EP0444415A1 - Detergent composition comprising partially dehydrated disilicate - Google Patents

Detergent composition comprising partially dehydrated disilicate Download PDF

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Publication number
EP0444415A1
EP0444415A1 EP91100795A EP91100795A EP0444415A1 EP 0444415 A1 EP0444415 A1 EP 0444415A1 EP 91100795 A EP91100795 A EP 91100795A EP 91100795 A EP91100795 A EP 91100795A EP 0444415 A1 EP0444415 A1 EP 0444415A1
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Prior art keywords
weight
water
sodium disilicate
amorphous
disilicate
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German (de)
French (fr)
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EP0444415B1 (en
Inventor
Franz-Josef Dr. Dany
Werner Gohla
Gerhard Kalteyer
Joachim Dr. Kandler
Hans Krämer
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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    • 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the invention relates to detergents with 5 to 50% by weight, preferably 1o to 3o% by weight, at least one surfactant, 0.5 to 60% by weight of a builder and conventional washing aids.
  • Sodium silicates have long been used as builders in detergents, especially in conjunction with soda, but in the course of modern detergent development they have been used with substances with better builder properties, e.g. condensed phosphates, detached.
  • zeolite 4A in combination with polycarboxylates is the basic builder for many detergent products.
  • amorphous sodium disilicate in the form of water glass or as a powder in an amount of 5% by weight is still common today in the majority of the detergents manufactured.
  • the task assigned to sodium disilicate is not limited to its corrosion-inhibiting effect. It also serves as a builder with good absorption properties for liquid components and improves the dirt-carrying capacity of the wash liquor due to its dispersing effect. It also binds some of the hardness constituents in the wash water and thereby also favors the washing result.
  • amorphous sodium disilicate with water contents of 0.3 to 6% by weight, preferably from 0.5 to 2% by weight, e.g. the powdery amorphous sodium disilicate with a water content of 15 to 23% by weight in a tilted rotary furnace equipped with devices for moving solid matter, in which it is treated with flue gas at temperatures of 25o to 500 ° C for 1 to 6o minutes in countercurrent , wherein the rotary kiln is insulated so that the temperature of its outer wall is less than 60 ° C.
  • the amorphous sodium disilicate emerging from the rotary kiln can be crushed to a particle size of 0.1 to 12 mm using a mechanical crusher.
  • the comminuted sodium disilicate is preferably milled to a grain size of 2 to 400 ⁇ m, the mill being operated at a peripheral speed of 0.5 to 60 ⁇ m / s.
  • the detergent of the present invention is now characterized in that it contains an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight as a builder.
  • Detergents were produced according to the basic formulation below using the individual sodium disilicate species (NaDS; Examples I-VI):
  • the ash value as a measure of the tissue incrustation, was determined after 25 washes by determining the percentage of the residue on ignition at 800 ° C.
  • Table 2 summarizes the washing results obtained with the detergents (type A) based on the Na disilicate in accordance with Examples I-VI.
  • the detergents (type A) equipped with partially dewatered Na disilicate show a clear superiority over the detergent formulation based on the starting product (Example I, Na disilicate with 18% H 2 O).
  • the detergents (type A) produced on the basis of Examples I-VI were also subjected to a test for determining the storage stability.
  • the individual detergent samples were sealed in closed cardboard boxes (wax cardboard, water vapor permeability: approx. 10 gm -2 day -1 ) in a climatic cabinet at 37 ° C and 70% rel. Humidity stored for 4 weeks.
  • the flowability was assessed in accordance with Table 3.
  • Table 3 the detergents (type A) based on the partially dewatered products according to the invention (Examples 11-VI) are clearly superior in that they more or less retain their free-flowing properties, while the commercially available Na disilicate (Example I) below the selected storage conditions completely hardened.
  • Nonionic surfactants are understood to mean those compounds which have an organic, hydrophobic group and a hydrophilic radical, for example the condensation products of alkylphenols or higher fatty alcohols with ethylene oxide (fatty alcohol ethoxylates), the condensation products of polypropylene glycol with ethylene oxide or propylene oxide, the condensation products of ethylene oxide with the Reaction product from ethylenediamine and propylene oxide, as well as long-chain tertiary amine oxides
  • surfactants with a zwitterionic (ampholytic) character include the following compounds: derivatives of aliphatic, secondary and tertiary amines or quaternary ammonium compounds with 8 to 18 carbon atoms and a hydrophilic group in the aliphatic radical, e.g.
  • Suitable washing auxiliaries according to the invention are weakly acidic, neutral or alkaline inorganic or organic salts, in particular inorganic or organic complexing agents.
  • Useful, weakly acidic, neutral or alkaline-reacting salts are, for example, the bicarbonates or carbonates of the alkalis, and also the alkali salts of organic, non-capillary-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms.
  • the organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid or polyalkylene-polyamine-N-polycarboxylic acids.
  • Washing aids according to the invention further include products such as the alkali or ammonium salts of sulfuric acid, boric acid, alkylene, hydroxyalkylene or aminoalkylenephosphonic acid, as well as bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.
  • products such as the alkali or ammonium salts of sulfuric acid, boric acid, alkylene, hydroxyalkylene or aminoalkylenephosphonic acid, as well as bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.
  • the bleaching agents include sodium perborate or tetrahydrate, sodium percarbonate, the alkali metal salts of peroxomono- or peroxodisulfuric acid, the alkali metal salts of peroxodiphosphoric acid (H 4 P 2 0 8 ), and alkali metal salts of peroxocarboxylic acids, such as diperoxododecanedioic acid.
  • water-soluble, precipitated magnesium silicate, organic complexing agents such as the alkali metal salts of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and nitrilotrismethylenephosphonic acid act as stabilizers for these bleaching agents.
  • Washing aids that increase the dirt-carrying capacity of washing liquors, such as carboxymethyl cellulose, carboxymethyl starch, methyl cellulose or copolymers of maleic anhydride with methyl vinyl ether or acrylic acid, foam regulators, such as mono- and dialkyl phosphoric acid esters with 16 to 20 C atoms in the alkyl radical, and optical brighteners, disinfectants and enzymes, such as proteas , Amylases, lipases can also be additional components of the detergent of the invention.
  • foam regulators such as mono- and dialkyl phosphoric acid esters with 16 to 20 C atoms in the alkyl radical
  • optical brighteners disinfectants and enzymes, such as proteas , Amylases, lipases can also be additional components of the detergent of the invention.

