EP0541523B1 - Paste-like, phosphate-free detergent with reduced frothing tendency - Google Patents
Paste-like, phosphate-free detergent with reduced frothing tendency Download PDFInfo
- Publication number
- EP0541523B1 EP0541523B1 EP89912963A EP89912963A EP0541523B1 EP 0541523 B1 EP0541523 B1 EP 0541523B1 EP 89912963 A EP89912963 A EP 89912963A EP 89912963 A EP89912963 A EP 89912963A EP 0541523 B1 EP0541523 B1 EP 0541523B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- detergent
- constituent
- linear
- paste
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
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 work under particularly critical conditions, i.e. 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.
Aus der europäischen Patentanmeldung EP-A-0 273 377 sind pulverförmige Waschmittel bekannt, welche geringe Mengen an Alkylbenzolsulfonat, mindestens 2 verschiedene ethoxylierte Alkohole, Zeolith, wasserfreie Soda in Mengen von 40 bis 60 Gew.-%, Natriumsilikat in Mengen von 2 bis 7 Gew.-% und wasserlösliche Polymere mit vergrauungsinhibierender Wirkung enthalten. Diese Mittel eignen sich zum Waschen stark verschmutzter Arbeitskleidung.Powdered detergents are known from European patent application EP-A-0 273 377, which contain small amounts of alkylbenzenesulfonate, at least 2 different ethoxylated alcohols, zeolite, anhydrous soda in amounts of 40 to 60% by weight, sodium silicate in amounts of 2 to 7 % By weight and water-soluble polymers with graying-inhibiting action. These agents are suitable for washing heavily soiled work clothing.
Pastöse Waschmittel, insbesondere solche mit hohem Gehalt an stark alkalischen Bestandteilen, wie Natriummetasilikat bzw. Soda, 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 Suspensionsstabilisatoren 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 soda, have the advantage over powdery detergents that they can be handled and dosed without dust. They are particularly suitable for automatic dosing devices. Their problem is that they must be sufficiently flowable over a wide temperature range, which considerably limits the freedom from recipes, especially when 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 stabilizers to use 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:
- A) 1 bis 3 Gew.-% Natriumalkylbenzolsulfonat mit linearen, 9 bis 13 C-Atome aufweisenden Alkylketten,
- 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,
- 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,
- D) 50 bis 65 Gew.-% Natriumsilikat der Zusammensetzung Na₂O : SiO₂ = 1 : 0,8 bis 1 : 1,5
- E) 2 bis 8 Gew.-%, bezogen auf Natriumsalz, mindestens eines Komplexierungsmittels aus der Klasse der Nitrilotriessigsäure und der Polyphosphonsäuren,
- F) 0,5 bis 2,5 Gew.-% wasserlösliche Polymere mit vergrauungsinhibierender Wirkung,
- G) 0 bis 5 Gew.-% an sonstigen nichttensidischen bzw. nicht gerüststoffartige Waschmittelbestandteilen,
- H) weniger als 4 Gew.-% Wasser
1,5 bis 2,5 % Bestandteil A
15,0 bis 17,0 % Bestandteil B
13,0 bis 15,0 % Bestandteil C
55,0 bis 63,0 % Bestandteil D
3,0 bis 6,0 % Bestandteil E
0,7 bis 2,0 % Bestandteil F
0,1 bis 2,5 % Bestandteil G
weniger als 3 % Bestandteil H
Bestandteil (A) besteht aus einem Alkylbenzolsulfonat, das 10 bis 13 C-Atome in der linearen Alkylkette aufweist und üblicherweise als Dodecylbenzolsulfonat bezeichnet wird.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 to 3% by weight of sodium alkylbenzenesulfonate with linear alkyl chains having 9 to 13 carbon atoms,
- 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 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 to 65 wt .-% sodium silicate of 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 class of nitrilotriacetic acid and polyphosphonic acids,
- F) 0.5 to 2.5% by weight of water-soluble polymers with graying-inhibiting action,
- G) 0 to 5% by weight of other non-surfactant or non-structural detergent components,
- H) less than 4 wt% water
1.5 to 2.5% of component A.
15.0 to 17.0% component B
13.0 to 15.0% of component C.
55.0 to 63.0% component D.
