das Natriumsalz der 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) in Frage. Der Mengenberechnung wird das Tetranatriumsalz zugrunde gelegt. Brauchbar sind auch die Natriumsalze der Aminotrimethylenphosphonsäure (ATMP), Ethylendiamintetramethylenphosphonsäure (EDTMP), Diethylentriaminpentamethylenphosphonsäure (DTPMP) und deren höhere Homologen, jedoch ist EDTMP wegen ihrer z.Zt. ungeklärten Funktion im Abwasser weniger bevorzugt. Ihre Mengenberechnung basiert auf neutral reagierenden Natriumsalzen (Na₃-Salz bei ATMP, Na₅-Salz bei EDTMP, Na₆-Salz bei DTPMP). Die Summe der Komponenten B3 + B4 beträgt 3 bis 12 Gew.-%, vorzugsweise 6 bis 11 Gew.-%.The sodium salt of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is primarily suitable as the phosphonate. The quantity calculation is based on the tetrasodium salt. The sodium salts of aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs are also usable. unexplained function in wastewater less preferred. Your quantity calculation is based on neutral reacting sodium salts (Na₃ salt with ATMP, Na₅ salt with EDTMP, Na₆ salt with DTPMP). The sum of components B3 + B4 is 3 to 12% by weight, preferably 6 to 11% by weight.

Neben den vorgenannten Bestandteilen können die Mittel noch übliche, nicht als Tenside und Builder wirkende Waschmittelbestandteile enthalten. Hierzu zählen optische Aufheller in Anteilen bis zu 1 Gew.-%, vorzugsweise 0,05 bis 0,3 Gew.-%. Beispiele hierfür sind Derivate der Bis-(triazinylamino)-stilbendisulfonsäure, beispielsweise das Natriumsalz der 4,4'-Bis-(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure sowie der chlorierten Diphenyldistyryl-sulfonsäuren.In addition to the aforementioned constituents, the detergents can also contain conventional detergent constituents which do not act as surfactants and builders. These include optical brighteners in proportions of up to 1% by weight, preferably 0.05 to 0.3% by weight. Examples of these are derivatives of bis (triazinylamino) stilbene disulfonic acid, for example the sodium salt of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid and the chlorinated diphenyldistyrylsulfonic acids.

Weitere fakultative Bestandteile sind Enzyme, Duftstoffe, Farbstoffe, Hydrotrope und mit Wasser mischbare Lösungsmittel. Als Hydrotrope eignen sich z.B. Toluolsulfonat, Xylolsulfonat und Cumolsulfonat, jeweils in Form der Natriumsalze. Brauchbare Lösungsmittel sind beispielsweise Ethanol, Propanol, Isopropanol sowie Etheralkohole, wie Diglykol und C₁-C₃-Monoalkylether von C₂-C₄-Diolen. Die Hydrotrope können in Anteilen bis 6 Gew.-%, die Alkohole bzw. Etheralkohole in Anteilen bis 10 Gew.-% anwesend sein. Ferner können die Mittel Neutralsalze, wie Natriumsulfat und Natriumchlorid, als Begleitstoffe der eingesetzten Rohstoffe in untergeordneter Menge enthalten. Die Differenz bis 100 Gew.-% entfällt auf Wasser.Other optional components are enzymes, fragrances, dyes, hydrotropes and water-miscible solvents. Suitable hydrotropes are e.g. Toluene sulfonate, xylene sulfonate and cumene sulfonate, each in the form of the sodium salts. Usable solvents are, for example, ethanol, propanol, isopropanol and ether alcohols, such as diglycol and C₁-C₃ monoalkyl ethers of C₂-C₄ diols. The hydrotropes can be present in proportions up to 6% by weight, the alcohols or ether alcohols in proportions up to 10% by weight. The agents can also contain neutral salts, such as sodium sulfate and sodium chloride, as minor substances in the raw materials used. The difference of up to 100% by weight is water.