Abstract

Ein Waschmittel mit 5 bis 50 Gew% mindestens eines Tensids, 0,5 bis 60 Gew% eines Gerüststoffes sowie üblichen Waschhilfsstoffen enthält als Gerüststoff ein amorphes, wasserarmes Natriumdisilikat mit einem Wassergehalt von 0,3 bis 6 Gew%, das vorzugsweise durch Teilentwässerung von handelsüblichem pulverförmigem, amorphem Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% hergestellt wurde.A detergent with 5 to 50% by weight of at least one surfactant, 0.5 to 60% by weight of a builder and conventional washing aids contains an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight, preferably by partial dewatering of commercially available powdery, amorphous sodium disilicate with a water content of 15 to 23 wt% was produced.

Description

Die Erfindung betrifft Waschmittel mit 5 bis 5o Gew%, vorzugsweise 1o bis 3o Gew%, mindestens eines Tensids, 0,5 bis 60 Gew% eines Gerüststoffes sowie üblichen Waschhilfsstoffen.The invention relates to detergents with 5 to 50% by weight, preferably 1o to 3o% by weight, at least one surfactant, 0.5 to 60% by weight of a builder and conventional washing aids.

Es ist seit mehr als 8o Jahren Stand der Technik, Natriumsilikate, meist in Form ihrer wäßrigen Lösung, auch als Wasserglas bezeichnet, in Waschmittelformulierungen einzubauen.It has been state of the art for more than 80 years to incorporate sodium silicates, mostly in the form of their aqueous solution, also known as water glass, in detergent formulations.

Natriumsilikate wurden lange Zeit, vor allem in Verbindung mit Soda, als Gerüststoffe in Waschmitteln eingesetzt, im Laufe der modernen Waschmittelentwicklung jedoch durch Substanzen mit besseren Buildereigenschaften, wie z.B. kondensierte Phosphate, abgelöst.Sodium silicates have long been used as builders in detergents, especially in conjunction with soda, but in the course of modern detergent development they have been used with substances with better builder properties, e.g. condensed phosphates, detached.

Aufgrund der in vielen Ländern Europas und der USA in Kraft getretenen restriktiven Waschmittelphosphat-Gesetzgebung ist heute Zeolith 4A in Verbindung mit Polycarboxylaten der Basis-Gerüststoff für viele Waschmittelprodukte. Der Zusatz von amorphem Natriumdisilikat in Form von Wasserglas oder als Pulver in einer Menge um 5 Gew% ist bei der Mehrzahl der gefertigten Wachmittel auch heute noch üblich. Die dem Natriumdisilikat zufallende Aufgabe beschränkt sich dabei nicht auf seine korrosionsinhibierende Wirkung. Es dient auch als Gerüststoff mit guten Absorptionseigenschaften für Flüssigbestandteile und verbessert aufgrund seiner dispergierenden Wirkung das Schmutztragevermögen der Waschlauge. Außerdem bindet es einen Teil der Härtebildner des Waschwassers und begünstigt auch dadurch das Waschergebnis.Due to the restrictive detergent phosphate legislation that has come into force in many countries in Europe and the USA, zeolite 4A in combination with polycarboxylates is the basic builder for many detergent products. The addition of amorphous sodium disilicate in the form of water glass or as a powder in an amount of 5% by weight is still common today in the majority of the detergents manufactured. The task assigned to sodium disilicate is not limited to its corrosion-inhibiting effect. It also serves as a builder with good absorption properties for liquid components and improves the dirt-carrying capacity of the wash liquor due to its dispersing effect. It also binds some of the hardness constituents in the wash water and thereby also favors the washing result.

Wie nun überraschend gefunden wurde, können die waschtechnischen Eigenschaften handelsüblicher Natriumdisilikate, welche normalerweise Wassergehalte von 15 - 23 Gew% aufweisen, wesentlich gesteigert werden, wenn man eine Teilentwässerung dieser Produkte vornimmt.As has now surprisingly been found, the washing properties of commercially available sodium disilicate, which normally have water contents of 15-23% by weight, can be significantly increased if a partial dewatering of these products is carried out.

