EP0903401B1 - Antimicrobial additive for washing agents - Google Patents

Antimicrobial additive for washing agents Download PDF

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Publication number
EP0903401B1
EP0903401B1 EP19980810888 EP98810888A EP0903401B1 EP 0903401 B1 EP0903401 B1 EP 0903401B1 EP 19980810888 EP19980810888 EP 19980810888 EP 98810888 A EP98810888 A EP 98810888A EP 0903401 B1 EP0903401 B1 EP 0903401B1
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EP
European Patent Office
Prior art keywords
detergent additive
laundry detergent
additive according
formula
surfactant
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
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EP19980810888
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German (de)
French (fr)
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EP0903401A1 (en
Inventor
Rüdiger Hirsch
Werner Hölzl
Marcel Schnyder
Rainer Hans Traber
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BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Priority to EP19980810888 priority Critical patent/EP0903401B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen

Definitions

  • the present invention relates to an antimicrobial detergent additive, and a method for its manufacture.
  • DE-A-195 38 028 describes a detergent additive which has a swellable Layered silicate, an optical brightener and a surfactant contains.
  • Detergent particles consisting of nonionic surfactant and smectite or zeolite are described in GB-A-2182051.
  • JP-A-91 94 899 discloses detergent compositions containing a nonionic surfactant, an oil absorbing carrier, a clay material and an antimicrobial substance.
  • Textile fiber materials can be made antimicrobial in various ways, so e.g. during the washing process.
  • antimicrobial agents are susceptible to oxidation against the bleach components present in the detergent, e.g. perborates, so that the antimicrobial effect of such a detergent deteriorates significantly can become or even have no effect.
  • the present invention was therefore based on the object of an antimicrobial detergent additive to find the oxidation stable to the other detergent components remains and thus gives the detergent overall good storage stability and At the same time, the antimicrobial effect is fully developed during the washing process.
  • a detergent additive in agglomerate form which, in addition to the antimicrobial active substance, has at least one swellable Layered silicate and a surfactant contains these requirements, i.e. the in this Antimicrobial active substance contained in detergent is protected against oxidizing agents and after the agglomerate has dissolved in the wash liquor.
  • the detergent additive has a high storage stability, disintegrates well in water, and the antimicrobial active substance lies in the washing process homogeneous distribution.
  • the detergent additive may contain, in addition to the swellable layered silicate, the antimicrobial active substance and the surfactant an alkali salt, e.g. Alkali sulfate, alkali carbonate or alkali (poly) phosphate.
  • an alkali salt e.g. Alkali sulfate, alkali carbonate or alkali (poly) phosphate.
  • the swellable layered silicate is preferably a natural or synthetic clay mineral or a synthetic layered sodium silicate.
  • the swellable clay mineral is preferably montmorillonite, beidelite, saponite or hectorite.
  • Bentonite contains montmorillonite as its main mineral, which is a swellable dioctahedral natural layered silicate of the formula Na 0.66 (OH) 4 Si 8 (Al 3.34Mg 0.66 ) O 20 represents.
  • One layer is composed of three sub-elements, with two tetrahedral layers with Si as the central atom and an octahedron layer with Al as the central atom.
  • Al 3+ is partly isomorphically replaced by Mg 2+ .
  • the resulting excess charge is balanced between the layers by Na + or Ca 2+ .
  • the montmorillonite can be used in the sodium or calcium form or in the form of a calcium montmorillonite exchanged with Na + .
  • the bentonite powder preferably has a residual moisture content of about 10% by weight and a sieve residue of a maximum of 30% to 45 ⁇ m.
  • synthetically produced clay minerals can also be used from the groups mentioned above, such as synthetic layered sodium silicates (e.g. the commercial product SKS 6 from Hoechst AG).
  • the layered silicate is preferably used in an amount of 10 to 50% by weight, in particular 30 up to 50% by weight.
  • the swellable layered silicates have the property of swelling within crystals Polar agents intercalate between the silicate lamellae, which can be seen at higher concentrations noticeable in an increase in the layer spacing.
  • the surfactant used according to the invention is preferably an anionic or nonionic Surfactant.
  • the fatty alcohol ethoxylates are stored between the layers.
  • the non-ionic Surfactants in which the antimicrobial active substances are soluble favor them Transport between the lamellae of the swellable layered silicate.
  • the antimicrobial Active substances are intercalated between the layers of the layered silicate and so before protected from reaction with other detergent ingredients.
  • Layered silicates intercalated with surfactants and the antimicrobial active ingredient in Granulate form swell in water and give the tensides and antimicrobial active substance the solution in water free. Due to the swelling effect of the layered silicate agglomerate in Water, the agglomerates are blown up and distributed in the water.
  • the compound -2,4,4'-trichloro-2-hydroxydiphenyl ether (triclosan) is very particularly preferred, according to the formula or the compound of the formula (Diclosan).
  • the detergent additive according to the invention can be one or a mixture of several contain antimicrobial active substances.
  • Alkali salts include in particular alkali sulfate, alkali carbonate or alkali (poly) phosphate in the form of their sodium or potassium salts. Is very particularly preferred Sodium sulfate.
  • the alkali salt fulfills several functions: if the layered silicate is agglomerated with the surfactant, this gives a soft agglomerate that becomes sticky with increasing surfactant content, that is not free-flowing and not capable of ensiling. Due to the presence of the alkali salt the mechanical stability of the agglomerate is improved and its stickiness reduced.
