EP0541523A1 - Paste-like, phosphate-free detergent with reduced frothing tendency. - Google Patents

Paste-like, phosphate-free detergent with reduced frothing tendency.

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Publication number
EP0541523A1
EP0541523A1 EP89912963A EP89912963A EP0541523A1 EP 0541523 A1 EP0541523 A1 EP 0541523A1 EP 89912963 A EP89912963 A EP 89912963A EP 89912963 A EP89912963 A EP 89912963A EP 0541523 A1 EP0541523 A1 EP 0541523A1
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Prior art keywords
weight
component
linear
content
pct
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Granted
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EP89912963A
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German (de)
French (fr)
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EP0541523B1 (en
Inventor
Uwe Trabitzsch
Guenther Amberg
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains

Abstract

PCT No. PCT/EP89/01371 Sec. 371 Date May 24, 1991 Sec. 102(e) Date May 24, 1991 PCT Filed Nov. 15, 1989 PCT Pub. No. WO90/05773 PCT Pub. Date May 31, 1990.A paste-form, non-phosphate detergent which is particularly suitable for the washing of heavily soiled working apparel and which generates no troublesome foam essentially contains (A) 1 to 3% by weight sodium alkyl benzene sulfonate having linear C9-13 alkyl chains, (B) 14 to 18% by weight of a linear or 2-methyl-branched, saturated, primary C12-15 alcohol containing 2 to 4 ethylene glycol ether groups, (C) 12 to 16% by weight of a linear or 2-methyl-branched, saturated, primary C12-15 alcohol containing 6 to 8 ethylene glycol ether groups, (D) 50 to 65% by weight sodium silicate having the composition Na2O:SiO2=1:0.8 to 1:1.5, (E) 2 to 8% by weight, based on sodium salt, of at least one complexing agent from the group consisting of nitrilotriacetic acid and polyphosphonic acids, (F) 0.5 to 2.5% by weight water-soluble polymers having a redeposition-inhibiting effect, (G) 0 to 5% by weight other nonsurfactant and non-builder detergent constituents and (H) less than 4% by weight water. The paste can be introduced into washing machines by automatic dispensing systems.