Zur Teilentwässerung derartiger Natriumdisilikate zu amorphen Natriumdisilikaten mit Wassergehalten von 0,3 bis 6 Gew%, vorzugsweise von 0,5 bis 2 Gew%, bringt man z.B. das pulverförmige amorphe Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% in einen geneigt angeordneten, mit Einrichtungen zur Bewegung von Feststoff ausgerüsteten Drehrohrofen ein, in dem man es mit Rauchgas bei Temperaturen von 25o bis zu 500° C 1 bis 6o Minuten im Gegenstrom behandelt, wobei der Drehrohrofen derart isoliert ist, daß die Temperatur seiner Außenwand weniger als 60 ° C beträgt. Das aus dem Drehrohrofen austretende amorphe Natriumdisilikat kann mit Hilfe eines mechanischen Brechers auf Korngrößen von 0,1 bis 12 mm zerkleinert werden. Vorzugsweise wird das zerkleinerte Natriumdisilikat mit einer Mühle auf Korngrößen von 2 bis 400 pm gemahlen, wobei die Mühle mit einer Umfangsgeschwindigkeit von 0,5 bis 6o m/s betrieben wird.For partial dewatering of such sodium disilicate to amorphous sodium disilicate with water contents of 0.3 to 6% by weight, preferably from 0.5 to 2% by weight, e.g. the powdery amorphous sodium disilicate with a water content of 15 to 23% by weight in a tilted rotary furnace equipped with devices for moving solid matter, in which it is treated with flue gas at temperatures of 25o to 500 ° C for 1 to 6o minutes in countercurrent , wherein the rotary kiln is insulated so that the temperature of its outer wall is less than 60 ° C. The amorphous sodium disilicate emerging from the rotary kiln can be crushed to a particle size of 0.1 to 12 mm using a mechanical crusher. The comminuted sodium disilicate is preferably milled to a grain size of 2 to 400 μm, the mill being operated at a peripheral speed of 0.5 to 60 μm / s.

Im einzelnen ist das Waschmittel vorliegender Erfindung nunmehr dadurch gekennzeichnet, daß es als Gerüststoff ein amorphes, wasserarmes Natriumdisilikat mit einem Wassergehalt von 0,3 bis 6 Gew% enthält.In detail, the detergent of the present invention is now characterized in that it contains an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight as a builder.

Darüber hinaus kann das Waschmittel der Erfindung wahlweise und bevorzugt dadurch gekennzeichnet sein, daß

  • a) das amorphe Natriumdisilikat 0,5 bis 2 Gew% Wasser enthält;
  • b) das in ihm als Gerüststoff enthaltene amorphe, wasserarme Natriumdisilikat durch Teilentwässerung von handelsüblichem pulverförmigem, amorphem Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% hergestellt wurde;
  • c) das in ihm als Gerüststoff enthaltene amorphe, wasserarme Natriumdisilikat dadurch hergestellt wurde, daß man pulverförmiges, amorphes Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% in einem geneigt angeordneten, mit Einrichtungen zur Bewegung von Feststoff ausgerüsteten Drehrohrofen einbrachte, in welchem man es mit Rauchgas bei Temperaturen von 25o bis zu 500° C 1 bis 6o Minuten im Gegenstrom behandelte, wobei der Drehrohrofen derart isoliert war, daß die Temperatur seiner Außenwand weniger als 60 C betrug, und daß man das aus dem Drehrohrofen austretende amorphe Natriumdisilikat mit Hilfe eines mechanischen Brechers auf Korngrößen von 0,1 bis 12 mm zerkleinerte und anschließend mit einer Mühle auf Korngrößen von 2 bis 4oo pm mahlte.
In addition, the detergent of the invention may optionally and preferably be characterized in that
  • a) the amorphous sodium disilicate contains 0.5 to 2% by weight of water;
  • b) the amorphous, low-water sodium disilicate contained in it as a builder was prepared by partial dewatering of commercially available powdery, amorphous sodium disilicate with a water content of 15 to 23% by weight;
  • c) the amorphous, low-water sodium disilicate contained in it as a builder was prepared by introducing pulverulent, amorphous sodium disilicate with a water content of 15 to 23% by weight in an inclined rotary furnace equipped with devices for moving solids, in which it was placed treated with flue gas at temperatures from 25o to 500 ° C in countercurrent for 1 to 6o minutes, the rotary kiln being insulated in such a way that the temperature of its outer wall was less than 60 C, and that the amorphous sodium disilicate emerging from the rotary kiln was treated with the aid of a mechanical crusher crushed to grain sizes of 0.1 to 12 mm and then ground with a mill to grain sizes of 2 to 4oo pm.

Ausgehend von einem handelsüblichen Natriumdisilikat mit einem Wassergehalt von 18 Gew% wurden folgende teilentwässerte Produkte hergestellt:

Figure imgb0001
Starting from a commercially available sodium disilicate with a water content of 18% by weight, the following partially dewatered products were produced:
Figure imgb0001

Nach dem Sprühnebelmischverfahren wurden entsprechend der nachstehenden Basisformulierung mit den einzelnen Natriumdisilikat-Spezies (NaDS; Beispiele I - VI) Waschmittel gefertigt:

Figure imgb0002
Detergents were produced according to the basic formulation below using the individual sodium disilicate species (NaDS; Examples I-VI):
Figure imgb0002