  • the alkali salt in the detergent is desirable as a builder component.
  • the Alkali salt is preferably used in amounts of approximately 10 to 40% by weight, in particular approximately 12 up to 30% by weight.
  • the agglomerate particles of the detergent additive according to the invention preferably with synthetic zeolite or layered sodium silicate are encased, thereby increasing the flowability of the agglomerate particles. is improved.
  • the coating with zeolite or layered sodium silicate further improves the whiteness of the agglomerate.
  • the agglomerate preferably has a bulk density of more than 700 g / l and is due to This high bulk density is compatible with highly concentrated, high density detergents.
  • the swellable layered silicate is preferably mixed before the antimicrobial is added Active substance / surfactant with the alkali salt.
  • the powder components can e.g. in an intensive mixer, e.g. in an Eirich mixer be mixed together.
  • the antimicrobial active substance preferably as an aqueous dispersion
  • the surfactant under Whirling is added to the powder component.
  • the resulting agglomerate is sieved and can pass through Addition of further zeolite (in particular zeolite P) or layered sodium silicate coated in powder form on the surface to reduce stickiness.
  • the agglomerate obtained is readily dispersible in water.
  • the antimicrobial substance is protected from the oxidizing agents contained in the detergent and after dissolution of the agglomerate available in the wash liquor.
  • the present invention further relates to a detergent containing the above Detergent additive described in addition to conventional detergent components, such as anionic and non-ionic surfactants, builders (builders), polymers (co-builders), Graying inhibitors, bleaches and bleach activators, enzymes, foam inhibitors, optical brighteners and fragrances and / or dyes.
  • conventional detergent components such as anionic and non-ionic surfactants, builders (builders), polymers (co-builders), Graying inhibitors, bleaches and bleach activators, enzymes, foam inhibitors, optical brighteners and fragrances and / or dyes.
  • the powdered layered silicate and the powdered sodium salt become intense premixed. With intensive swirling of the powder mixture, the surfactant or a Solution of the surfactant added. At the same time, the antimicrobial active substance becomes a Mixture of various antimicrobial active substances as an aqueous dispersion (slurry) added. Alternatively, a solution of the antimicrobial active substance in one Surfactant solution can be added to the powder mixture.
  • the antimicrobial active substance is added as an aqueous dispersion, it agglomerates the mixture at a water content of about 20 to 30% by weight, based on the total mixture.
  • an agglomerate is obtained which is in a suitable dryer, preferably in a fluid bed dryer to a residual water content from about 2 to 15% by weight, preferably from about 5 to 10% by weight becomes.
  • the agglomerate obtained is sieved to a particle size of about 0.2 to 2.5 mm, preferably sieved from 0.5 to 1.7 mm. The fraction becomes ⁇ 0.2 mm fed back to the agglomeration.
  • Coarse grain is removed with a roller crusher crushed and placed again on the screening plant.
  • the antimicrobial active substance with the surfactant is added to the powder mixture, the antimicrobial active substance is first dissolved in powder form in the surfactant.
  • the weight ratio between surfactant and antimicrobial active substance can be 15: 2 to 4:10, preferably 10: 3 to 10: 8.
  • the solution or dispersion of the antimicrobial Active substance in the surfactant is added to the powder with intensive swirling, whereby at the same time further portions of the antimicrobial active substance in aqueous dispersion were added become.
  • the screened agglomerate can be placed in a drum mixer (e.g. a drum mixer from Telschig) or a granulating plate. Then about 3 to 15% by weight, preferably about 5 to 10% by weight, of a synthetic Zeolite or a synthetic layered silicate added in fine-grained form.
  • the average particle size of this powder should preferably be ⁇ 20 ⁇ m, in particular 3 to 10 ⁇ m be.
  • the detergent additive according to the invention thus produced has a bulk density that is greater than 700 g / l, so that it is compatible with detergents with a high bulk density.
  • the swelling effect of the layered silicate contained in the detergent additive disintegrates Agglomerates quickly in water.
  • the active components surfactant and antimicrobial active substance are therefore available in the detergent.
  • Due to the presence of layered silicate and alkali salt the agglomerate is mechanically stable.
  • the agglomerate can be subsequently Add detergent, which makes up essential parts of the detergent production system not be contaminated with the antimicrobial active substance.
  • Another advantage of the detergent additive according to the invention is that the application to a carrier the dosing accuracy of the active substance in the production of detergents is increased.
  • the sample is dried for 4 hours at 65 ° C in a vacuum and then over 3 sieves sieved with mesh sizes of 2, 1 and 0.5 mm.
  • the sample is dried for 4 hours at 65 ° C in a vacuum and then over 3 sieves sieved with mesh sizes of 2, 1 and 0.5 mm.
  • Examples 5 to 10 The procedure is as described in Examples 1 to 4, but the following compounds are used instead of triclosan: example antimicrobial active substance 5 Diclosan (compound of formula (6)) 6 dichlorophen
  • Example 7 Determination of the oxidation stability of triclosan in various triclosan-bentonite compound / detergent mixtures
  • This detergent has the following composition (%): Linear Na alkyl benzene sulfonate 8.0 Mg silicate 1.9 Tallow tetra-ethylene glycol ether dean 2.9 carboxymethylcellulose 1.2 Na-soap 3.5 EDTA 0.2 Na-triphosphate 43.8 Na sulphate 21.2 Na-silicate 7.5 water 9.8
  • the reference mixture has the following composition 0.15% triclosan 12% Na perborate x 1 H 2 O 3% TAED ECE ad 100%.
  • the target content of triclosan in the detergent compositions was determined analytically before the start of the test.