Description

"Pastöses, phosphatfreies Waschmittel mit verringerter  "Pasty, phosphate-free detergent with reduced
Schaumneiounc"  Schaumneiounc "
Die vorliegende Erfindung betrifft ein pastöses, phosphatfreies Waschmittel, das sich insbesondere zum Waschen stark verunreinigter, beispielsweise mit Mineralöl verschmutzter Arbeitskleidung eignet und bei seiner Anwendung in Waschautomaten keine störenden Schaummengen entwickelt. Dabei soll das Mittel auch unter besonders kritischen Bedingungen, d. h. auch bei Verwendung von enthärtetem Wasser, wie es in gewerblichen Wäschereien üblicherweise benutzt wird, sowohl im Hauptwaschgang als auch in der Nachspülphase nur unwesentlich schäumen, so daß es in den automatischen Waschanlagen nicht zu Betriebsstörungen kommt. The present invention relates to a pasty, phosphate-free detergent, which is particularly suitable for washing heavily soiled work clothes, for example contaminated with mineral oil, and does not develop any disruptive amounts of foam when used in automatic washing machines. The agent should also under particularly critical conditions, i. H. Even when using softened water, as is usually used in commercial laundries, foam only insignificantly both in the main wash cycle and in the post-rinse phase, so that there are no malfunctions in the automatic washing systems.
Pastöse Waschmittel, insbesondere solche mit hohem Gehalt an stark alkalischen Bestandteilen, wie Natriummεtasilikat bzw. Sods, besitzen gegenüber pulverförmigen Mitteln den Vorteil, daß sie staubfrei gehandhabt und dosiert werden können. Sie eignen sich besonders für automatische Dosiervorrichtungen. Ihre Problematik besteht darin, daß sie in einem größeren Temperaturbereich hinreichend fließfähig sein müssen, was die Rezepturfreiheit erheblich einengt, insbesondere wenn hohe Anteile an festen Wirkstoffen in die Paste eingearbeitet werden sollen. Weiterhin wird verlangt, daß sich die Mittel während der Lagerung nicht entmischen. Weiterhin wird angestrebt, keine Lösungsmittel und Suspensionsstabi lisatoren zu verwenden, da sie bei der Anwendung nichts zur Waschleistung beitragen. Pasty detergents, in particular those with a high content of strongly alkaline constituents, such as sodium metasilicate or sodas, have the advantage over powdered agents that they can be handled and metered without dust. They are particularly suitable for automatic dosing devices. Their problem is that they have to be sufficiently flowable over a wide temperature range, which considerably limits the freedom from recipes, especially if high proportions of solid active ingredients are to be incorporated into the paste. It is also required that the agents do not separate during storage. Furthermore, the aim is to avoid solvents and suspension stabilization lisators because they do not contribute to the washing performance when used.
Gegenstand der Erfindung, mit der diese Aufgabe gelöst wird, ist ein pastöses, phosphatfreies Waschmittel, gekennzeichnet durch einen Gehalt an folgenden Bestandteilen: The object of the invention with which this object is achieved is a pasty, phosphate-free detergent, characterized by a content of the following components:
A) 1 bis 3 Gew.-% Natriumalkylbenzolsulfonat mit linearen, 9 bis 13 C-Atome aufweisenden Alkylketten,  A) 1 to 3% by weight of sodium alkylbenzenesulfonate with linear alkyl chains having 9 to 13 carbon atoms,