Jeweils 2,5 g bzw. 4,5 g der Na-Disilikate entsprechend den Beispielen I - VI wurden zwecks Feststellung ihres Wasserhärte-Bindevermögens (verbleibende Rest-Wasserhärte) in 1ooo ml Wasser der Härte 18° dH gelöst, die Lösung genau 1/2 Stunde bei 60° C mittels eines Magnetrührers mit ca. 5oo Upm gerührt, dann in Eiswasser schnell auf 20°C abgekühlt und anschließend über ein Membranfilter mit einer Porenweite von 0,45 µm vom unlöslichen Rückstand befreit. Die gleiche Prozedur wurde auch mit dem verwendeten Wasser von 18° dH ohne Na-Disilikat-Zusatz durchgeführt, um den Fehler zu eliminieren, der durch eine mögliche Ausfällung von Ca und Mg als Carbonat zustande käme.In each case 2.5 g or 4.5 g of the Na disilicates according to Examples I - VI were dissolved in 1ooo ml of water with a hardness of 18 ° dH to determine their water hardness binding capacity (remaining residual water hardness), the solution exactly 1 / Stirred for 2 hours at 60 ° C using a magnetic stirrer at approx. 500 rpm, then quickly cooled to 20 ° C in ice water and then freed from the insoluble residue using a membrane filter with a pore size of 0.45 µm. The same procedure was also carried out with the water used at 18 ° dH without the addition of Na disilicate in order to eliminate the error which would result from a possible precipitation of Ca and Mg as carbonate.

In gleicher Weise wurden jeweils 1o g der Waschmittel auf der Grundlage vorstehender Basisformulierung mit Na-Disilikat entsprechend den Beispielen I-VI in Wasser von 18° dH gelöst und die Lösungen wie oben beschrieben behandelt. Die Basisformulierung ohne Na-Disilikat-Zusatz wurde als Blindprobe in die Versuchsreihe mit einbezogen.In the same way, 10 g of the detergents based on the above basic formulation were dissolved with Na disilicate in accordance with Examples I-VI in water at 18 ° dH and the solutions were treated as described above. The basic formulation without the addition of Na disilicate was included in the test series as a blank sample.

In den Filtraten der einzelnen Lösungen sowie in dem identisch behandelten und filtrierten Wasser ohne Zusatz wurden mittels Atomabsorption die Rest-Gehalte an Calcium und Magnesium bestimmt, die in Tabelle 1 zusammengestellt sind:

Figure imgb0003
In the filtrates of the individual solutions and in the identically treated and filtered water without addition, the residual contents of calcium and magnesium were determined by means of atomic absorption, which are summarized in Table 1:
Figure imgb0003

Aus den gefundenen Werten für die Rest-Wasserhärte geht eindeutig die Überlegenheit der teilentwässerten Na-Disilikate (Beispiel II-VI) gegenüber den Ausgangsprodukten mit 18 Gew% H20 (Beispiel I) hervor.The values found for the residual water hardness clearly show the superiority of the partially dewatered Na disilicates (Example II-VI) compared to the starting products with 18% by weight H 2 0 (Example I).

Da im allgemeinen ein höheres Vermögen, die Wasserhärte zu binden, auch eine Verbesserung der Waschergebnisse erwarten läßt, wurden mit den Waschmitteln (Typ A), die entsprechend den Beispielen I - IV mit den einzelnen Na-Disilikat-Spezies ausgestattet waren, Waschversuche in einer Haushaltswaschmaschine unter folgenden Bedingungen durchgeführt:

Figure imgb0004
Verwendete Testgewebe:

  • (EMPA = Eidgenössische Materialprüfungsanstalt St. Gallen, Schweiz;
  • WFK = Wäschereiforschung Krefeld)
Since in general a higher ability to bind the water hardness can also be expected to improve the washing results, the detergents (type A) which were equipped with the individual Na disilicate species in accordance with Examples I-IV were used in one test Household washing machine carried out under the following conditions:
Figure imgb0004
 Test fabrics used:
  • (EMPA = Federal Material Testing Institute St. Gallen, Switzerland;
  • WFK = laundry research Krefeld)

a) Für Primärwaschwirkung (Schmutzentfernung und Bleiche):

Figure imgb0005
a) For primary washing effects (dirt removal and bleaching):
Figure imgb0005

b) Für Sekundärwaschwirkung:

  • EMPA - Baumwolle
  • WFK - Frottee
b) For secondary washing action:
  • EMPA - cotton
  • WFK - Terrycloth

Die Prüfung der Primärwaschwirkung wurde mittels optischer Remissionsmessung vorgenommen und in Form der Remissionsdifferenz ausgedrückt, die sich aus der Differenz der Werte nach und vor dem Waschen ergibt:

Figure imgb0006

  • Δ R = Remissionsdifferenz (%)
  • Rn = Remission nach dem Waschen (%)
  • Rv = Remission vor dem Waschen (%)
The primary washing effect was checked by means of optical reflectance measurement and expressed in the form of the reflectance difference, which results from the difference between the values after and before washing:
Figure imgb0006
  • Δ R = reflectance difference (%)
  • R n = remission after washing (%)
  • R v = remission before washing (%)

Der Aschewert, als Maß für die Gewebeinkrustation, wurde nach 25 Waschgängen bestimmt, indem der prozentuale Glührückstand bei 800° C ermittelt wurde.The ash value, as a measure of the tissue incrustation, was determined after 25 washes by determining the percentage of the residue on ignition at 800 ° C.