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  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)

Description

Die vorliegende Erfindung betrifft einen antimikrobiellen Waschmittelzusatz, und ein Verfahren zu dessen Herstellung.The present invention relates to an antimicrobial detergent additive, and a method for its manufacture.

DE-A-195 38 028 beschreibt ein Waschmittelzusatz, der ein quellfähiges Schichtsilikat, einen optischen Aufheller und ein Tensid enthält.DE-A-195 38 028 describes a detergent additive which has a swellable Layered silicate, an optical brightener and a surfactant contains.

Waschmittelteilchen bestehend aus nichtionischem Tensid und Smectit oder Zeolith sind in GB-A-2182051 beschrieben.Detergent particles consisting of nonionic surfactant and smectite or zeolite are described in GB-A-2182051.

JP-A-91 94 899 offenbart Waschmittelzusammensetzungen enthaltend ein nichtionisches Tensid, einen ölabsorbierenden Carrier, ein Tonmaterial und eine antimikrobielle Substanz.JP-A-91 94 899 discloses detergent compositions containing a nonionic surfactant, an oil absorbing carrier, a clay material and an antimicrobial substance.

Textile Fasermaterialien lassen sich auf verschiedene Art und Weise antimikrobiell ausrüsten, so z.B. beim Waschprozess. Leider sind antimikrobielle Wirksubstanzen oxidationsanfällig gegen die im Waschmittel vorhandenen Bleichmittelkomponenten, wie z.B. Perborate, so dass die antimikrobielle Wirkung eines solchen Waschmittels deutlich verschlechtert werden kann oder sogar ohne Wirkung ist.Textile fiber materials can be made antimicrobial in various ways, so e.g. during the washing process. Unfortunately, antimicrobial agents are susceptible to oxidation against the bleach components present in the detergent, e.g. perborates, so that the antimicrobial effect of such a detergent deteriorates significantly can become or even have no effect.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, einen antimikrobiellen Waschmittelzusatz zu finden, der gegenüber den übrigen Waschmittelkomponenten oxidationsstabil bleibt und somit dem Waschmittel insgesamt eine gute Lagerstabilität verleiht und gleichzeitig bewirkt, dass die antimikrobielle Wirkung beim Waschprozess voll entfaltet wird.The present invention was therefore based on the object of an antimicrobial detergent additive to find the oxidation stable to the other detergent components remains and thus gives the detergent overall good storage stability and At the same time, the antimicrobial effect is fully developed during the washing process.

Überraschenderweise wurde gefunden, dass ein Waschmittelzusatz in Agglomeratform (Granulatform), der neben der antimikrobiellen Wirksubstanz mindestens ein quellfähiges Schichtsilikat und ein Tensid enthält, diese Voraussetzungen erfüllt, d.h. die in diesem Waschmittelzusatz enthaltene antimikrobielle Wirksubstanz ist gegen Oxidationsmittel geschützt und nach der Auflösung des Agglomerats in der Waschlauge verfügbar. Der Waschmittelzusatz weist bei guter mechanischer Stabilität eine hohe Lagerstabilität auf, zerfällt gut in Wasser, und die antimikrobielle Wirksubstanz liegt beim Waschprozess in homogener Verteilung vor.Surprisingly, it was found that a detergent additive in agglomerate form (Granular form) which, in addition to the antimicrobial active substance, has at least one swellable Layered silicate and a surfactant contains these requirements, i.e. the in this Antimicrobial active substance contained in detergent is protected against oxidizing agents and after the agglomerate has dissolved in the wash liquor. The With good mechanical stability, the detergent additive has a high storage stability, disintegrates well in water, and the antimicrobial active substance lies in the washing process homogeneous distribution.

Gegenstand der vorliegenden Erfindung ist daher ein Waschmittelzusatz in Agglomeratform, der dadurch gekennzeichnet ist, dass er mindestens ein quellfähiges Schichtsilikat, eine antimikrobielle Wirksubstanz der Formel

Figure 00010001
worin

X
Sauerstoff, Schwefel oder -CH2-,
Y
Chlor oder Brom,
Z
SO2H, NO2 oder C1-C4-Alkyl,
r
0 bis 3,
o
0 bis 3,
p
0 oder 1,
m
0 oder 1 und
n
0 oder 1 bedeuten,
und ein Tensid enthält.The present invention therefore relates to a detergent additive in agglomerate form, which is characterized in that it contains at least one swellable layered silicate, an antimicrobial active substance of the formula
Figure 00010001
wherein
X
Oxygen, sulfur or -CH 2 -,
Y
Chlorine or bromine,
Z
SO 2 H, NO 2 or C 1 -C 4 alkyl,
r
0 to 3,
O
0 to 3,
p
0 or 1,
m
0 or 1 and
n
0 or 1 mean
and contains a surfactant.

Gegebenenfalls enthält der Waschmittelzusatz neben dem quellfähigen Schichtsilikat, der antimikrobiellen Wirksubstanz und dem Tensid ein Alkalisalz, wie z.B. Alkalisulfat, Alkalicarbonat oder Alkali(poly)phosphat.The detergent additive may contain, in addition to the swellable layered silicate, the antimicrobial active substance and the surfactant an alkali salt, e.g. Alkali sulfate, alkali carbonate or alkali (poly) phosphate.

Der erfindungsgemässe Waschmittelzusatz enthält vorzugsweise

  • (a) 5 bis 60 Gew.% quellfähiges Schichtsilikat;
  • (b) 5 bis 35 Gew.% Tensid;
  • (c) 0,1 bis 20 Gew.% einer antimikrobiellen Wirksubstanz; und
  • (c) 0 bis 60 Gew.% Alkalisalz.
    • The detergent additive according to the invention preferably contains
  • (a) 5 to 60% by weight of swellable layered silicate;
  • (b) 5 to 35 wt% surfactant;
  • (c) 0.1 to 20% by weight of an antimicrobial active substance; and
  • (c) 0 to 60 wt% alkali salt.

    • Vorzugsweise stellt das quellfähige Schichtsilikat ein natürliches oder synthetisches Tonmineral oder ein synthetisches schichtförmiges Natriumsilikat dar. Das quellfähige Tonmineral ist vorzugsweise Montmorillonit, Beidelit, Saponit oder Hectorit.The swellable layered silicate is preferably a natural or synthetic clay mineral or a synthetic layered sodium silicate. The swellable clay mineral is preferably montmorillonite, beidelite, saponite or hectorite.

    Ganz besonders wird als Schichtsilicat feingemahlener Bentonit verwendet. Bentonit enthält als Hauptmineral Montmorillonit, welcher ein quellfähiges dioktaedrisches natürliches Schichtsilikat der Formel Na0,66(OH)4Si8(Al3,34·Mg0,66)O20 darstellt. Jeweils eine Schicht setzt sich aus drei Teilelementen zusammen, wobei zwei Tetraederschichten mit Si als Zentralatom eine Oktaederschicht mit Al als Zentralatom einschliessen. Wie aus der allgemeinen Formel ersichtlich, ist Al3+ teilweise isomorph durch Mg2+ ersetzt. Der hierdurch entstehende Ladungsüberschuss wird zwischen den Schichten durch Na+ bzw. Ca2+ ausgeglichen. Der Montmorillonit kann in der Natrium- oder Calciuimform bzw. in Form eines mit Na+ ausgetauschten Calcium-Montmorillonits verwendet werden.Particularly finely ground bentonite is used as the layer silicate. Bentonite contains montmorillonite as its main mineral, which is a swellable dioctahedral natural layered silicate of the formula Na 0.66 (OH) 4 Si 8 (Al 3.34Mg 0.66 ) O 20 represents. One layer is composed of three sub-elements, with two tetrahedral layers with Si as the central atom and an octahedron layer with Al as the central atom. As can be seen from the general formula, Al 3+ is partly isomorphically replaced by Mg 2+ . The resulting excess charge is balanced between the layers by Na + or Ca 2+ . The montmorillonite can be used in the sodium or calcium form or in the form of a calcium montmorillonite exchanged with Na + .