B) 14 bis 18 Gew.-% eines linearen oder in 2-Stellung methylverzweigten gesättigten, primären Alkohols mit 12 bis 15 C-Atomen, enthaltend 2 bis 4 Ethylenglykolethergruppen,  B) 14 to 18% by weight of a linear or in the 2-position methyl branched saturated primary alcohol having 12 to 15 carbon atoms, containing 2 to 4 ethylene glycol ether groups,
C) 12 bis 16 Gew.-% eines linearen oder in 2-Stellung methylverzweigten, gesättigten, primären Alkohols mit 12 bis 15 C-Atomen, enthaltend 6 bis 8 Ethylenglykolethergruppen,  C) 12 to 16% by weight of a linear or, in the 2-position methyl branched, saturated, primary alcohol with 12 to 15 C atoms, containing 6 to 8 ethylene glycol ether groups,
D) 50 bis 65 Gew.-% Natriumsilikat der Zusammensetzung Na2O : SiO2 = 1 : 0,8 bis 1 : 1,5 D) 50 to 65% by weight sodium silicate of the composition Na 2 O: SiO 2 = 1: 0.8 to 1: 1.5
E) 2 bis 8 Gew.-%, bezogen auf Natriumsalz, mindestens eines Kom- plexierungsmittels aus der Klasse der Nitrilotriessigsäure und der Polyphosphonsäuren,  E) 2 to 8% by weight, based on sodium salt, of at least one complexing agent from the class of nitrilotriacetic acid and polyphosphonic acids,
F) 0,5 bis 2,5 Gew.-% wasserlösliche Polymere mit vergrauungsinhibierender Wirkung,  F) 0.5 to 2.5% by weight of water-soluble polymers with graying-inhibiting action,
G) 0 bis 5 Gew.-% an sonstigen nichttensidischen bzw. nicht gerüststoffartige Waschmittelbestandteilen,  G) 0 to 5% by weight of other non-surfactant or non-structural detergent components,
H) weniger als 4 Gew.-% Wasser  H) less than 4 wt% water
Vorzugsweise weist das Mittel die folgende Zusammensetzung auf: The composition preferably has the following composition:
1,5 bis 2,5% Bestandteil A 1.5 to 2.5% of component A.
15,0 bis 17,0 % Bestandteil B  15.0 to 17.0% component B
13,0 bis 15,0% Bestandteil C  13.0 to 15.0% of component C.
55,0 bis 63,0% Bestandteil D 3,0 bis 6,0 % Bestandteil E 55.0 to 63.0% component D. 3.0 to 6.0% component E
0,7 bis 2,0 % Bestandteil F  0.7 to 2.0% component F
0,1 bis 2,5 % Bestandteil G  0.1 to 2.5% component G
weniger als 3 % Bestandteil H  less than 3% ingredient H
Bestandteil (A) besteht aus einem Alkylbenzolsulfonat, das 10 bis 13 C-Atome in der linearen Alkylkette aufweist und üblicherweise als Dodecylbenzolsulfonat bezeichnet wird. Component (A) consists of an alkylbenzenesulfonate which has 10 to 13 carbon atoms in the linear alkyl chain and is usually referred to as dodecylbenzenesulfonate.
Bestandteil (B) weist 12 bis 15 C-Atome im Alkoholrest auf und kann sich von nativen oder synthetischen Alkoholen (Oxoalkoholen) ableiten. Letztere bestehen üblicherweise aus einem Gemisch aus linearen und in 2-Stellung methylverzweigten Alkoholen, wobei der Anteil der linearen uberwiegen soll. Component (B) has 12 to 15 carbon atoms in the alcohol residue and can be derived from native or synthetic alcohols (oxo alcohols). The latter usually consist of a mixture of linear and methyl-branched alcohols in the 2-position, the proportion of the linear being intended to predominate.
Bestandteil (C) leitet sich von den gleichen Alkoholen bzw. Alkoholgemischen wie Bestandteil (B) ab. Im Interesse einer geringen Schaumbildung beträgt vorzugsweise der Anteil an C12-Alkohol in den Alkoholresten der Komponenten (B) und (C) nicht mehr als 50 Gew.-% und der Gehalt der Mittel an ethoxylierten C16-C18-Alko- holen insgesamt nicht mehr als 2 Gew.-%, insbesondere weniger als 1 Gew.-%. Component (C) is derived from the same alcohols or alcohol mixtures as component (B). In the interest of low foaming, the proportion of C 12 alcohol in the alcohol residues of components (B) and (C) is preferably not more than 50% by weight and the content of the agents in ethoxylated C 16 -C 18 alcohols in total not more than 2% by weight, in particular less than 1% by weight.