In der Tabelle 2 sind die Waschergebnisse zusammengefaßt, die mit den Waschmitteln (Typ A) auf Basis der Na-Disilikate entsprechend den Beispielen I-VI erhalten wurden. Erwartungsgemäß zeigen die mit teilentwässertem Na-Disilikat ausgestatteten Waschmittel (Typ A) eine deutliche Überlegenheit gegenüber der Waschmittelformulierung auf Basis des Ausgangsproduktes (Beispiel I, Na-Disilikat mit 18 % H2O).Table 2 summarizes the washing results obtained with the detergents (type A) based on the Na disilicate in accordance with Examples I-VI. As expected, the detergents (type A) equipped with partially dewatered Na disilicate show a clear superiority over the detergent formulation based on the starting product (Example I, Na disilicate with 18% H 2 O).

Die auf Basis der Beispiele I - VI hergestellten Waschmittel (Typ A) wurden auch einem Test zur Ermittlung der Lagerstabilität unterworfen. Hierbei wurden die einzelnen Waschmittelproben in geschlossenen Pappkartons (Wachs-Karton, Wasserdampfdurchlässigkeit: ca. 1o g m-2 Tag -1) in einem Klimaschrank bei 37 °C und 7o % rel. Luftfeuchte 4 Wochen gelagert. Die Rieselfähigkeit wurde entsprechend Tabelle 3 beurteilt. Wie Tabelle 3 zu entnehmen ist, zeigen sich die Waschmittel (Typ A) auf Basis der erfindungsgemäßen teilentwässerten Produkte (Beispiele 11 - VI) klar überlegen, indem sie ihre Rieselfähigkeit mehr oder weniger beibehalten, während das handelsübliche Na-Disilikat (Beispiel I) unter den gewählten Lagerbedingungen vollkommen verhärtet.

Figure imgb0007
Figure imgb0008
 The detergents (type A) produced on the basis of Examples I-VI were also subjected to a test for determining the storage stability. The individual detergent samples were sealed in closed cardboard boxes (wax cardboard, water vapor permeability: approx. 10 gm -2 day -1 ) in a climatic cabinet at 37 ° C and 70% rel. Humidity stored for 4 weeks. The flowability was assessed in accordance with Table 3. As can be seen in Table 3, the detergents (type A) based on the partially dewatered products according to the invention (Examples 11-VI) are clearly superior in that they more or less retain their free-flowing properties, while the commercially available Na disilicate (Example I) below the selected storage conditions completely hardened.
Figure imgb0007
Figure imgb0008

Unter anionischen Tensiden sind die wasserlöslichen Salze höherer Fettsäuren oder Harzsäuren, wie Natrium- oder Kaliumseifen von Kokos-, Palmkern- oder Rüböl sowie von Talg und Gemischen davon zu verstehen. Weiterhin zählen dazu höhere alkylsubstituierte, aromatische Sulfonate, wie Alkylbenzolsulfonate mit 9 bis 14 C-Atomen im Alkylrest, Alkylnaphthalinsulfonate, Alkyltoluolsulfonate, Alkylxylolsulfonate oder Alkylphenolsulfonate; Fettalkoholsulfate (R-CH2-O-SO3Na; R = C11-17) oder Fettalkoholethersulfate, wie Alkalilaurylsulfat oder Alkalihexadecylsulfat, Triethanolaminlaurylsulfat, Natrium- oder Kaliumoleylsulfat, Natrium- oder Kaliumsalze von mit 2 bis 6 Mol Ethylenoxid ethoxyliertem Laurylsulfat. Weitere geeignete anionische Tenside sind sekundäre lineare Alkansulfonate sowie a-Olefinsulfonate mit einer Kettenlänge von 12-2o C-Atomen.Anionic surfactants are to be understood as meaning the water-soluble salts of higher fatty acids or resin acids, such as sodium or potassium soaps from coconut, palm kernel or turnip oil, and from tallow and mixtures thereof. These also include higher alkyl-substituted aromatic sulfonates, such as alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl radical, alkylnaphthalenesulfonates, alkyltoluenesulfonates, alkylxylenesulfonates or alkylphenolsulfonates; Fatty alcohol sulfates (R-CH 2 -O-SO3Na; R = C 11-17 ) or fatty alcohol ether sulfates, such as alkali lauryl sulfate or alkali hexadecyl sulfate, triethanolamine lauryl sulfate, sodium or potassium oleyl sulfate, sodium or potassium salts of lauryl ethoxylated with 2 to 6 moles of ethylene sulfate. Other suitable anionic surfactants are secondary linear alkane sulfonates and a-olefin sulfonates with a chain length of 12-2o C atoms.

Unter nichtionischen Tensiden sind solche Verbindungen zu verstehen, die eine organische, hydrophobe Gruppe sowie einen hydrophilen Rest aufweisen, z.B. die Kondensationsprodukte von Alkylphenolen oder höheren Fettalkoholen mit Ethylenoxid (Fettalkoholethoxylate), die Kondensationsprodukte von Polypropylenglykol mit Ethylenoxid oder Propylenoxid, die Kondensationsprodukte von Ethylenoxid mit dem Reaktionsprodukt aus Ethylendiamin und Propylenoxid, sowie langkettige tertiäre Aminoxide

Figure imgb0009
Nonionic surfactants are understood to mean those compounds which have an organic, hydrophobic group and a hydrophilic radical, for example the condensation products of alkylphenols or higher fatty alcohols with ethylene oxide (fatty alcohol ethoxylates), the condensation products of polypropylene glycol with ethylene oxide or propylene oxide, the condensation products of ethylene oxide with the Reaction product from ethylenediamine and propylene oxide, as well as long-chain tertiary amine oxides
Figure imgb0009