Die Mittel sind haltbare, gießbare Flüssigkeiten, die sich sowohl zur automatischen Dosierung als auch zum Ansetzen von Vorratslösungen (Stammlaugen) eignen. Die Konzentrate sind bis zu Temperaturen von -10 °C noch flüssig und gegen Entmischen beständig. Ihre Anwendungskonzentration beträgt im allgemeinen 2 bis 10, vorzugsweise 3 bis 7 g/l.The agents are long-lasting, pourable liquids that are suitable for automatic dosing as well as for the preparation of stock solutions (base liquors). The concentrates are still liquid down to temperatures of -10 ° C and are resistant to segregation. Their application concentration is generally 2 to 10, preferably 3 to 7 g / l.

BeispieleExamples

Es wurden Waschmittel folgender Zusammensetzung hergestellt. Im Alkylglucosid war R ein Gemisch von C₈₋₁₀-Alkylgruppen und x = 1,8, hergestellt nach der Methode der Direktsynthese.

Figure imgb0001
Detergents of the following composition were produced. In the alkyl glucoside, R was a mixture of C₈₋₁₀ alkyl groups and x = 1.8, prepared by the direct synthesis method.
Figure imgb0001

Eine Waschmaschine (Typ Frista (R)) wurde mit leicht verschmutzter Füllwäsche (einmal benutzte Bett- und Tischwäsche) und Testlappen mit folgenden Anschmutzungen beladen:

  • A1 Staub-Wollfett auf Baumwolle,
  • A2 Blut-Milch-Tusche auf Baumwolle,
  • A3 Blut auf Baumwolle,
  • A4 Milchkakao auf Baumwolle,
  • A5 Staub-Hautfett auf veredelter Baumwolle,
  • A6 Staub-Hautfett auf Mischgewebe aus veredelter Baumwolle und Polyester,
  • A7 Staub-Wollfett auf Mischgewebe (wie A6).
A washing machine (type Frista (R) ) was loaded with lightly soiled filling laundry (once used bed and table linen) and test rags with the following soiling:
  • A1 dust-wool grease on cotton,
  • A2 blood-milk ink on cotton,
  • A3 blood on cotton,
  • A4 milk cocoa on cotton,
  • A5 dusty skin fat on refined cotton,
  • A6 Dust-skin fat on mixed fabrics made from refined cotton and polyester,
  • A7 Dust-wool grease on mixed fabrics (like A6).

Die Wäschemenge betrug 7,5 kg, die Wasserhärte 0 °dH, Normalprogramm (ohne Vorwäsche), Waschmittelkonzentration 4 g/l, 5 Minuten bei 40 °C und 15 Minuten bei 90 °C, dreimaliges Nachspülen, geringe Schaumentwicklung.The amount of laundry was 7.5 kg, the water hardness 0 ° dH, normal program (without prewash), detergent concentration 4 g / l, 5 minutes at 40 ° C and 15 minutes at 90 ° C, three rinsing, low foaming.

Die prozentuale Remission (gegen Weißstandard) wurde photometrisch ausgewertet. Die Zahlenwerte sind Mittelwerte aus 3 Parallelbestimmungen (Streuung 2 %). De Ergebnisse sind in der folgenden Tabelle 2 zusammengestellt. Zum Vergleich V wurde ein ähnlich zusammengesetztes Mittel des Handels (ohne Glucosid) herangezogen. Vergleichbar gute Waschergebnisse wurden auch erhalten, wenn anstelle des Alkylglucosids mit x = 1,8 solche mit x = 1,4 und x = 2,2 eingesetzt wurden.