Die Komponente (D) besteht aus Natriumsilikat, das ein Na2O : SiO2-Verhältnis von 1 : 0,8 bis 1 : 1,5, vorzugsweise 1 : 0,9 bis 1 : 1,1 aufweist. Das Natriumsilikat kommt als wasserfreies Salz zum Einsatz. Component (D) consists of sodium silicate, which has an Na 2 O: SiO 2 ratio of 1: 0.8 to 1: 1.5, preferably 1: 0.9 to 1: 1.1. The sodium silicate is used as an anhydrous salt.
Als Bestandteil (F) dienen bekannte nichtionische oder anionische Polymere mit vergrauungsinhibierender Wirkung. Besonders geeignet sind Celluloseether, wie Na-Carboxymethylcellulose und deren Gemische mit anderen Celluloseethern, wie Methylcellulose, Ethyl- cellulose, Hydroxyethylcellulose, Hydroxypropylcellulose oder Mischether, wie Methyl-hydroxyethylcellulose, Methyl-carboxyme- thylcellulose oder Ethyl-hydroxyethylcellulose. Weitere geeignete Polymere sind Polyacrylsäure, Copolymere aus Acrylsäure und Vi- nylethern, Copolymere aus Acrylsäure und Vinylethern, Copolymere aus Acrylsäure und Maleinsäure (Sokalan(R)) in Form der Natriumsalze sowie andere bekannte Copolymere der Acrylsäure mit copolymerisierbaren olefinischen Verbindungen. Celluloseether und synthetische Polymere können auch gemeinsam verwendet werden. Als besonders brauchbar haben sich Gemische der Carboxymethylcellulose mit Methylcellulose oder Methyl-hydroxyethylcellulose erwiesen. Known nonionic or anionic polymers with a graying-inhibiting effect serve as constituent (F). Cellulose ethers such as Na-carboxymethyl cellulose and their are particularly suitable Mixtures with other cellulose ethers, such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or mixed ethers, such as methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or ethyl hydroxyethyl cellulose. Other suitable polymers are polyacrylic acid, copolymers of acrylic acid and vinyl ethers, copolymers of acrylic acid and vinyl ethers, copolymers of acrylic acid and maleic acid (Sokalan (R) ) in the form of the sodium salts and other known copolymers of acrylic acid with copolymerizable olefinic compounds. Cellulose ethers and synthetic polymers can also be used together. Mixtures of carboxymethyl cellulose with methyl cellulose or methyl hydroxyethyl cellulose have proven to be particularly useful.
Komponente (E) besteht aus mindestens einem Komplexierungsmittel aus der Klasse der Nitrilotriessigsäure (NTA) und der Polyphosphonsäuren in Fomr der Natriumsalz, wie Ethylendiamin-tetra- methylenphosphonsäure (EDTMP), Diethylentriamin-pentamethylen- phosphonsäure (DTPMP), Aminotrimethylenphosphonsäure (ADTMP) und insbesondere der 1-Hydroxyethan-1,1-diphosphonsäure (HEDP). Vorzugsweise enthält das Mittel 3 bis 6 NTA (Na-Salz) und 0,5 bis 2 Gew.-% HEDP (Na-Salz). Component (E) consists of at least one complexing agent from the class of nitrilotriacetic acid (NTA) and the polyphosphonic acids in form of the sodium salt, such as ethylenediamine-tetra-methylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylene-phosphonic acid (DTPMP), aminotrimethylenephosphonic acid (ADTMP) and in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP). The agent preferably contains 3 to 6 NTA (Na salt) and 0.5 to 2% by weight of HEDP (Na salt).