Schließlich umfassen Tenside mit zwitterionischem (ampholytischem) Charakter folgende Verbindungen: Derivate von aliphatischen, sekundären und tertiären Aminen oder quaternären Ammoniumverbindungen mit 8 bis 18 C-Atomen und einer hydrophilen Gruppe im aliphatischen Rest, wie z.B. Natrium-3-dodecylaminopropionat, Natrium-3-dodecylaminopropansulfonat, 3-(N,N-Dimethyl-N-hexadecyl-amino)-propan-1-sulfonat oder Fettsäureaminoalkyl-N,N-dimethylacetobetain, wobei die Fettsäure 8 bis 18 C-Atome und der Alkylrest 1 - 3 C-Atome enthält.Finally, surfactants with a zwitterionic (ampholytic) character include the following compounds: derivatives of aliphatic, secondary and tertiary amines or quaternary ammonium compounds with 8 to 18 carbon atoms and a hydrophilic group in the aliphatic radical, e.g. Sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate, 3- (N, N-dimethyl-N-hexadecylamino) propane-1-sulfonate or fatty acid aminoalkyl-N, N-dimethylacetobetaine, the fatty acid being 8 to 18 C- Atoms and the alkyl radical contains 1 - 3 carbon atoms.

Als Waschhilfsstoffe gemäß der Erfindung eignen sich schwach sauer, neutral oder alkalisch reagierende anorganische oder organische Salze, insbesondere anorganische oder organische Komplexbildner.Suitable washing auxiliaries according to the invention are weakly acidic, neutral or alkaline inorganic or organic salts, in particular inorganic or organic complexing agents.

Brauchbare, schwach sauer, neutral oder alkalisch reagierende Salze sind beispielsweise die Bicarbonate oder Carbonate der Alkalien, weiterhin die Alkalisalze von organischen, nicht kapillaraktiven, 1 bis 8 C-Atome enthaltenden Sulfonsäuren, Carbonsäuren und Sulfocarbonsäuren. Hierzu gehören beispielsweise wasserlösliche Salze der Benzol-, Toluol- oder Xylolsulfonsäure, wasserlösliche Salze der Sulfoessigsäure, Sulfobenzoesäure oder Salze von Sulfodicarbonsäuren sowie die Salze der Essigsäure, Milchsäure, Zitronensäure, Weinsäure, Oxydiessigsäure (HOOC-CHz-0-CHz-COOH), Oxydibernsteinsäure, 1,2,3,4-Cyclopentantetracarbonsäure, Polycarboxylate, Polyacrylsäure und Polymaleinsäure. Zu den organischen Komplexbildnern gehören beispielsweise Nitrilotriessigsäure, Ethylendiamintetraessigsäure, N-Hydroxyethylethylendiamintriessigsäure oder Polyalkylen-polyamin-N-polycarbonsäuren.Useful, weakly acidic, neutral or alkaline-reacting salts are, for example, the bicarbonates or carbonates of the alkalis, and also the alkali salts of organic, non-capillary-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of acetic acid, lactic acid, citric acid, tartaric acid, oxydiacetic acid (HOOC-CH z -0-CH z -COOH) , Oxydisuccinic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polycarboxylates, polyacrylic acid and polymaleic acid. The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid or polyalkylene-polyamine-N-polycarboxylic acids.

Waschhilfsstoffe gemäß der Erfindung umfassen ferner Produkte wie die Alkali- oder Ammoniumsalze der Schwefelsäure, Borsäure, Alkylen-, Hydroxyalkylen- oder Aminoalkylenphosphonsäure sowie Bleichmittel, Stabilisatoren für Peroxidverbindungen (Bleichmittel) und wasserlösliche organische Komplexbildner.Washing aids according to the invention further include products such as the alkali or ammonium salts of sulfuric acid, boric acid, alkylene, hydroxyalkylene or aminoalkylenephosphonic acid, as well as bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.

Im einzelnen gehören zu den Bleichmitteln Natriumperboratmono- oder tetrahydrat, Na-Percarbonat, die Alkalisalze der Peroxomono- oder Peroxodischwefelsäure, die Alkalisalze der Peroxodiphoshorsäure (H4P208), und Alkalisalze von Peroxocarbonsäuren, wie Diperoxododekandisäure. Als Stabilisatoren für diese Bleichmittel fungieren z.B. wasserlösliches, gefälltes Magnesiumsilikat, organische Komplexbildner wie die Alkalisalze der Iminodiessigsäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure, Methylendiphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure und Nitrilotrismethylenphosphonsäure.In particular, the bleaching agents include sodium perborate or tetrahydrate, sodium percarbonate, the alkali metal salts of peroxomono- or peroxodisulfuric acid, the alkali metal salts of peroxodiphosphoric acid (H 4 P 2 0 8 ), and alkali metal salts of peroxocarboxylic acids, such as diperoxododecanedioic acid. For example, water-soluble, precipitated magnesium silicate, organic complexing agents such as the alkali metal salts of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and nitrilotrismethylenephosphonic acid act as stabilizers for these bleaching agents.