    Das Bentonitpulver weist vorzugsweise einen Restfeuchtegehalt von etwa 10 Gew.% und einen Siebrückstand von maximal 30% auf 45µm auf.The bentonite powder preferably has a residual moisture content of about 10% by weight and a sieve residue of a maximum of 30% to 45µm.

    Neben diesen natürlichen Mineralien können auch synthetisch hergestellte Tonmineralien aus den vorstehend genannten Gruppen eingesetzt werden, wie z.B. synthetische schichtförmige Natriumsilicate (z.B. das Handelsprodukt SKS 6 der Firma Hoechst AG).In addition to these natural minerals, synthetically produced clay minerals can also be used from the groups mentioned above, such as synthetic layered sodium silicates (e.g. the commercial product SKS 6 from Hoechst AG).

    Das Schichtsilikat wird vorzugsweise in einer Menge von 10 bis 50 Gew.%, insbesondere 30 bis 50 Gew.% eingesetzt.The layered silicate is preferably used in an amount of 10 to 50% by weight, in particular 30 up to 50% by weight.

    Die quellfähigen Schichtsilikate besitzen die Eigenschaft, unter innerkristalliner Quellung polare Agenzien zwischen die Silicatlamellen zu intercalieren, was sich bei höheren Konzentrationen in einer Erhöhung des Schichtabstands bemerkbar macht. The swellable layered silicates have the property of swelling within crystals Polar agents intercalate between the silicate lamellae, which can be seen at higher concentrations noticeable in an increase in the layer spacing.

    Vorzugsweise ist das erfindungsgemäss verwendete Tensid ein anionisches oder nichtionogenes Tensid.The surfactant used according to the invention is preferably an anionic or nonionic Surfactant.

    Als anionische Tenside kommen vorzugsweise Verbindungen in Betracht, die aus der Gruppe der

    • sauren Ester oder deren Salze von Alkylenoxidaddukten der Formel
      Figure 00040001
      worin
    • X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure, wie z.B. Schwefelsäure oder vorzugsweise Phosphorsäure, oder auch den Rest einer organischen Säure und
    • Y C1-C12-Alkyl, Aryl oder Aralkyl bedeuten,
    • "Alkylen" für den Ethylenrest oder Propylenrest steht, und
    • m 1 bis 4 und
    • n 4 bis 50 sind;
    • Polystyrolsulfonate,
    • Fettsäuretauride,
    • alkylierten Diphenyloxid-mono- oder di-sulfonate,
    • Sulfonate von Polycarbonsäureestern,
    • mit einer organischen Dicarbonsäure, oder einer anorganischen mehrbasischen Säure in einen sauren Ester übergeführte Anlagerungsprodukte von 1 bis 60, vorzugsweise 2 bis 30 Mol, Ethylenoxid und/oder Propylenoxid an Fettamine, Fettamide, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen,
    • Ligninsulfonate und
    • Formaldehyd-Kondensationsprodukte ausgewählt sind.
    As anionic surfactants, preference is given to compounds which come from the group of
    • acidic esters or their salts of alkylene oxide adducts of the formula
      Figure 00040001
      wherein
    • X is the acid residue of an inorganic, oxygen-containing acid, such as sulfuric acid or preferably phosphoric acid, or the rest of an organic acid and
    • YC 1 -C 12 alkyl, aryl or aralkyl,
    • "Alkylene" represents the ethylene radical or propylene radical, and
    • m 1 to 4 and
    • n is 4 to 50;
    • polystyrene sulfonates,
    • taurides,
    • alkylated diphenyl oxide mono- or disulfonates,
    • Sulfonates of polycarboxylic acid esters,
    • adducts of 1 to 60, preferably 2 to 30 mol, ethylene oxide and / or propylene oxide with fatty amines, fatty amides, fatty acids or fatty alcohols, each with 8 to 22 carbon atoms or with three- to hexavalent alkanols with 3 to 6 carbon atoms,
    • Lignin sulfonates and
    • Formaldehyde condensation products are selected.

    Als nichtionogene Tenside kommen vorzugsweise Fettalkohol-Ethoxylate der Formel (2)   R-O-(EO)y-H, in Betracht, worin

    R
    einen Kohlenwasserstoffrest von 10 bis 18, insbesondere 12 bis 18 Kohlenstoffatomen; oder einen Rest der Formel (2a)
    Figure 00050001
    EO
    eine Ethylenoxidgruppe;
    Y1
    C1-C12-Alkyl, Aryl oder Aralkyl;
    m1
    1 bis 4;
    und
    y
    eine Zahl von 2 bis 20, insbesondere von 3 bis 10;
    bedeuten.Preferred nonionic surfactants are fatty alcohol ethoxylates of the formula (2) RO- (EO) y -H, considering where
    R
    a hydrocarbon radical of 10 to 18, in particular 12 to 18, carbon atoms; or a radical of the formula (2a)
    Figure 00050001
    EO
    an ethylene oxide group;
    Y 1
    C 1 -C 12 alkyl, aryl or aralkyl;
    m 1
    1 to 4;
    and
    y
    a number from 2 to 20, in particular from 3 to 10;
    mean.

    Weiterhin können als nichtionogene Tenside

    • Alkylenoxidaddukte an gesättigte oder ungesättigte 1-6-wertige aliphatische Alkohole, Fettsäuren, Fettamine, Fettamide, Diamine und Sorbitanester,
    • Alkylenoxid-Kondensationsprodukte (Blockpolymerisate),
    • Polymerisate von Vinylpyrrolidon, Vinylacetat oder Vinylalkohol und
    • Co- oder Terpolymere von Vinylpyrrolidon mit Vinylacetat und/oder Vinylalkohol erfindungsgemäss eingesetzt werden.
    Can also be used as nonionic surfactants
    • Alkylene oxide adducts with saturated or unsaturated 1-6-valent aliphatic alcohols, fatty acids, fatty amines, fatty amides, diamines and sorbitan esters,
    • Alkylene oxide condensation products (block polymers),
    • Polymers of vinyl pyrrolidone, vinyl acetate or vinyl alcohol and
    • Copolymers or terpolymers of vinylpyrrolidone with vinyl acetate and / or vinyl alcohol are used according to the invention.