Figure imgb0002
The percentage remission (against white standard) was evaluated photometrically. The numerical values are mean values from 3 parallel determinations (spread 2%). The results are summarized in Table 2 below. For comparison V a similar composition of the trade (without glucoside) was used. Comparably good washing results were also obtained if, instead of the alkyl glucoside with x = 1.8, those with x = 1.4 and x = 2.2 were used.
Figure imgb0002

Claims (8)

  1. A liquid, aqueous, non-phosphate detergent concentrate containing 5 to 20% by weight of a nonionic surfactant component (A), 15 to 40% by weight of a builder component (B), 0 to 1% by weight optical brighteners, 0 to 6% by weight hydrotropes, 0 to 10% by weight water-miscible alcohols or ether alcohols and other non-surface-active and non-builder-containing detergent ingredients and water (balance to 100% by weight), characterized in that the components have the following composition, based on the detergent:
    A1) 4 to 20% by weight of an alkyl glucoside corresponding to formula I



            R-O-Gx   (I)



    where R = a C₈₋₁₄ alkyl radical, G = a glucose unit and x = a number of 1.2 to 5,
    A2) 0 to 2% by weight of at least one nonionic surfactant from the class of alkyl polyglycol ethers containing C₁₂₋₁₈ alkyl groups and 5 to 10 ethylene glycol ether groups,
    B1) 4 to 20% by weight sodium hydroxide,
    B2) 0.5 to 12% by weight sodium silicate having the composition Na₂O : SiO₂ = 1:1 to 1:3.4,
    B3) 2 to 12% by weight sodium nitrilotriacetate,
    B4) 0 to 3.5% by weight of the sodium salt of at least one phosphonic acid, with the proviso that the content of constituents (B3 + B4) is from 3 to 12% by weight.
  2. A detergent as claimed in claim 1, characterized in that the individual components are present in the following quantities:
    A1) 5 to 12 % by weight
    A2) 0.5 to 1.5 % by weight
    B1) 6 to 15 % by weight
    B2) 0.5 to 3 % by weight
    B3) 3 to 10 % by weight
    B4) 0.2 to 2 % by weight
  3. A detergent as claimed in claim 1 or 2, characterized in that, in formula (I), R = C₈₋₁₂ alkyl radicals and x = a number of 1.3 to 3.
  4. A detergent as claimed in one or more of claims 1 to 3, characterized in that the nonionic surfactant of component (A2) has an HLB value of 12 to 18.
  5. A detergent as claimed in one or more of claims 1 to 4, characterized in that component (B4) consists of the sodium salt of 1-hydroxyethane-1,1-diphosphonic acid.
  6. A detergent as claimed in claim 5, characterized in that component (B4) additionally contains the sodium salt of diethylenetriamine pentamethylene phosphonic acid.
  7. A detergent as claimed in one or more of claims 1 to 6, characterized in that the content of component (B3) is from 5 to 10% by weight.
  8. A detergent as claimed in claims 5 to 7, characterized in that the sum of components (B3 + B4) is from 6 to 11% by weight.
EP89121135A 1988-12-07 1989-11-15 Highly alkaline phosphate-free liquid detergent Expired - Lifetime EP0377807B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89121135T ATE101412T1 (en) 1988-12-07 1989-11-15 PHOSPHATE-FREE LIQUID DETERGENT WITH HIGH ALKALINE.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3841129 1988-12-07
DE3841129A DE3841129A1 (en) 1988-12-07 1988-12-07 Phosphate-free, liquid detergent with high alkalinity
DE19893906766 DE3906766A1 (en) 1989-03-03 1989-03-03 Phosphate-free liquid detergent of high alkalinity
DE3906766 1989-03-03

Publications (2)

Publication Number Publication Date
EP0377807A1 EP0377807A1 (en) 1990-07-18
EP0377807B1 true EP0377807B1 (en) 1994-02-09

Family

ID=25874879

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89912958A Pending EP0447413A1 (en) 1988-12-07 1989-11-15 Phosphate-free liquid washing agent with high alkalinity
EP89121135A Expired - Lifetime EP0377807B1 (en) 1988-12-07 1989-11-15 Highly alkaline phosphate-free liquid detergent

