WO1990006353A1 - Phosphate-free liquid washing agent with high alkalinity - Google Patents

Phosphate-free liquid washing agent with high alkalinity Download PDF

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Publication number
WO1990006353A1
WO1990006353A1 PCT/EP1989/001370 EP8901370W WO9006353A1 WO 1990006353 A1 WO1990006353 A1 WO 1990006353A1 EP 8901370 W EP8901370 W EP 8901370W WO 9006353 A1 WO9006353 A1 WO 9006353A1
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Prior art keywords
weight
composition according
component
sodium
alkyl
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PCT/EP1989/001370
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German (de)
French (fr)
Inventor
Uwe Trabitzsch
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Henkel Kommanditgesellschaft Auf Aktien
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Publication date
Priority claimed from DE3841129A external-priority patent/DE3841129A1/en
Priority claimed from DE19893906766 external-priority patent/DE3906766A1/en
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1990006353A1 publication Critical patent/WO1990006353A1/en
Priority to FI912463A priority Critical patent/FI912463A0/en
Priority to DK101291A priority patent/DK101291A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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

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 bu il 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 for safety reasons in the household.
  • 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.
  • the invention 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 bullder component (B), bis 3% by weight of other non-surfactant and non-builder-type detergent components and water (difference up to 100% by weight), characterized in that the components, based on the detergent, are composed as follows:
  • SiO 2 1: 1 to 1: 3.4
  • B4 0 to 3% by weight of sodium salt of at least one phosphonic acid, with the proviso that the proportion of the constituents (B3 + B4) is 3 to 12% by weight.
  • the content of the detergents in the individual components is preferably
  • Component (A1) consists of alkyl glucosides or alkyl oligoglucosides, as are known, for example, from US Pat. Nos. 35 47 828, 37 72 259 and 38 39 313. They can be obtained by reacting glucose or depolymerized starch and alcohols with C 8-14 -alkyl radicals, without or in the presence of lower alcohols or glycols, such as butanol or propylene glycol, and also from 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 mixtures thereof.
  • 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. Examples include octyl, nonyl, decyl, undecyl, dodecyl and tridecyl alcohol and their mixtures with one another.
  • R is preferably a C 8-12 alkyl radical, in particular a C 8-10 alkyl radical.
  • the glucose or glucose-containing starch degradation products are reacted with the alcohols, the glucose is partially oligomerized in the presence of acidic acetalization catalysts, mixtures of alkyl monoglucosides and alkyl oligoglucosides being formed.
  • the parameter x according to formula I thus denotes an average degree of oligomerization. This should preferably be 1.3 to 3. Mixtures of this type are meant when aikylglucosides are generally mentioned in connection with the invention.
  • 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 polyether groups (EO).
  • EO ethylene polyether 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 Nitri lotriessigklare (NTA) and possibly phosphonic acids (components B3 and B4).
  • the Na 2 O: SiO 2 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.
  • Also useful are the sodium salts of aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologues. unclarified function in wastewater less preferred.
  • Their quantity calculation is based on neutral sodium salts (Na 3 salt with ATMP, Na 5 salt with EDTMP, Na 5 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, for example, toluenesulfonate, 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 C 1-3 monoalkyl ethers of C 2-4 diols.
  • the hydrotropes can be present in proportions of up to 5% by weight, the alcohols or ether alcohols in proportions of 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 essentially 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 escape.
  • Their application concentration is generally 2 to 10, preferably 3 to 7 g / l.
  • a washing machine (type Frista (R) ) was slightly soiled
  • A7 Dust-wool grease on mixed fabrics (like A5).
  • 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.

Abstract

A washing agent concentrate suitable for preparing liquid concentrated stock solutions contains (A) 5 to 20 wt. % of non-ionic tensides, including (A1) 4 to 20 wt.-% of alkylglucosides of formula R-O-Gx? and (A2) 0 to 2 wt.% of C12-18? alkyl polyglycol ether with 5 to 9 ethylene glycol ether groups, (B1) 4 to 20 wt. % of sodium hydroxyde, (B2) 0.5 to 12 wt. % of sodium silicate Na2?O:SiO2? = 1:1 to 1:3.4, (B3) 2 to 12 wt. % of sodium nitrilotriacetate and 0 to 3 wt. % of at least one phosphonic acid in the form of the sodium salt. In the formula R-O-Gx?, R denotes a C8-14? alkyl residue, G a glucose residue and the index x numbers between 1.2 and 5. The sum of the constituents (B3) and (B4) is between 3 and 12 wt. %.