Als weitere nichttensidische bzw. nicht als Gerüststoff wirkende Bestandteile (G) kommen Enzyme, Duftstoffe und übliche optische Aufheller in Frage, insbesondere optische Aufheller mit Substan- tivität für Cellulosefasern (Baumwolle) in Anteilen von 0,05 bis 0,5 Gew.-%. Enzymes, fragrances and customary optical brighteners are possible as further non-surfactant components (G) which do not act as builders, in particular optical brighteners with substantivity for cellulose fibers (cotton) in proportions of 0.05 to 0.5% by weight. .
Der Wassergehalt der Mittel soll möglichst gering sein, da freies Wasser die Viskosität der Mittel erhöht und somit die Verarbeitung und die Dosierung der Mittel erschwert. Wassergehalte von 2 Gew.-% oder weniger sind daher besonders bevorzugt. Die Herstellung der Mittel erfolgt durch Mischen und Homogenisieren der festen, feinteiligen Bestandteile mit den flüssigen nichtionischen Tensiden (Komponenten B und C). Überraschenderweise wurde festgestellt, daß auch die festen Alkylbenzolsulfonate etwa zur Hälfte ihres Anteils sich wie flüssige Bestandteile verhalten und somit das Einarbeiten hoher Feststoffanteile begünstigen. Zweckmäßigerweise wird das Gemisch anschließend vermählen, beispielsweise in einer Kolloidmühle bzw. auf einem Walzenstuhl, so daß die Korngröße der suspendierten Feststoffe zwischen 5 und 80 μm, vorzugsweise 10 bis 50 μm liegt. Der Anteil grober Teilchen (über 80 μm) soll bevorzugt unter 10 Gew.-% liegen. The water content of the agents should be as low as possible, since free water increases the viscosity of the agents and thus complicates the processing and metering of the agents. Water contents of 2% by weight or less are therefore particularly preferred. The agents are produced by mixing and homogenizing the solid, finely divided constituents with the liquid nonionic surfactants (components B and C). Surprisingly, it was found that about half of the solid alkylbenzenesulfonates behave like liquid constituents and thus favor the incorporation of high solids contents. The mixture is then expediently ground, for example in a colloid mill or on a roller mill, so that the grain size of the suspended solids is between 5 and 80 μm, preferably 10 to 50 μm. The proportion of coarse particles (over 80 μm) should preferably be below 10% by weight.
Die Mittel werden im allgemeinen in einer Konzentration von 5 bis 12 g/l, vorzugsweise 8 bis 10 g/l eingesetzt, wobei zweckmäßigerweise enthärtetes, d. h. auf einen Härtegrad von weniger als 2 °dH, insbesondere weniger als 1 °dH enthärtetes Wasser, zum Ansetzen der Waschlauge verwendet wird. The agents are generally used in a concentration of 5 to 12 g / l, preferably 8 to 10 g / l, with suitably softened water, ie water softened to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH Preparation of the wash liquor is used.
B e i s p i e l e B e i s p i e l e
Es wurde ein Waschmittel der nachstehenden Zusammensetzung geprüft. Die nichtionischen Tenside B und C leiteten sich von Oxo- alkoholen der Kettenlänge C12-C15 ab. EO bedeutet angelagertes Ethylenoxid. Die Komponente (F) bestand aus einem 2 : 1-Gemisch aus Na-Carboxymethylcellulose und Methylhydroxyethylcellulose (Hydroxyethyl-Gehalt 0,8 Gew.-%). Als optische Aufheller kam das Na-Salz der 4,4'-Bis-(2-aniIino-4-morpholino-1,3,5-triazin-6- yl-amino)-stilben-2,2'-disulfonsäure zum Einsatz. Das Wasser entstammt dem Feuchtigkeitsgehalt der verwendeten Rohstoffe. A detergent of the following composition was tested. The nonionic surfactants B and C were derived from oxo alcohols with a chain length of C 12 -C 15 . EO means attached ethylene oxide. Component (F) consisted of a 2: 1 mixture of sodium carboxymethyl cellulose and methyl hydroxyethyl cellulose (hydroxyethyl content 0.8% by weight). The Na salt of 4,4'-bis (2-aniino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid was used as the optical brightener . The water comes from the moisture content of the raw materials used.