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89912958A Pending EP0447413A1 (en) 1988-12-07 1989-11-15 Phosphate-free liquid washing agent with high alkalinity

Country Status (9)

Country Link
EP (2) EP0447413A1 (en)
JP (1) JPH04502337A (en)
AU (1) AU626954B2 (en)
CA (1) CA2004895A1 (en)
DE (1) DE58906948D1 (en)
DK (1) DK101291A (en)
ES (1) ES2061894T3 (en)
PT (1) PT92396A (en)
WO (1) WO1990006353A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4009533A1 (en) * 1990-03-24 1991-09-26 Henkel Kgaa LOW-EFFICIENT NON-ionic surfactant mix
DE4225224A1 (en) * 1992-07-30 1994-02-03 Henkel Kgaa Process for the production of storage-stable nonionic surfactants
US5503754A (en) * 1993-11-10 1996-04-02 Henkel Corporation Wet treatment of leather hides
US5542950A (en) * 1994-11-10 1996-08-06 Henkel Corporation Alkyl polyglycosides in textile scour/bleach processing
US5525256A (en) * 1995-02-16 1996-06-11 Henkel Corporation Industrial and institutional liquid cleaning compositions containing alkyl polyglycoside surfactants
FR2744132B1 (en) 1996-01-31 1998-04-24 Rhone Poulenc Chimie BASIC SYSTEM OF A NON-IONIC SURFACTANT AND AN ALKALINE METAL SILICATE, IN THE FORM OF A DISPERSION OR PELLETS AND ITS USE IN DETERGENCE
US6194371B1 (en) 1998-05-01 2001-02-27 Ecolab Inc. Stable alkaline emulsion cleaners
US6369021B1 (en) * 1999-05-07 2002-04-09 Ecolab Inc. Detergent composition and method for removing soil
US7041177B2 (en) 2002-08-16 2006-05-09 Ecolab Inc. High temperature rapid soil removal method
US20170369819A1 (en) * 2016-06-27 2017-12-28 The Procter & Gamble Company Removal of hydrophilic body soils

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0202638A2 (en) * 1985-05-24 1986-11-26 BASF Aktiengesellschaft Liquid cleaning concentrate for strongly alkaline cleaning formulations
EP0282863A2 (en) * 1987-03-14 1988-09-21 Henkel Kommanditgesellschaft auf Aktien Liquid alkaline cleaning concentrates

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772259A (en) 1965-07-12 1973-11-13 American Cyanamid Co 2-vinyl-1-cycloamidinepropionamide polymers
US3547828A (en) 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
US3721633A (en) * 1969-10-06 1973-03-20 Atlas Chem Ind Aqueous built liquid detergents containing alkyl glycosides
US3839318A (en) 1970-09-27 1974-10-01 Rohm & Haas Process for preparation of alkyl glucosides and alkyl oligosaccharides
GR76286B (en) * 1981-09-28 1984-08-04 Procter & Gamble
FR2540511B1 (en) * 1983-02-04 1985-08-09 Henkel France LIQUID CLEANING COMPOSITION AND METHOD FOR CLEANING USING THE SAME
WO1987006949A1 (en) * 1986-05-06 1987-11-19 A. E. Staley Manufacturing Company Built liquid laundry detergent containing alkyl glycoside surfactant

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0202638A2 (en) * 1985-05-24 1986-11-26 BASF Aktiengesellschaft Liquid cleaning concentrate for strongly alkaline cleaning formulations
EP0282863A2 (en) * 1987-03-14 1988-09-21 Henkel Kommanditgesellschaft auf Aktien Liquid alkaline cleaning concentrates