3.0 to 6.0% component E
0.7 to 2.0% component F
0.1 to 2.5% component G
less than 3% ingredient H
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 überwiegen 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 linear alcohols being said 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-Alkoholen 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 C₁₂ alcohol in the alcohol residues of components (B) and (C) is preferably not more than 50% by weight and the total content of the agents in ethoxylated C₁₆-C₁₈ alcohols is 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 a Na₂O: SiO₂ 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, Ethylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose oder Mischether, wie Methyl-hydroxyethylcellulose, Methyl-carboxymethylcellulose oder Ethyl-hydroxyethylcellulose. Weitere geeignete Polymere sind Polyacrylsäure, Copolymere aus Acrylsäure und Vinylethern, 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-tetramethylenphosphonsäure (EDTMP), Diethylentriamin-pentamethylenphosphonsäure (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 the form of the sodium salt, such as ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP), aminotrimethylenephosphonic acid (ADTMPy) and in particular 1 -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 Substantivität 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.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.
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 vermahlen, beispielsweise in einer Kolloidmühle bzw. auf einem Walzenstuhl, so daß die Korngröße der suspendierten Feststoffe zwischen 5 und 80 »m, vorzugsweise 10 bis 50 »m liegt. Der Anteil grober Teilchen (über 80 »m) soll bevorzugt unter 10 Gew.-% liegen.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 »m, preferably 10 to 50» m. The proportion of coarse particles (over 80 »m) 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. Beispiele The agents are generally used in a concentration of 5 to 12 g / l, preferably 8 to 10 g / l, with softened water, ie softened to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH, for Preparation of the wash liquor is used. Examples
Es wurde ein Waschmittel der nachstehenden Zusammensetzung geprüft. Die nichtionischen Tenside B und C leiteten sich von Oxoalkoholen 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-anilino-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 of chain length C₁₂-C₁₅. 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-anilino-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 Gek. -% an wasserfreier Substanz.
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 »m 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 »m on. The viscosity (according to Brookfield) was 15 Pa · s at 20 ° C.
Zum Vergleich wurde ein pulverförmiges Waschmittel gemäß DE 36 44 808 A1 (Beispiel 1) herangezogen.A powder detergent according to DE 36 44 808 A1 (Example 1) was used for comparison.
Waschautomat mit Frontbeladung (Modell FRISTA(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 ( FRISTA (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 Flüssigkeitsniveau 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.
Claims (7)
- A paste-form, non-phosphate detergent, characterized in that it contains the following constituents: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 of other non-surfactant and non-builder detergent constituents,H) less than 4% by weight water.
- A detergent as claimed in claim 1, characterized by a content of
1.5 to 2.5 % constituent A
15.0 to 17.0 % constituent B
13.0 to 15.0 % constituent C
55.0 to 63.0 % constituent D
3.0 to 6.0 % constituent E
0.7 to 2.0 % constituent F
0.1 to 2.5 % constituent G
less than 3 % constituent H. - A detergent, characterized in that it contains 3 to 6% by weight nitrilotriacetic acid, expressed as sodium salt.
- A detergent, characterized in that it contains 0.5 to 2% by weight 1-hydroxyethane-1,1-diphosphonic acid, expressed as sodium salt.
- A detergent as claimed in claims 1 to 4, characterized in that it contains 0.05 to 0.5% optical brighteners.
- A detergent as claimed in claims 1 to 6, characterized in that it is free from organic solvents and dispersion stabilizers.
- A process for the production of the detergent claimed in one or more of claims 1 to 6, characterized in that a mixture of the constituents is size-reduced to a particle size of the solids of 5 to 50 »m, the percentage of particles larger than 80 »m in size being less than 10% by weight.