Die angegebenen Prozentzahlen beziehen sich auf Gew.-% an wasserfreier Substanz. The percentages given relate to% by weight of anhydrous substance.
Bestandteil Gew.-%Component weight%
A Na-DodecyIbenzo1suIfonat 2,3 A Na-DodecyIbenzo1sulfonate 2.3
B C12-C15-Alkohol + 3 E0 16,0 B C 12- C 15 alcohol + 3 E0 16.0
C C12-C15-Alkohol + 7 E0 14,0 CC 12 -C 15 alcohol + 7 E0 14.0
D Na2O : SiO2 = 1 : 1 59,2 D Na 2 O: SiO 2 = 1: 1 59.2
E1 NTA (Trinatriumsalz) 4,4 E 1 NTA (trisodium salt) 4.4
E1 HEDP (Tetranatriumsalz) 1,2  E1 HEDP (tetrasodium salt) 1.2
F Celluloseether 1,0  F cellulose ether 1.0
G opt. Aufheller 0,1  G opt. Brightener 0.1
H Wasser 1,8  H water 1.8
Das Gemisch in einer Mahlvorrichtung (Kolloidmühle) während 30 Minuten gemahlen. Das Mahlprodukt wies anschließend eine Temperatur von ca. 45 ° und eine mittlere Korngröße der Feststoffe von 30 μm auf. Die Viskosität (nach Brookfield) betrug 15 Pa · s bei 20 °C. The mixture was ground in a grinder (colloid mill) for 30 minutes. The ground product then had a temperature of approximately 45 ° and an average grain size of the solids of 30 μm. The viscosity (according to Brookfield) was 15 Pa · s at 20 ° C.
Zum Vergleich wurde ein pulverförmiges Waschmittel gemäß DE 3644808 A1 (Beispiel 1) herangezogen. A powder detergent according to DE 3644808 A1 (Example 1) was used for comparison.
Waschbedingungen Washing conditions
Waschautomat mit Frontbeladung (Modell FRISTÄ(R)); Waschmittelkonzentration 10 g/l; Beladungsverhältnis 1 : 14,5; Verhältnis von kg Textilgut zu Liter Waschlauge 1 : 5; Wasserhärte 1 °dH; Vorwäsche 20 Minuten bei 70 °C; Klarwäsche 10 Minuten bei 50 bis 60 °C; 3maliges Nachspülen; 2 mal mit enthärtetem Wasser, abschließend mit Leitungswasser. Als Textilgewebe wurde veredelte Baumwolle (Bv) verwendet, die mit gebrauchtem Motorenöl (Mineralöl) angeschmutzt worden war. Front loading washing machine ( FRISTÄ (R) model ); Detergent concentration 10 g / l; Loading ratio 1: 14.5; Ratio of kg textile goods to liters of wash liquor 1: 5; Water hardness 1 ° dH; Prewash for 20 minutes at 70 ° C; Wash for 10 minutes at 50 to 60 ° C; 3 rinsing; 2 times with softened water, finally with tap water. Refined cotton (Bv), which had been soiled with used motor oil (mineral oil), was used as the textile fabric.
Die Ergebnisse der Waschversuche und Schaummessungen (Schaumhöhe in cm Schaumsäule über dem Flussigkeitsniveau während des 1. und 2. Waschganges sowie die im 3. Nachspülgang) sind Tabelle I zu entnehmen. Das Vergleichsprodukt zeigt zwar ein etwas günstigeres Schaumverhalten, wird jedoch hinsichtlich seiner Waschleistung von dem erfindungsgemäßen Mittel übertroffen. Grundsätzlich stört die geringe Schaumentwicklung auch bei dem erfindungsgemäßen Mittel nicht. Von Vorteil ist auch die automatische Dosierbarkeit aus einem Pasten-Vorratsbehälter. The results of the washing tests and foam measurements (foam height in cm of foam column above the liquid level during the 1st and 2nd wash cycle and those in the 3rd rinse cycle) can be found in Table I. The comparative product shows a somewhat more favorable foaming behavior, but its washing performance is exceeded by the agent according to the invention. Basically, the low foaming does not interfere with the agent according to the invention. Automatic metering from a paste storage container is also an advantage.