Description

"Phosphatfreies, flüssiges Waschmittel mit hoher Alkalität"  "Phosphate-free, liquid detergent with high alkalinity"
In gewerblichen Wäschereien anzuwendende Textilwaschmittel unterscheiden sich in 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 Bu i l dersalze und Alkalien, wie Natriummetasilikat und Natriumhydroxid, die zwar vom Fachmann gefahrlos gehandhabt werden können, im Haushalt jedoch aus Sicherheitsgründen unangebracht sind. Diese hochalkalischen Bestandteils können ihrerseits mit den üblicherweise anwesenden Tensiden, insbesondere den Nonionics aus der Klasse der Alkyl- polyglykolether, 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 räumlichen Trennung von Tensid- und Alkalikomponente 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. 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. 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 bu il 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 for safety reasons in the household. 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, because there is no 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. Another aspect is the greatest possible use of surfactants, which are available from natural, ie renewable, raw materials 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.
Gegenstand der Erfindung, mit der diese Probleme gelöst werden, ist ein flüssiges, wäßriges, phosphatfreies Waschmittelkonzentrat, enthaltend 5 bis 20 Gew.-% einer nichtioni sehen Tensidkomponente (A), 15 bis 40 Gew.-% einer Bullderkomponente (B), bis 3 Gew.-% an sonstigen nicht tensidischen und nicht builderartigen Waschmit- telbestanuteilen sowie Wasser (Differenz bis 100 Gew.-%), dadurch gekennzeichnet, daß die Komponenten, bezogen auf das Waschmittel, wie folgt zusammengesetzt sind: The invention, with which these 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 bullder component (B), bis 3% by weight of other non-surfactant and non-builder-type detergent components and water (difference up to 100% by weight), characterized in that the components, based on the detergent, are composed as follows:
A1) 4 bis 20 Gew.-% eines Alkylglucosids der Formel I A1) 4 to 20% by weight of an alkyl glucoside of the formula I.
R-O-Gx (I) mit R = C8-14-Alkylrest, G = Glucoserest und ROG x (I) with R = C 8-14 alkyl, G = glucose and
x = Zahlen von 1,2 bis 5,  x = numbers from 1.2 to 5,
A2) 0 bis 2 Gew.-% mindestens eines nichtionischen Tensids aus der Klasse der Alkylpolyglykolether mit C12 -18-Alylgruppen und 5 bis 9 Ethylenglykolethergruppen, A2) 0 to 2 wt .-% of at least one nonionic surfactant from the class of alkyl polyglycol ethers with C 12 -18 -Alylgruppen and 5 to 9 ethylene glycol ether groups,
B1) 4 bis 20 Gew.-% Natriumhydroxid, B2) 0,5 bis 12 Gew.-% Natriumsilikat der Zusammensetzung Na2O :B1) 4 to 20% by weight of sodium hydroxide, B2) 0.5 to 12% by weight sodium silicate of the composition Na 2 O:
SiO2 = 1:1 bis 1:3,4 SiO 2 = 1: 1 to 1: 3.4
B3) 2 bis 12 Gew.-% Natrium-nitrilotriacetat,  B3) 2 to 12% by weight of sodium nitrilotriacetate,
B4) 0 bis 3 Gew.-% Natriumsalz mindestens einer Phosphonsäure, mit der Maßgabe, daß der Anteil der Bestandteile (B3 + B4) 3 bis 12 Gew.-% beträgt.  B4) 0 to 3% by weight of sodium salt of at least one phosphonic acid, with the proviso that the proportion of the constituents (B3 + B4) is 3 to 12% by weight.
Vorzugsweise beträgt der Gehalt der Mittel an den Einzelkomponenten The content of the detergents in the individual components is preferably
A1) 5 bis 12 Gew.-%  A1) 5 to 12% by weight
A2) 0,5 bis 1,5 Gew.-%  A2) 0.5 to 1.5% by weight
B1) 6 bis 15 Gew.-%  B1) 6 to 15% by weight
B2) 0,5 bis 3 Gew.-%  B2) 0.5 to 3% by weight
B3) 3 bis 10 Gew.-%  B3) 3 to 10% by weight
B4) 0,2 bis 2 Gew.-%  B4) 0.2 to 2% by weight
Die Komponente (A1) besteht aus Alkylglucosiden bzw. Alkyloligoglucosiden, wie sie beispielsweise aus den US-Patentschriften 35 47 828, 37 72 259 und 38 39 313 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 oder Propylenglykol, sowie von sauren Acetalisierungs-Katalysatoren erhältlich. Als Fettalkohole werden bevorzugt aus nativen Fetten, wie Kokos- oder Palmkernfett, gewonnene Alkohole oder Alkoholgemische eingesetzt. Beispiele 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. Beispiele hierfür sind Octyl-, Nonyl-, Decyl-, Undecyl, Dodecyl- und Tridecylalkohol sowie deren Gemische untereinander. Vorzugsweise 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 Alkyloligoglucosiden 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 Aikylglucosiden die Rede ist. Component (A1) consists of alkyl glucosides or alkyl oligoglucosides, as are known, for example, from US Pat. Nos. 35 47 828, 37 72 259 and 38 39 313. They can be obtained by reacting glucose or depolymerized starch and alcohols with C 8-14 -alkyl radicals, without or in the presence of lower alcohols or glycols, such as butanol or propylene glycol, and also from 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 mixtures thereof. As an alternative to this, 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. Examples include octyl, nonyl, decyl, undecyl, dodecyl and tridecyl alcohol and their mixtures with one another. R is preferably a C 8-12 alkyl radical, in particular a C 8-10 alkyl radical. When the glucose or glucose-containing starch degradation products are reacted with the alcohols, the glucose is partially oligomerized in the presence of acidic acetalization catalysts, mixtures of alkyl monoglucosides and alkyl oligoglucosides being formed. The parameter x according to formula I thus denotes an average degree of oligomerization. This should preferably be 1.3 to 3. Mixtures of this type are meant when aikylglucosides are generally mentioned in connection with the invention.