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 EP0541523A1 (en) | 1993-05-19 |
EP0541523B1 true 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)
Country | Link |
---|---|
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) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3812041A (en) * | 1972-06-23 | 1974-05-21 | Colgate Palmolive Co | Non-gelling heavy duty liquid laundry detergent |
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 |
-
1988
- 1988-11-24 DE DE3839602A patent/DE3839602A1/en not_active Withdrawn
-
1989
- 1989-11-13 TR TR89/0960A patent/TR24150A/en unknown
- 1989-11-15 BR BR898907784A patent/BR8907784A/en not_active IP Right Cessation
- 1989-11-15 DE DE58908953T patent/DE58908953D1/en not_active Expired - Fee Related
- 1989-11-15 EP EP89912963A patent/EP0541523B1/en not_active Expired - Lifetime
- 1989-11-15 EP EP89121136A patent/EP0374472A1/en active Pending
- 1989-11-15 AT AT89912963T patent/ATE117719T1/en not_active IP Right Cessation
- 1989-11-15 US US07/688,508 patent/US5234628A/en not_active Expired - Fee Related
- 1989-11-15 ES ES89912963T patent/ES2066883T3/en not_active Expired - Lifetime
- 1989-11-15 KR KR1019900701605A patent/KR900701990A/en not_active Application Discontinuation
- 1989-11-15 AU AU46261/89A patent/AU626955B2/en not_active Ceased
- 1989-11-15 WO PCT/EP1989/001371 patent/WO1990005773A1/en active IP Right Grant
- 1989-11-15 JP JP2500170A patent/JP2682534B2/en not_active Expired - Lifetime
- 1989-11-21 CA CA002003519A patent/CA2003519C/en not_active Expired - Fee Related
- 1989-11-22 NZ NZ231480A patent/NZ231480A/en unknown
- 1989-11-23 PT PT92395A patent/PT92395A/en not_active Application Discontinuation
- 1989-11-23 ZA ZA898950A patent/ZA898950B/en unknown
-
1991
- 1991-05-22 DK DK91965A patent/DK96591D0/en not_active Application Discontinuation
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 |
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 |
EP0541523A1 (en) | 1993-05-19 |
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 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0541523B1 (en) | Paste-like, phosphate-free detergent with reduced frothing tendency | |
DE2215371C2 (en) | laundry detergent | |
EP0448581B1 (en) | Washing agent containing bleach, in liquid to paste form | |
EP0549632B1 (en) | Non-ionic liquid surfactant combination with improved cold stability | |
EP0120421B1 (en) | Use of a pasty cleaning agent in dishwashers | |
EP0200953A2 (en) | Granular detergent | |
EP0344629A1 (en) | Granular adsorption material with improved flushing property | |
DE4009533A1 (en) | LOW-EFFICIENT NON-ionic surfactant mix | |
EP0900266B1 (en) | Method of producing compact cleaning agents for industrial dish washing machines | |
EP0054894B1 (en) | Surfactant-containing mixture for cleaning hard surfaces | |
DE2507926B2 (en) | ||
DE19507532C2 (en) | Pasty detergent | |
EP0425804B1 (en) | Granular additive containing nonionic surfactents for detergent and cleaning agents with improved rinsing properties | |
EP0377807B1 (en) | Highly alkaline phosphate-free liquid detergent | |
DE2544019C3 (en) | ||
EP0758678A2 (en) | Cleaning agent for protective working garment | |
DE2015435A1 (en) | Detergents and cleaning agents | |
DE3644808A1 (en) | PHOSPHATE-FREE DETERGENT WITH REDUCED FOAM PRIORITY | |
EP0079105B1 (en) | Foam-controlled washing agents | |
EP0407626A1 (en) | Phosphate-free liquid washing and cleaning composition | |
DE3905671C2 (en) | Detergent granules suitable for the production of aqueous concentrates | |
EP0460035B1 (en) | Water-softening agent in granular to powder form | |
EP0157320B1 (en) | Manual and mechanical applicable cold washing agent | |
EP0118658A1 (en) | Process for the production of a pasty detergent | |
EP0395976A1 (en) | Pasty, phosphate-free, effectively water-free detergent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19910516 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE |
|
XX | Miscellaneous (additional remarks) |
Free format text: VERBUNDEN MIT 89121136.9/0374472 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 19.08.93. |
|
17Q | First examination report despatched |
Effective date: 19930827 |
|
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 GR IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19950125 |
|
REF | Corresponds to: |
Ref document number: 117719 Country of ref document: AT Date of ref document: 19950215 Kind code of ref document: T |
|
XX | Miscellaneous (additional remarks) |
Free format text: VERBUNDEN MIT 89121136.9/0374472 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) DURCH ENTSCHEIDUNG VOM 19.08.93. |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 58908953 Country of ref document: DE Date of ref document: 19950309 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2066883 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950427 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20011203 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030603 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20031002 Year of fee payment: 15 Ref country code: GB Payment date: 20031002 Year of fee payment: 15 Ref country code: AT Payment date: 20031002 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20031105 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20031106 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20031119 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20031216 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20031219 Year of fee payment: 15 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041115 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041115 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041116 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041116 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041130 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041130 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041130 |
|
BERE | Be: lapsed |
Owner name: *HENKEL K.G.A.A. Effective date: 20041130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050601 |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20041115 |
|
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: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050729 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20050601 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
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 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20041116 |
|
BERE | Be: lapsed |
Owner name: *HENKEL K.G.A.A. Effective date: 20041130 |