Claims

P a te n t a n s p r ü c h e P a te nt claims
1. Pastöses, phosphatfreies Waschmittel, gekennzeichnet durch einen Gehalt an folgenden Bestandteilen: 1. Pasty, phosphate-free detergent, characterized by a content of the following components:
A) 1 bis 3 Gew.-% Natriumalkylbenzolsulfonat mit linearen, 9 bis 13 C-Atome aufweisenden Alkylketten,  A) 1 to 3% by weight of sodium alkylbenzenesulfonate with linear alkyl chains having 9 to 13 carbon atoms,
B) 14 bis 18 Gew.-% eines linearen oder in 2-Stellung methylverzweigten gesättigten, primären Alkohols mit 12 bis 15 C-Atomen, enthaltend 2 bis 4 Ethylenglykolethergruppen, B) 14 to 18% by weight of a linear or in the 2-position methyl branched saturated primary alcohol having 12 to 15 carbon atoms, containing 2 to 4 ethylene glycol ether groups,
C) 12 bis 16 Gew.-% eines linearen oder in 2-Stellung methylverzweigten, gesättigten, primären Alkohols mit 12 bis 15 C-Atomen, enthaltend 5 bis 8 Ethylenglykolethergruppen,C) 12 to 16% by weight of a linear or, in the 2-position methyl branched, saturated, primary alcohol having 12 to 15 C atoms, containing 5 to 8 ethylene glycol ether groups,
D) 50 bis 65 Gew.-% Natriumsilikat der Zusammensetzung Na2O : D) 50 to 65% by weight sodium silicate of the composition Na 2 O:
SiO2 = 1 : 0,8 bis 1 : 1,5, SiO 2 = 1: 0.8 to 1: 1.5,
E) 2 bis 8 Gew.-%, bezogen auf Natriumsalz, mindestens eines Komplexierungsmittels aus der Klasse der Nitrilotriessig- säure und der Polyphosphonsäuren,  E) 2 to 8% by weight, based on sodium salt, of at least one complexing agent from the class of nitrilotriacetic acid and polyphosphonic acids,
F) 0,5 bis 2,5 Gew.-% wasserlösliche Polymere mit vergrauungsinhibierender Wirkung,  F) 0.5 to 2.5% by weight of water-soluble polymers with graying-inhibiting action,
G) 0 bis 5 Gew.-% an sonstigen nichttensidisehen bzw. nicht gerüststoffartigen Waschmittelbestandteilen,  G) 0 to 5% by weight of other non-surfactant or non-structural detergent components,
H) weniger als 4 Gew.-% Wasser.  H) less than 4 wt% water.
2. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an2. Composition according to claim 1, characterized by a content of
1,5 bis 2,5 % Bestandteil A 1.5 to 2.5% of component A.
15,0 bis 17,0 % Bestandteil B  15.0 to 17.0% component B
13,0 bis 15,0 % Bestandteil C  13.0 to 15.0% of component C.
55,0 bis 63,0 % Bestandteil D  55.0 to 63.0% component D.
3,0 bis 6,0 % Bestandteil E 0,7 bis 2,0 % Bestandteil F 3.0 to 6.0% component E 0.7 to 2.0% component F
0,1 bis 2,5 % Bestandteil G  0.1 to 2.5% component G
weniger als 3 % Bestandteil H.  less than 3% component H.
3. Mittel, gekennzeichnet durch einen Gehalt an 3 bis 6 Gew.-% an Nitrilotriessigsäure, gerechnet als Natriumsalz. 3. Agent, characterized by a content of 3 to 6 wt .-% of nitrilotriacetic acid, calculated as the sodium salt.
4. Mittel, gekennzeichnet durch einen Gehalt an 0,5 bis 2 Gew.-% an 1-Hydroxyethan-1,1-diphosphonsäure, gerechnet als Natriumsalz. 4. Agent, characterized by a content of 0.5 to 2 wt .-% of 1-hydroxyethane-1,1-diphosphonic acid, calculated as the sodium salt.
5. Mittel nach Anspruch 1 bis 4, gekennzeichnet durch einen Gehalt von 0,05 bis 0,5 % an optischen Aufhellern. 5. Composition according to claim 1 to 4, characterized by a content of 0.05 to 0.5% of optical brighteners.
6. Mittel nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß es frei von organischen Lösungsmitteln und Dispersionsstabilisatoren ist. 6. Composition according to claim 1 to 6, characterized in that it is free of organic solvents and dispersion stabilizers.
7. Verfahren zur Herstellung der Mittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man ein Gemisch der Bestandteile auf eine Korngröße der Feststoffe von 5 bis 50 μm zerkleinert, wobei der Anteil von Teilchen über 80 μm unter 10 Gew.-% liegt. 7. A process for the preparation of the agent according to one or more of claims 1 to 6, characterized in that a mixture of the components is comminuted to a particle size of the solids of 5 to 50 microns, the proportion of particles over 80 microns below 10 wt. -% lies.
EP89912963A 1988-11-24 1989-11-15 Paste-like, phosphate-free detergent with reduced frothing tendency Expired - Lifetime EP0541523B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3839602 1988-11-24
DE3839602A DE3839602A1 (en) 1988-11-24 1988-11-24 PASTOESES, PHOSPHATE-FREE DETERGENT WITH REDUCED FOAM PRIORITY
PCT/EP1989/001371 WO1990005773A1 (en) 1988-11-24 1989-11-15 Paste-like, phosphate-free detergent with reduced frothing tendency

Publications (2)

Publication Number Publication Date
EP0541523A1 true EP0541523A1 (en) 1993-05-19
EP0541523B1 EP0541523B1 (en) 1995-01-25

Family

ID=6367758

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89912963A Expired - Lifetime EP0541523B1 (en) 1988-11-24 1989-11-15 Paste-like, phosphate-free detergent with reduced frothing tendency
EP89121136A Pending EP0374472A1 (en) 1988-11-24 1989-11-15 Low-foaming pasty phosphate-free detergent

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89121136A Pending EP0374472A1 (en) 1988-11-24 1989-11-15 Low-foaming pasty phosphate-free detergent

Country Status (16)

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US (1) US5234628A (en)
EP (2) EP0541523B1 (en)
JP (1) JP2682534B2 (en)
KR (1) KR900701990A (en)
AT (1) ATE117719T1 (en)
AU (1) AU626955B2 (en)
BR (1) BR8907784A (en)
CA (1) CA2003519C (en)
DE (2) DE3839602A1 (en)
DK (1) DK96591D0 (en)
ES (1) ES2066883T3 (en)
NZ (1) NZ231480A (en)
PT (1) PT92395A (en)
TR (1) TR24150A (en)
WO (1) WO1990005773A1 (en)
ZA (1) ZA898950B (en)