Von ihrer Herstellung her können die Alkylglucoside noch geringe Mengen an freiem Fettalkohol und Glucose enthalten. Vorzugsweise werden solche Alkylglucoside eingesetzt, deren Gehalt an FettalIcoholen 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 Ethylenpolykolethergruppen (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 polyether 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 Nitri lotriessigsäure (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 Nitri lotriessigsäure (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 the sodium silicate, the Na 2 O: SiO 2 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), Ethylendiamintetramethylenphosρhonsaure (EDTMP) , Diethylentria minpentamethylenphosphonsäure (DTPMP) und deren höhere Homologen, jedoch ist EDTMP wegen ihrer z.Zt. ungekiärten Funktion im Abwasser weniger bevorzugt. Ihre Mengenberechnung basiert auf neutral reagierenden Natriumsalzen (Na3-Salz bei ATMP, Na5-Salz bei EDTMP, Na5-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. Also useful are the sodium salts of aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologues. unclarified function in wastewater less preferred. Their quantity calculation is based on neutral sodium salts (Na 3 salt with ATMP, Na 5 salt with EDTMP, Na 5 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, bei spielsweise 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 C1-3-Monoalkylether von C2-4-Diolen. Die Hydrotrope können in Anteilen bis 5 Gew.-%, die Alkohole bzw. Etheralkohole in Anteilen bis 10 Gew.-% anwesend sein. Femer können die Mittel Neutralsalze, wie Natriumsulfat und Natriumchlorid, als Begleitstoffe der eingesetzten Rohstoffe in untergeordneter Menge enthalten. Die Differenz bis 100 Gew.-% ent- fällt im wesentlichen auf Wasser. Other optional components are enzymes, fragrances, dyes, hydrotropes and water-miscible solvents. Suitable hydrotropes are, for example, toluenesulfonate, 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 C 1-3 monoalkyl ethers of C 2-4 diols. The hydrotropes can be present in proportions of up to 5% by weight, the alcohols or ether alcohols in proportions of 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 essentially 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 Entrnischen beständig. Ihre Anwendungskonzentration beträgt im allgemeinen 2 bis 10, vorzugs- weise 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 escape. Their application concentration is generally 2 to 10, preferably 3 to 7 g / l.
B e i s p i e l e
Figure imgf000009_0002
Examples
Figure imgf000009_0002
Es wurden Waschmittel folgender Zusammensetzung hergestellt. Im Detergents of the following composition were produced. in the
Alkylglucosid war R ein Gemisch von C8-10-Alkylgruppen und x = R was a mixture of C 8-10 alkyl groups and x = alkyl glucoside
1,8, hergestellt nach der Methode der Direktsynthese.  1.8, produced by the direct synthesis method.
Figure imgf000009_0001
Figure imgf000009_0001
Eine Waschmaschine (Typ Frista (R)) wurde mit leicht verschmutzter A washing machine (type Frista (R) ) was slightly soiled
Füllwäsche (einmal benutzte Bett- und Tischwäsche) und Testlappen  Filling linen (bed and table linen once used) and test rags
mit folgenden Anschmutzungen beladen: A1 Staub-Wollfett auf Baumwolle, loaded with the following soiling: A1 dust-wool grease on cotton,
A2 Blut-Milch-Tusche auf Baumwolle,  A2 blood-milk ink on cotton,
A3 Blut auf Baumwolle,  A3 blood on cotton,
A4 Milchkakao auf Baumwolle,  A4 milk cocoa on cotton,
A5 Staub-Hautfett auf veredelter Baumwolle,  A5 dusty skin fat on refined cotton,
A6 Staub-Hautfett auf Mischgewebe aus veredelter Baumwolle und A6 Dust-skin grease on mixed fabrics made from refined cotton and
Polyester, Polyester,
A7 Staub-Wollfett auf Mischgewebe (wie A5).  A7 Dust-wool grease on mixed fabrics (like A5).
Die Wäschemenge betrug 7,5 kg, die Wasserhärte 0 °dH, Normalprogramm (ohne Vorwäsche), Waschmittelkonzentralion 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 Parallelbestimm ungen (Streuung 2 %). Die Ergeumsse sind in der τolgendnn Tabelle 2 zusammengestent. 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. 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 imgf000011_0001
Figure imgf000011_0001