Also Published As

Publication number Publication date
CA2004895A1 (en) 1990-06-07
EP0447413A1 (en) 1991-09-25
DK101291D0 (en) 1991-05-28
JPH04502337A (en) 1992-04-23
ES2061894T3 (en) 1994-12-16
PT92396A (en) 1990-06-29
AU626954B2 (en) 1992-08-13
EP0377807A1 (en) 1990-07-18
DE58906948D1 (en) 1994-03-24
DK101291A (en) 1991-05-28
AU4626089A (en) 1990-06-26
WO1990006353A1 (en) 1990-06-14

Similar Documents

Publication Publication Date Title
EP0201016B1 (en) Builder-free liquid detergents with softening properties
EP0272574B1 (en) Mixtures of liquid non-ionic surfactants
DE69325589T2 (en) CLEAN WITH SHORT-CHAIN SURFACES
EP0448581B1 (en) Washing agent containing bleach, in liquid to paste form
DE69330446T2 (en) Particulate laundry softeners and detergents
DE4029777A1 (en) LIQUID, NON-TENSID COMBINATION WITH IMPROVED CELL TESTABILITY
DE1926422A1 (en) Detergents and cleaning agents
EP0435903A1 (en) Washing agents for low temperatures
DE4009533A1 (en) LOW-EFFICIENT NON-ionic surfactant mix
EP0377807B1 (en) Highly alkaline phosphate-free liquid detergent
SE437999B (en) POWDER-DETERGENT COMPOSITION FOR AUTOMATIC WASHERS
EP0024340B1 (en) Washing process
EP0541523B1 (en) Paste-like, phosphate-free detergent with reduced frothing tendency
DE2257642A1 (en) BIODEGRADABLE DETERGENTS AND DETERGENTS
DE3486155T2 (en) Laundry detergent.
WO1992019711A1 (en) Liquid washing agent
DE4011487A1 (en) TENSID MIXTURE FOR USE IN WASHING AND CLEANING AGENTS
WO1990001534A1 (en) Low-phosphate builder salt combination
EP0288461B1 (en) Fabric softening liquid washing product, substantially free of buildersalts and having an improved washing performance
DE2502433A1 (en) DETERGENTS AND DETERGENTS, IN PARTICULAR FOR THE REMOVAL OF GREASE AND OIL STAINS
DE3644808A1 (en) PHOSPHATE-FREE DETERGENT WITH REDUCED FOAM PRIORITY
DE3841129A1 (en) Phosphate-free, liquid detergent with high alkalinity
DE3906766A1 (en) Phosphate-free liquid detergent of high alkalinity
DE2916656A1 (en) Optical brightener-free textile detergent compsn. - contg. aliphatic polyglycol ether(s), alkyl-pyridinium salt and standard additives
DE3920480A1 (en) FLUESSIGWASCHMITTEL

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): ES

17P Request for examination filed

Effective date: 19910109

RBV Designated contracting states (corrected)

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

XX Miscellaneous (additional remarks)

Free format text: VERBUNDEN MIT 89912958.9/0447413 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 18.11.91.

17Q First examination report despatched

Effective date: 19920224

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 ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 101412

Country of ref document: AT

Date of ref document: 19940215

Kind code of ref document: T

XX Miscellaneous (additional remarks)

Free format text: VERBUNDEN MIT 89912958.9/0447413 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 18.11.91.

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940207

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58906948

Country of ref document: DE

Date of ref document: 19940324

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19941115

Ref country code: AT

Effective date: 19941115

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

Ref country code: SE

Effective date: 19941116

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19941116

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

Ref country code: LI

Effective date: 19941130

Ref country code: CH

Effective date: 19941130

Ref country code: BE

Effective date: 19941130

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

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2061894

Country of ref document: ES

Kind code of ref document: T3

EAL Se: european patent in force in sweden

Ref document number: 89121135.1

26N No opposition filed
BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19941130

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

Ref country code: NL

Effective date: 19950601

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19941115

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: DE

Effective date: 19950801

EUG Se: european patent has lapsed

Ref document number: 89121135.1

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010301

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 NON-PAYMENT OF DUE FEES;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: 20051115