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DE4332849A1 (en) * 1993-09-27 1995-03-30 Henkel Kgaa Pasty detergent
DK0663439T3 (en) * 1994-01-17 2000-09-18 Procter & Gamble Process for the preparation of detergent granules
JP2960310B2 (en) * 1994-09-09 1999-10-06 花王株式会社 Detergent composition
DE19636035A1 (en) * 1996-09-05 1998-03-12 Henkel Ecolab Gmbh & Co Ohg Paste-like detergent and cleaning agent
JP4407779B2 (en) 2000-03-27 2010-02-03 信越化学工業株式会社 Binder for hydraulic composition for extrusion molding, hydraulic composition and method for producing extruded product
US20050006245A1 (en) * 2003-07-08 2005-01-13 Applied Materials, Inc. Multiple-step electrodeposition process for direct copper plating on barrier metals
US20070125657A1 (en) * 2003-07-08 2007-06-07 Zhi-Wen Sun Method of direct plating of copper on a substrate structure
US20060283716A1 (en) * 2003-07-08 2006-12-21 Hooman Hafezi Method of direct plating of copper on a ruthenium alloy
US20050085031A1 (en) * 2003-10-15 2005-04-21 Applied Materials, Inc. Heterogeneous activation layers formed by ionic and electroless reactions used for IC interconnect capping layers
US7205233B2 (en) * 2003-11-07 2007-04-17 Applied Materials, Inc. Method for forming CoWRe alloys by electroless deposition
US20050161338A1 (en) * 2004-01-26 2005-07-28 Applied Materials, Inc. Electroless cobalt alloy deposition process
US20050170650A1 (en) * 2004-01-26 2005-08-04 Hongbin Fang Electroless palladium nitrate activation prior to cobalt-alloy deposition
US20060246217A1 (en) * 2005-03-18 2006-11-02 Weidman Timothy W Electroless deposition process on a silicide contact
US20060251801A1 (en) * 2005-03-18 2006-11-09 Weidman Timothy W In-situ silicidation metallization process
US7651934B2 (en) 2005-03-18 2010-01-26 Applied Materials, Inc. Process for electroless copper deposition
WO2007035880A2 (en) * 2005-09-21 2007-03-29 Applied Materials, Inc. Method and apparatus for forming device features in an integrated electroless deposition system

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GB1562801A (en) * 1976-01-02 1980-03-19 Procter & Gamble Liquid detergent composition
GB2188058B (en) * 1986-03-22 1990-06-13 Abster Company Limited The Liquid hand cleaner containing solid phase
DE3621536A1 (en) * 1986-06-27 1988-01-07 Henkel Kgaa LIQUID DETERGENT AND METHOD FOR THE PRODUCTION THEREOF
DE3643895A1 (en) * 1986-12-22 1988-06-30 Henkel Kgaa LIQUID NON-ionic surfactant blends
DE3644808A1 (en) * 1986-12-31 1988-07-14 Henkel Kgaa PHOSPHATE-FREE DETERGENT WITH REDUCED FOAM PRIORITY

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Also Published As

Publication number Publication date
NZ231480A (en) 1992-05-26
AU626955B2 (en) 1992-08-13
ATE117719T1 (en) 1995-02-15
JPH04502172A (en) 1992-04-16
DK96591A (en) 1991-05-22
US5234628A (en) 1993-08-10
CA2003519A1 (en) 1990-05-24
WO1990005773A1 (en) 1990-05-31
KR900701990A (en) 1990-12-05
EP0374472A1 (en) 1990-06-27
EP0541523B1 (en) 1995-01-25
ES2066883T3 (en) 1995-03-16
PT92395A (en) 1990-05-31
DK96591D0 (en) 1991-05-22
TR24150A (en) 1991-04-25
JP2682534B2 (en) 1997-11-26
DE3839602A1 (en) 1990-05-31
ZA898950B (en) 1990-07-25
DE58908953D1 (en) 1995-03-09
BR8907784A (en) 1991-08-27
CA2003519C (en) 2000-04-18
AU4626189A (en) 1990-06-12

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