Claims

P a t e n t a n s n r ü c h e 1. Flüssiges, wäßriges, phosphatfreies Waschmittelkonzentrat, enthaltend 5 bis 20 Gew.-% einer nichtionischen Tensidkomponente (A), 15 bis 40 Gew.-% einer Builderkomponente (B), bis 3 Gew.-% an sonstigen nicht tensidischen und nicht bui 1derartigen Waschmittelbestandteilen sowie Wasser (Differenz bis 100 Gew.-%), dadurch gekennzeichnet, daß die Komponenten, bezogen auf das Waschmittel, wie folgt zusammengesetzt sind: P atentansnr ü che 1. Liquid, aqueous, phosphate-free detergent concentrate, containing 5 to 20 wt .-% of a nonionic surfactant component (A), 15 to 40 wt .-% of a builder component (B), up to 3 wt .-% of other not Surfactant and non-powdery detergent components and water (difference up to 100% by weight), characterized in that the components, based on the detergent, are composed as follows:
A1 ) 4 bis 20 Gew. -% eines Alkylglucos ids der Formel I  A1) 4 to 20% by weight of an alkylglucose id of the formula I.
R-O-Gx (I ) mit R = C8-14-Alkylrest, G = Glucoserest und ROG x (I) with R = C 8 -14-alkyl residue, G = glucose residue and
x = Zahlen von 1,2 bis 5,  x = numbers from 1.2 to 5,
A2) 0 bis 2 Gew.-% mindestens eines nichtiomschen Tensids aus der Klasse der Alkylpolyglykolether mit C12-18-A2) 0 to 2% by weight of at least one non-ionic surfactant from the class of the alkyl polyglycol ethers with C 12-18 -
Alkylgruppen und 5 bis 9 Ethylenglykolethergruppen, B1) 4 bis 20 Gew.-% Natriumhydroxid, Alkyl groups and 5 to 9 ethylene glycol ether groups, B1) 4 to 20% by weight sodium hydroxide,
B2) 0,5 bis 12 Gew.-% Natriumsilikat der Zusammensetzung  B2) 0.5 to 12% by weight sodium silicate of the composition
Na2O : SiO2 = 1:1 bis 1:3,4 Na 2 O: SiO 2 = 1: 1 to 1: 3.4
B3) 2 bis 12 Gew.-% Natrium-nitrilotriacetat,  B3) 2 to 12% by weight of sodium nitrilotriacetate,
B4) 0 bis 3 Gew.-% Natriumsalz mindestens einer Phosphonsäure, mit der Maßgabe, daß der Anteil der Bestandteile B4) 0 to 3% by weight of sodium salt of at least one phosphonic acid, with the proviso that the proportion of the constituents
(B3 + B4) 3 bis 12 Gew.-% beträgt. (B3 + B4) is 3 to 12% by weight.
2. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an den Einzelkomponenten: 2. Composition according to claim 1, characterized by a content of the individual components:
A1) 5 bis 12 Gew.-%  A1) 5 to 12% by weight
A2) 0,5 bis 1,5 Gew.-%  A2) 0.5 to 1.5% by weight
B1) 6 bis 15 Gew.-%  B1) 6 to 15% by weight
B2) 0,5 bis 3 Gew.-%  B2) 0.5 to 3% by weight
B3) 3 bis 10 Gew.-%  B3) 3 to 10% by weight
B4) 0,2 bis 2 Gew.-%  B4) 0.2 to 2% by weight
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß in der Formel (I) R = C8-12-Alkylreste und x Zahlen von 1,3 bis3. Composition according to claim 1 or 2, characterized in that in the formula (I) R = C 8-12 alkyl radicals and x numbers from 1.3 to
3 bedeuten. 3 mean.