Waschhilfsstoffe, die das Schmutztragevermögen von Waschflotten erhöhen, wie Carboxymethylcellulose, Carboxymethylstärke, Methylcellulose oder Copolymere von Maleinsäureanhydrid mit Methylvinylether oder Acrylsäure, Schaumregulatoren, wie Mono- und Dialkylphosphorsäureester mit 16 bis 20 C-Atomen im Alkylrest sowie optische Aufheller, Desinfizienzien und Enzyme, wie Proteasen, Amylasen, Lipasen, können ebenfalls zusätzliche Bestandteile des Waschmittels der Erfindung sein.Washing aids that increase the dirt-carrying capacity of washing liquors, such as carboxymethyl cellulose, carboxymethyl starch, methyl cellulose or copolymers of maleic anhydride with methyl vinyl ether or acrylic acid, foam regulators, such as mono- and dialkyl phosphoric acid esters with 16 to 20 C atoms in the alkyl radical, and optical brighteners, disinfectants and enzymes, such as proteas , Amylases, lipases can also be additional components of the detergent of the invention.

Patentansprüche

  • 1. Waschmittel mit 5 bis 50 Gew% mindestens eines Tensids, 0,5 bis 6o Gew% eines Gerüststoffes sowie üblichen Waschhilfsstoffen, dadurch gekennzeichnet, daß es als Gerüststoff ein amorphes, wasserarmes Natriumdisilikat mit einem Wassergehalt von 0,3 bis 6 Gew% enthält.
  • 2. Waschmittel nach Anspruch 1, dadurch gekennzeichnet, daß das amorphe Natriumdisilikat 0,5 bis 2 Gew% Wasser enthält.
  • 3. Waschmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das in ihm als Gerüststoff enthaltene amorphe, wasserarme Natriumdisilikat durch Teilentwässerung von handelsüblichem pulverförmigem, amorphem Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% hergestellt wurde.
  • 4. Waschmittel nach Anspruch 3, dadurch gekennzeichnet, daß das in ihm als Gerüststoff enthaltene amorphe, wasserarme Natriumdisilikat dadurch hergestellt wurde, daß man pulverförmiges, amorphes Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% in einem geneigt angeordneten, mit Einrichtungen zur Bewegung von Feststoff ausgerüsteten Drehrohrofen einbrachte, in welchem man es mit Rauchgas bei Temperaturen von 25o bis zu 500 °C 1 bis 6o Minuten im Gegenstrom behandelte, wobei der Drehrohrofen derart isoliert war, daß die Temperatur seiner Außenwand weniger als 60 C betrug, und daß man das aus dem Drehrohrofen austretende amorphe Natriumdisilikat mit Hilfe eines mechanischen Brechers auf Korngrößen von 0,1 bis 12 mm zerkleinerte und anschließend mit einer Mühle auf Korngrößen von 2 bis 400 µm mahlte.
Claims
  • 1. Detergent with 5 to 50% by weight of at least one surfactant, 0.5 to 6o% by weight of a builder and conventional washing aids, characterized in that it contains an amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight .
  • 2. Detergent according to claim 1, characterized in that the amorphous sodium disilicate contains 0.5 to 2% by weight of water.
  • 3. Detergent according to claim 1 or 2, characterized in that the amorphous, low-water sodium disilicate contained in it as a builder was prepared by partial dewatering of commercially available powdered, amorphous sodium disilicate with a water content of 15 to 23% by weight.
  • 4. Detergent according to claim 3, characterized in that the amorphous, low-water sodium disilicate contained in it as a builder was prepared in that powdered, amorphous sodium disilicate with a water content of 15 to 23% by weight in an inclined arrangement with devices for moving Solid rotary kiln was introduced, in which it was treated with flue gas at temperatures from 25o to 500 ° C for 1 to 6o minutes in countercurrent, the rotary kiln being insulated so that the temperature of its outer wall was less than 60 C, and that Amorphous sodium disilicate emerging from the rotary kiln was ground to a particle size of 0.1 to 12 mm using a mechanical crusher and then ground to a particle size of 2 to 400 μm using a mill.

Claims (4)

1. Verfahren zur Herstellung eines Waschmittels, dadurch gekennzeichnet, daß man 5 bis 5o Gewichts% mindestens eines Tensids und 0,5 bis 6o Gewichts% amorphes, wasserarmes Natriumdisilikat mit einem Wassergehalt von 0,3 bis 6 Gewichts% als Gerüststoff zusammen mit üblichen Waschhilfsstoffen intensiv vermischt.1. A process for the preparation of a detergent, characterized in that 5 to 5o% by weight of at least one surfactant and 0.5 to 6o% by weight amorphous, low-water sodium disilicate with a water content of 0.3 to 6% by weight as a builder together with conventional washing aids intensely mixed. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das amorphe Natriumdisilikat 0,5 bis 2 Gewichts% Wasser enthält.2. The method according to claim 1, characterized in that the amorphous sodium disilicate contains 0.5 to 2% by weight of water. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das amorphe, wasserarme Natriumdisilikat durch Teilentwässerung von handelsüblichem pulverförmigem, amorphem Natriumdisilikat mit einem Wassergehalt von 15 bis 23 Gew% hergestellt wurde.3. The method according to claim 1 or 2, characterized in that the amorphous, low-water sodium disilicate was produced by partial dewatering of commercially available powdered, amorphous sodium disilicate with a water content of 15 to 23% by weight. 4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das amorphe, wasserarme Natriumdisilikat erhalten wurde durch Einbringen des pulverförmigen, amorphen Natriumdisilikates mit einem Wassergehalt von 15 bis 23 Gew% in einen geneigt angeordneten, mit Einrichtungen zur Bewegung von Feststoff ausgerüsteten Drehrohrofen, durch 1 bis 60minutiges Behandeln im Drehrohrofen mit Rauchgas bei Temperaturen von 25o bis zu 500°C im Gegenstrom, wobei der Drehrohrofen derart isoliert war, daß die Temperatur seiner Außenwand weniger als 60 ° C betrug, sowie durch Zerkleinern des aus dem Drehrohrofen austretenden amorphen Natriumdisilikates mit Hilfe eines mechanischen Brechers auf Korngrößen von 0,1 bis 12 mm und anschließendes Mahlen auf Korngrößen von 2 bis 4oo µm.4. The method according to claim 3, characterized in that the amorphous, low-water sodium disilicate was obtained by introducing the powdery, amorphous sodium disilicate with a water content of 15 to 23% by weight in an inclined, equipped with devices for moving solid rotary kiln by 1 up to 60 minutes of treatment in a rotary kiln with flue gas at temperatures of 25o to 500 ° C in countercurrent, the rotary kiln being insulated in such a way that the temperature of its outer wall was less than 60 ° C, and by crushing the amorphous sodium disilicate emerging from the rotary kiln with the help a mechanical crusher to grain sizes from 0.1 to 12 mm and subsequent grinding to grain sizes from 2 to 4oo µm.
EP91100795A 1990-02-15 1991-01-23 Detergent composition comprising partially dehydrated disilicate Expired - Lifetime EP0444415B1 (en)