    Es können auch gezielt Mischungen aus den oben genannten anionischen und nichtionogenen Tensiden hergestellt und erfindungsgemäss verwendet werden.Mixtures of the above-mentioned anionic and nonionic can also be used Surfactants are produced and used according to the invention.

    Bevorzugt werden nichtionogene Tenside der Formel (2) eingesetzt, worin

    R
    C12-C15-Alkyl; oder einen Rest der Formel (2a); und
    y
    3 bis 10;
    bedeuten.Nonionic surfactants of the formula (2) are preferably used, in which
    R
    C 12 -C 15 alkyl; or a radical of the formula (2a); and
    y
    3 to 10;
    mean.

    Die Fettalkohol-Ethoxylate werden zwischen den Schichten eingelagert. Die nichtionogenen Tenside, in denen die antimikrobiellen Wirksubstanzen löslich sind, begünstigen deren Transport zwischen den Lamellen des quellfähigen Schichtsilicats. Die antimikrobiellen Wirksubstanzen werden zwischen den Lamellen des Schichtsilicats intercaliert und so vor der Reaktion mit anderen Waschmittelbestandteilen geschützt. The fatty alcohol ethoxylates are stored between the layers. The non-ionic Surfactants in which the antimicrobial active substances are soluble favor them Transport between the lamellae of the swellable layered silicate. The antimicrobial Active substances are intercalated between the layers of the layered silicate and so before protected from reaction with other detergent ingredients.

    Die mit Tensiden und der antimikrobiellen Wirksubstanz intercalierten Schichtsilikate in Granulatform quellen in Wasser auf und geben die Tenside und antimikrobielle Wirksubstanz der Lösung in Wasser frei. Durch die Quellwirkung des Schichtsilicats-Agglomerats in Wasser werden die Agglomerate gesprengt und im Wasser verteilt.Layered silicates intercalated with surfactants and the antimicrobial active ingredient in Granulate form swell in water and give the tensides and antimicrobial active substance the solution in water free. Due to the swelling effect of the layered silicate agglomerate in Water, the agglomerates are blown up and distributed in the water.

    Bei den antimikrobiellen Wirksubstanzen handelt es sich um Verbindungen der Formel

    Figure 00060001
    worin

    X
    Sauerstoff, Schwefel oder -CH2-,
    Y
    Chlor oder Brom,
    Z
    SO2H,NO2 oder C1-C4-Alkyl,
    r
    0 bis 3,
    0
    0 bis 3,
    p
    0 oder 1,
    m
    0 oder 1 und
    n
    0 oder 1 bedeuten.
    The antimicrobial active substances are compounds of the formula
    Figure 00060001
    wherein
    X
    Oxygen, sulfur or -CH 2 -,
    Y
    Chlorine or bromine,
    Z
    SO 2 H, NO 2 or C 1 -C 4 alkyl,
    r
    0 to 3,
    0
    0 to 3,
    p
    0 or 1,
    m
    0 or 1 and
    n
    0 or 1 mean.

    Solche Verbindungen sind in WO-A-96/06153 beschrieben.Such compounds are described in WO-A-96/06153.

    Besonders interessant sind Verbindungen der Formel (3), worin

    X
    Sauerstoff, Schwefel oder -CH2- und
    Y
    Chlor oder Brom,
    m
    0,
    n
    0 oder 1,
    o
    1 oder 2,
    r
    1 oder 2 und
    p
    0
    bedeuten.Compounds of the formula (3) in which
    X
    Oxygen, sulfur or -CH 2 - and
    Y
    Chlorine or bromine,
    m
    0
    n
    0 or 1,
    O
    1 or 2,
    r
    1 or 2 and
    p
    0
    mean.

    Besonders interessante Diphenylether entsprechen der Formel

    Figure 00070001
    worin

    X
    -O- oder -CH2-;
    m
    1 bis 3; und
    n
    1 oder 2;
    bedeuten.Particularly interesting diphenyl ethers correspond to the formula
    Figure 00070001
    wherein
    X
    -O- or -CH 2 -;
    m
    1 to 3; and
    n
    1 or 2;
    mean.

    Ganz besonders bevorzugt ist die Verbindung -2,4,4'-Trichloro-2-hydroxydiphenylether (Triclosan), entsprechend der Formel

    Figure 00070002
    oder die Verbindung der Formel
    Figure 00070003
    (Diclosan).The compound -2,4,4'-trichloro-2-hydroxydiphenyl ether (triclosan) is very particularly preferred, according to the formula
    Figure 00070002
    or the compound of the formula
    Figure 00070003
    (Diclosan).

    Der erfindungsgemässe Waschmittelzusatz kann eine oder eine Mischung von mehreren antimikrobiellen Wirksubstanzen enthalten. The detergent additive according to the invention can be one or a mixture of several contain antimicrobial active substances.

    Als Alkalisalze kommen insbesondere Alkalisulfat, Alkalicarbonat oder Alkali(poly)phosphat in Form ihrer Natrium- oder Kaliumsalze in Betracht. Ganz besonders bevorzugt ist Natriumsulfat.Alkali salts include in particular alkali sulfate, alkali carbonate or alkali (poly) phosphate in the form of their sodium or potassium salts. Is very particularly preferred Sodium sulfate.

    Das Alkalisalz erfüllt mehrere Funktionen: wird das Schichtsilikat mit dem Tensid agglomeriert, so erhält man ein weiches, mit zunehmendem Gehalt an Tensid klebriges Agglomerat, das nicht rieselfähig und nicht silierfähig ist. Durch die Anwesenheit des Alkalisalzes wird die mechanische Stabilität des Agglomerats verbessert und dessen Klebrigkeit vermindert. Ausserdem ist das Alkalisalz im Waschmittel als Builderkomponente erwünscht. Das Alkalisalz wird vorzugsweise in Mengen von etwa 10 bis 40 Gew.%, insbesondere von ca. 12 bis 30 Gew.% verwendet.The alkali salt fulfills several functions: if the layered silicate is agglomerated with the surfactant, this gives a soft agglomerate that becomes sticky with increasing surfactant content, that is not free-flowing and not capable of ensiling. Due to the presence of the alkali salt the mechanical stability of the agglomerate is improved and its stickiness reduced. In addition, the alkali salt in the detergent is desirable as a builder component. The Alkali salt is preferably used in amounts of approximately 10 to 40% by weight, in particular approximately 12 up to 30% by weight.