4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch oekennzeichnet, daß das nichtionische Tensid gemäß Komponente (A2) einen HLB-Wert von 12 bis 18 aufweist. 4. Composition according to one or more of claims 1 to 3, characterized in that the nonionic surfactant according to component (A2) has an HLB value of 12 to 18.
5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Komponente (B4) aus dem Natriumsalz der 1-Hydroxyethan-1,1-diphosphonsäure besteht. 5. Composition according to 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. Mittel nach Anspruch 5, dadurch gekennzeichnet, daß die Komponente (B4) zusätzlich das Natriumsalz der Diethylentriaminpentamethylenphosphonsäure enthält. 6. Composition according to claim 5, characterized in that component (B4) additionally contains the sodium salt of diethylenetriaminepentamethylenephosphonic acid.
7. Mittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Anteil der Komponente (B3) 5 bis 10 Gew.-% beträgt. 7. Composition according to one or more of claims 1 to 6, characterized in that the proportion of component (B3) is 5 to 10 wt .-%.
8. Mittel nach Anspruch 5 bis 7, daß die Summe der Komponenten (B3 + B4) 6 bis 11 Gew.-% beträgt. 8. Composition according to claim 5 to 7, that the sum of the components (B3 + B4) is 6 to 11 wt .-%.
PCT/EP1989/001370 1988-12-07 1989-11-15 Phosphate-free liquid washing agent with high alkalinity WO1990006353A1 (en)

Priority Applications (2)

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FI912463A FI912463A0 (en) 1988-12-07 1991-05-21 SYNNERLIGEN BASISKT, FOSFATLOEST, FLYTANDE TVAETTMEDEL.
DK101291A DK101291A (en) 1988-12-07 1991-05-28 PHOSPHATE-FREE, HIGH-ALKALINITY LIQUID DETERGENT

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DE3841129A DE3841129A1 (en) 1988-12-07 1988-12-07 Phosphate-free, liquid detergent with high alkalinity
DEP3841129.6 1988-12-07
DE19893906766 DE3906766A1 (en) 1989-03-03 1989-03-03 Phosphate-free liquid detergent of high alkalinity
DEP3906766.1 1989-03-03

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WO1991014760A1 (en) * 1990-03-24 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Weakly foaming, nonionic tenside mixture
US6291420B1 (en) 1996-01-31 2001-09-18 Rhodia Chimie System containing a non-ionic surfactant and an alkali metal silicate

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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
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

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US3547828A (en) 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
US3839318A (en) 1970-09-27 1974-10-01 Rohm & Haas Process for preparation of alkyl glucosides and alkyl oligosaccharides

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Publication number Priority date Publication date Assignee Title
WO1991014760A1 (en) * 1990-03-24 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Weakly foaming, nonionic tenside mixture
US6291420B1 (en) 1996-01-31 2001-09-18 Rhodia Chimie System containing a non-ionic surfactant and an alkali metal silicate

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