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WO1995018766A2 (en) * 1994-01-03 1995-07-13 Henkel Kommanditgesellschaft Auf Aktien Silicate builders and their use in washing or cleaning agents
EP0665815A1 (en) * 1993-08-23 1995-08-09 PQ Corporation Amorphous alkali metal silicate, process and uses
FR2743085A1 (en) * 1995-12-29 1997-07-04 Rhone Poulenc Chimie Washing agent for laundry applications
US5814597A (en) * 1994-03-01 1998-09-29 Henkel Kommanditgesellschaft Auf Aktien Multicomponent mixtures based on water-soluble alkali metal silicate compounds and their use, more particularly as builders in detergents
EP1416040A1 (en) * 2002-11-02 2004-05-06 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Water soluble builders with a specific particle size for use in detergents and cleaning agents
EP1416039A1 (en) * 2002-11-02 2004-05-06 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Use of water soluble builders with a specific particle size in bleach free laundry detergents

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USRE35045E (en) * 1991-07-17 1995-10-03 Church & Dwight Co., Inc. Method for removing soldering flux with alkaline metal carbonate salts and an alkali metal silicate
USRE35017E (en) * 1991-07-17 1995-08-15 Church & Dwight Co., Inc. Method for removing soldering flux with alkaline salts, an alkali metal silicate and anionic polymer
US5264047A (en) * 1991-07-17 1993-11-23 Church & Dwight Co., Inc. Low foaming effective hydrotrope
US5264046A (en) * 1991-07-17 1993-11-23 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and cleaning method
US5433885A (en) * 1991-07-17 1995-07-18 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5431847A (en) * 1991-07-17 1995-07-11 Charles B. Barris Aqueous cleaning concentrates
US5234505A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Stabilization of silicate solutions
US5234506A (en) * 1991-07-17 1993-08-10 Church & Dwight Co., Inc. Aqueous electronic circuit assembly cleaner and method
USRE35115E (en) * 1991-07-17 1995-12-12 Church & Dwight Co. Inc. Low foaming effective hydrotrope
US5261967A (en) * 1991-07-17 1993-11-16 Church & Dwight Co, Inc. Powdered electric circuit assembly cleaner
EP0639639B2 (en) * 1993-08-17 2010-07-28 The Procter & Gamble Company Detergent compositions comprising percarbonate bleaching agents
DE4415362A1 (en) * 1994-05-02 1995-11-09 Henkel Kgaa Process for the production of silicate builder granules with increased bulk density
US5747439A (en) * 1996-04-02 1998-05-05 Church & Dwight Co, Inc. Aqueous sodium salt metal cleaner
MX2010010247A (en) * 2008-04-07 2010-10-20 Ecolab Inc Ultra-concentrated solid degreaser composition.

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EP0665815A1 (en) * 1993-08-23 1995-08-09 PQ Corporation Amorphous alkali metal silicate, process and uses
EP0665815A4 (en) * 1993-08-23 1995-11-15 Pq Corp Amorphous alkali metal silicate, process and uses.
WO1995018766A2 (en) * 1994-01-03 1995-07-13 Henkel Kommanditgesellschaft Auf Aktien Silicate builders and their use in washing or cleaning agents
WO1995018766A3 (en) * 1994-01-03 1995-07-27 Henkel Kgaa Silicate builders and their use in washing or cleaning agents
US5780420A (en) * 1994-01-03 1998-07-14 Henkel Kommanditgesselschaft Auf Aktien Silicate-based builders and their use in detergents and multicomponent mixtures for use in this field
US5814597A (en) * 1994-03-01 1998-09-29 Henkel Kommanditgesellschaft Auf Aktien Multicomponent mixtures based on water-soluble alkali metal silicate compounds and their use, more particularly as builders in detergents
FR2743085A1 (en) * 1995-12-29 1997-07-04 Rhone Poulenc Chimie Washing agent for laundry applications
EP1416040A1 (en) * 2002-11-02 2004-05-06 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Water soluble builders with a specific particle size for use in detergents and cleaning agents
EP1416039A1 (en) * 2002-11-02 2004-05-06 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Use of water soluble builders with a specific particle size in bleach free laundry detergents

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