    Wegen der hygroskopischen Eigenschaften des Tensids können die Agglomerat-Teilchen des erfindungsgemässen Waschmittelzusatzes vorzugsweise mit synthetischem Zeolith oder schichtförmigem Natriumsilicat umhüllt werden, wodurch die Rieselfähigkeit der Agglomerat-Teilchen. verbessert wird. Die Umhüllung mit Zeolith oder schichtförmigem Natriumsilicat verbessert weiterhin den Weissgrad des Agglomerats.Because of the hygroscopic properties of the surfactant, the agglomerate particles of the detergent additive according to the invention preferably with synthetic zeolite or layered sodium silicate are encased, thereby increasing the flowability of the agglomerate particles. is improved. The coating with zeolite or layered sodium silicate further improves the whiteness of the agglomerate.

    Das Agglomerat hat vorzugsweise eine Schüttdichte von mehr als 700 g/l und ist aufgrund dieser hohen Schüttdichte mit hochkonzentrierten Waschmitteln mit hoher Dichte kompatibel.The agglomerate preferably has a bulk density of more than 700 g / l and is due to This high bulk density is compatible with highly concentrated, high density detergents.

    Gegenstand der vorliegenden Erfindung ist weiterhin ein Verfahren zur Herstellung des vorstehend beschriebenen Waschmittelzusatzes in Agglomeratform. Das Verfahren ist dadurch gekennzeichnet, dass man

  • (a) die antimikrobielle Wirksubstanz als wässrige Dispersion gleichzeitig mit dem Tensid zu dem Schichtsilikat gibt oder
  • (b) mindestens einen Teil der antimikrobiellen Wirksubstanz zuvor in dem Tensid löst und die Lösung dem Schichtsilicat zusetzt.
    • The present invention furthermore relates to a process for producing the detergent additive described above in agglomerate form. The process is characterized in that one
  • (a) the antimicrobial active substance is added to the layered silicate as an aqueous dispersion simultaneously with the surfactant or
  • (b) previously dissolves at least part of the antimicrobial active substance in the surfactant and the solution is added to the layered silicate.

    • Vorzugsweise mischt man das quellfähige Schichtsilikat vor der Zugabe der antimikrobiellen Wirksubstanz/Tensids mit dem Alkalisalz. The swellable layered silicate is preferably mixed before the antimicrobial is added Active substance / surfactant with the alkali salt.

    Die Pulverkomponenten können z.B. in einem Intensivmischer, z.B. in einem Eirich-Mischer miteinander gemischt werden. Anschliessend werden gleichzeitig oder nacheinander die antimikrobielle Wirksubstanz (bevorzugt als wässrige Dispersion) und das Tensid unter Durchwirbelung zu der Pulverkomponente gegeben. Hierbei bildet sich ein Agglomerat, welches bei niedriger Mischgeschwindigkeit mit dem Zeolith oder einem schichtförmigen Natriumsilicat abgepudert wird. Das entstandene Agglomerat wird gesiebt und kann durch Zugabe von weiterem Zeolith (insbesondere Zeolith P) oder schichtförmigem Natriumsilicat in Pulverform oberflächlich zur Verringerung der Klebrigkeit beschichtet werden.The powder components can e.g. in an intensive mixer, e.g. in an Eirich mixer be mixed together. Subsequently, the antimicrobial active substance (preferably as an aqueous dispersion) and the surfactant under Whirling is added to the powder component. This forms an agglomerate which at low mixing speed with the zeolite or a layered Sodium silicate is powdered. The resulting agglomerate is sieved and can pass through Addition of further zeolite (in particular zeolite P) or layered sodium silicate coated in powder form on the surface to reduce stickiness.

    Das erhaltene Agglomerat ist in Wasser gut dispergierbar. Die antimikrobielle Wirksub stanz ist vor den im Waschmittel enthaltenen Oxidationsmitteln geschützt und nach der Auflösung des Agglomerats in der Waschlauge verfügbar.The agglomerate obtained is readily dispersible in water. The antimicrobial substance is protected from the oxidizing agents contained in the detergent and after dissolution of the agglomerate available in the wash liquor.

    Gegenstand der vorliegenden Erfindung ist ferner ein Waschmittel, enthaltend den vorstehend beschriebenen Waschmittelzusatz neben üblichen Waschmittelkomponenten, wie anionische und nichtionogene Tenside, Gerüstsubstanzen (Builder), Polymere (Co-Builder), Vergrauungsinhibitoren, Bleichmittel und Bleichmittelaktivatoren, Enzyme, Schauminhibitoren, optische Aufheller sowie Duftstoffe und/oder Farbstoffe.The present invention further relates to a detergent containing the above Detergent additive described in addition to conventional detergent components, such as anionic and non-ionic surfactants, builders (builders), polymers (co-builders), Graying inhibitors, bleaches and bleach activators, enzymes, foam inhibitors, optical brighteners and fragrances and / or dyes.

    Das bevorzugte Herstellungsverfahren ist nachfolgend beschrieben.The preferred manufacturing process is described below.

    Das pulverförmige Schichtsilikat und das pulverförmige Natriumsalz werden intensiv vorgemischt. Unter intensiver Durchwirbelung der Pulvermischung wird das Tensid oder eine Lösung des Tensids zugegeben. Gleichzeitig wird die antimikrobielle Wirksubstanz bzw. ein Gemisch verschiedener antimikrobieller Wirksubstanzen als wässrige Dispersion (slurry) zugegeben. Alternativ kann eine Lösung der antimikrobiellen Wirksubstanz in einer Tensidlösung zu dem Pulvergemisch gegeben werden.The powdered layered silicate and the powdered sodium salt become intense premixed. With intensive swirling of the powder mixture, the surfactant or a Solution of the surfactant added. At the same time, the antimicrobial active substance becomes a Mixture of various antimicrobial active substances as an aqueous dispersion (slurry) added. Alternatively, a solution of the antimicrobial active substance in one Surfactant solution can be added to the powder mixture.

    Wird die antimikrobielle Wirksubstanz als wässrige Dispersion zugegeben, so agglomeriert die Mischung bei einem Wassergehalt von etwa 20 bis 30 Gew.%, bezogen auf die Gesamtmischung. Nach einer Mischzeit von ca. 2 bis 5 Minuten erhält man ein Agglomerat, das in einem geeigneten Trockner, vorzugsweise in einem Fliessbetttrockner auf einen Restwassergehalt von ca. 2 bis 15 Gew.%, vorzugsweise von ca. 5 bis 10 Gew.% getrocknet wird. Das erhaltene Agglomerat wird mit einer Siebmaschine auf eine Teilchengrösse von ca. 0,2 bis 2,5 mm, vorzugsweise von 0,5 bis 1,7 mm gesiebt. Die Fraktion <0,2 mm wird erneut der Agglomeration zugeführt. Entstehendes grobes Korn wird mit einem Walzenbrecher zerkleinert und erneut auf die Siebanlage gegeben.If the antimicrobial active substance is added as an aqueous dispersion, it agglomerates the mixture at a water content of about 20 to 30% by weight, based on the total mixture. After a mixing time of approx. 2 to 5 minutes, an agglomerate is obtained which is in a suitable dryer, preferably in a fluid bed dryer to a residual water content from about 2 to 15% by weight, preferably from about 5 to 10% by weight becomes. The agglomerate obtained is sieved to a particle size of about 0.2 to 2.5 mm, preferably sieved from 0.5 to 1.7 mm. The fraction becomes <0.2 mm fed back to the agglomeration. Coarse grain is removed with a roller crusher crushed and placed again on the screening plant.

    Wird ein Teil der antimikrobiellen Wirksubstanz mit dem Tensid zu dem Pulvergemisch gegeben, so wird zunächst die antimikrobielle Wirksubstanz in Pulverform im Tensid gelöst. Das Gewichtsverhältnis zwischen Tensid und antimikrobieller Wirksubstanz kann 15:2 bis 4:10, vorzugsweise 10:3 bis 10:8 betragen. Die Lösung bzw. Dispersion der antimikrobiellen Wirksubstanz im Tensid wird unter intensiver Durchwirbelung zum Pulver gegeben, wobei gleichzeitig weitere Anteile der antimikrobiellen Wirksubstanz in wässriger Dispersion zugegeben werden.If part of the antimicrobial active substance with the surfactant is added to the powder mixture, the antimicrobial active substance is first dissolved in powder form in the surfactant. The weight ratio between surfactant and antimicrobial active substance can be 15: 2 to 4:10, preferably 10: 3 to 10: 8. The solution or dispersion of the antimicrobial Active substance in the surfactant is added to the powder with intensive swirling, whereby at the same time further portions of the antimicrobial active substance in aqueous dispersion were added become.

    Nach einer Mischzeit von ca. 2 bis 5 Minuten bildet sich ein Agglomerat, welches jedoch durch die Anwesenheit des Tensids etwas klebrig sein kann und deshalb zu Anbackungen neigt. Durch Zugabe von ca. 0,5 bis 5 Gew.% eines synthetischen Zeoliths oder eines feinkörnigen Natriumsilicats (z.B. des Handelsprodukts SKS 6 der Firma Hoechst AG) während der letzten 30 Sekunden des Agglomerationsprozesses wird die Klebrigkeit des Agglomerats soweit herabgesetzt, dass das Agglomerat im Fliessbett getrocknet und wie beschrieben, abgesiebt werden kann.After a mixing time of approx. 2 to 5 minutes, an agglomerate forms, which however can be a little sticky due to the presence of the surfactant and therefore cause caking inclines. By adding approx. 0.5 to 5% by weight of a synthetic zeolite or a fine-grained one Sodium silicate (e.g. the commercial product SKS 6 from Hoechst AG) during The last 30 seconds of the agglomeration process will make the agglomerate sticky reduced so far that the agglomerate dried in the fluid bed and as described, can be screened.

    Als zusätzlicher Schritt kann das abgesiebte Agglomerat in einen Trommelmischer (z.B. einem Trommelmischer der Firma Telschig) oder einen Granulierteller gegeben werden. Dann werden ca. 3 bis 15 Gew.%, vorzugsweise ca. 5 bis 10 Gew.% eines synthetischen Zeoliths oder eines synthetischen Schichtsilikats in feinkörniger Form zugegeben. Die mittlere Teilchengrösse dieses Pulvers soll vorzugsweise <20 µm, insbesondere 3 bis 10 µm betragen. Beim Mischen des Agglomerats mit dem Pulver lagert sich letzteres an der äusseren Oberfläche des Agglomerats an.As an additional step, the screened agglomerate can be placed in a drum mixer (e.g. a drum mixer from Telschig) or a granulating plate. Then about 3 to 15% by weight, preferably about 5 to 10% by weight, of a synthetic Zeolite or a synthetic layered silicate added in fine-grained form. The average particle size of this powder should preferably be <20 μm, in particular 3 to 10 μm be. When the agglomerate is mixed with the powder, the powder settles on the powder outer surface of the agglomerate.

    Der so hergestellte erfindungsgemässe Waschmittelzusatz hat eine Schüttdichte, die grösser ist als 700 g/l, so dass er mit Waschmitteln hoher Schüttdichte kompatibel ist. Durch die Quellwirkung des im Waschmittelzusatz enthaltenen Schichtsilikats zerfallen die Agglomerate rasch in Wasser. Die Aktivkomponenten Tensid und antimikrobielle Wirksubstanz sind damit im Waschmittel verfügbar. Durch die Anwesenheit von Schichtsilikat und Alkalisalz ist das Agglomerat mechanisch stabil. Das Agglomerat lässt sich nachträglich dem Waschmittel beimischen, wodurch wesentliche Teile der Waschmittel-Produktionsanlage nicht mit der antimikrobiellen Wirksubstanz kontaminiert werden.The detergent additive according to the invention thus produced has a bulk density that is greater than 700 g / l, so that it is compatible with detergents with a high bulk density. By the swelling effect of the layered silicate contained in the detergent additive disintegrates Agglomerates quickly in water. The active components surfactant and antimicrobial active substance are therefore available in the detergent. Due to the presence of layered silicate and alkali salt the agglomerate is mechanically stable. The agglomerate can be subsequently Add detergent, which makes up essential parts of the detergent production system not be contaminated with the antimicrobial active substance.

    Ein weiterer Vorteil des erfindungsgemässen Waschmittelzusatzes besteht darin, dass durch das Aufbringen auf einen Träger die Dosiergenauigkeit der Wirksubstanz bei der Waschmittelherstellung erhöht wird.Another advantage of the detergent additive according to the invention is that the application to a carrier the dosing accuracy of the active substance in the production of detergents is increased.

    Die nachfolgenden Beispiele erläutern die Erfindung, ohne sie auf diese zu beschränken.The following examples illustrate the invention without restricting it to them.

    Herstellung des erfindungsgemässen WaschmittelzusatzesProduction of the detergent additive according to the invention Beispiel 1:Example 1:

    60 g60 g Bentonit werden mitBe bentonite with 20,0 g20.0 g Natriumsulfat (wasserfrei) in einem Mixerglas mit Flügelrüher ca. 2 min verrührt. Innerhalb einer Minute lässt man eine Lösung ausSodium sulfate (anhydrous) stirred in a blender with a mixer for approx. 2 min. A solution is left out within a minute 20,1 g20.1 g einer 15%igen Lösung von Triclosan in C12-C15-Oxoalkoholethoxylat mit 5 Ethylenoxideinheiten zutropfen. Das zum Teil körnige Gemisch wird für ca. 1,5 Minuten im Mixer gut gemischt, wobei es sich stark erwärmt. Jetzt gibt manAdd a 15% solution of triclosan in C 12 -C 15 oxo alcohol ethoxylate with 5 ethylene oxide units. The partly granular mixture is mixed well in the mixer for approx. 1.5 minutes, during which it heats up considerably. Now you give 8,1 g8.1 g deionisiertes Wasser tropfenweise über das Loch im Mixerglas hinzu und vermengt die Masse gut. Es entsteht ein gräuliches Granulat.Deionized water is added dropwise through the hole in the blender glass and mixes the mass well. A grayish granulate is formed.

    Das Muster wird 4 Stunden bei 65°C im Vakuum getrocknet und anschliessend über 3 Siebe mit Maschenweiten von 2, 1 und 0,5 mm gesiebt.The sample is dried for 4 hours at 65 ° C in a vacuum and then over 3 sieves sieved with mesh sizes of 2, 1 and 0.5 mm.

    Beispiel 2Example 2

    60 g Bentonit werden mit 20,0 g Natriumsulfat (wasserfrei) in einem Mixerglas mit Flügelrüher ca. 2 min verrührt. Innerhalb einer Minute lässt man eine Lösung aus 20,1 g einer 15%igen Lösung von Triclosan in Nonylphenylethoxylat mit 6,5 Ethylenoxideinheiten zutropfen. Das zum Teil körnige Gemisch wird für ca. 1,5 Minuten im Mixer gut gemischt, wobei es sich stark erwärmt. Jetzt gibt man 5,4 g deionisiertes Wasser tropfenweise über das Loch im Mixerglas hinzu und vermengt die Masse gut. Es entsteht ein gräuliches Granulat. Das Muster wird 4 Stunden bei 65°C im Vakuum getrocknet und anschliessend über 3 Siebe mit Maschenweiten von 2, 1 und 0,5 mm gesiebt. 60 g Be bentonite with 20.0 g Sodium sulfate (anhydrous) stirred in a blender with a mixer for approx. 2 min. A solution is left out within a minute 20.1 g a 15% solution of triclosan in nonylphenyl ethoxylate with 6.5 ethylene oxide units. The partly granular mixture is mixed well in the mixer for approx. 1.5 minutes, during which it heats up considerably. Now you give 5.4 g Deionized water is added dropwise through the hole in the blender glass and mixes the mass well. A grayish granulate is formed. The sample is dried in a vacuum at 65 ° C. for 4 hours and then sieved through 3 sieves with mesh sizes of 2, 1 and 0.5 mm.

    Beispiel 3Example 3

    60 g Bentonit werden mit 20,0 g Natriumsulfat (wasserfrei) in einem Mixerglas mit Flügelrüher ca. 2 min verrührt. Innerhalb einer Minute lässt man eine Lösung aus 20,1 g einer 15%igen Lösung von Triclosan in C12-C15-Oxoalkoholethoxylat mit 5 Ethylenoxideinheiten zutropfen. Das zum Teil körnige Gemisch wird für ca. 1,5 Minuten im Mixer gut gemischt, wobei es sich stark erwärmt. Jetzt gibt man 8,1g deionisiertes Wasser tropfenweise über das Loch im Mixerglas hinzu und vermengt die Masse gut. Es entsteht ein gräuliches Granulat. Das Muster wird 4 Stunden bei 65°C im Vakuum getrocknet und anschliessend über 3 Siebe mit Maschenweiten von 2, 1 und 0,5 mm gesiebt. 60 g Be bentonite with 20.0 g Sodium sulfate (anhydrous) stirred in a blender with a mixer for approx. 2 min. A solution is left out within a minute 20.1 g dropwise a 15% solution of triclosan in C 12 -C 15 oxo alcohol ethoxylate with 5 ethylene oxide units. The partly granular mixture is mixed well in the mixer for approx. 1.5 minutes, during which it heats up considerably. Now you give 8.1 g Deionized water is added dropwise through the hole in the blender glass and mixes the mass well. A grayish granulate is formed. The sample is dried in a vacuum at 65 ° C. for 4 hours and then sieved through 3 sieves with mesh sizes of 2, 1 and 0.5 mm.

    Beispiel 4Example 4

    60 g60 g Bentonit werden mitBe bentonite with 20,0 g20.0 g Natriumsulfat (wasserfrei) in einem Mixerglas mit Flügelrüher ca. 2 min verrührt. Innerhalb einer Minute lässt man eine Lösung ausSodium sulfate (anhydrous) stirred in a blender with a mixer for approx. 2 min. A solution is left out within a minute 20,0 g20.0 g einer 15%igen Lösung von Triclosan in Nonylphenylethoxylat mit 6,5 Ethylenoxideinheiten zutropfen. Das zum Teil körnige Gemisch wird für ca. 1,5 Minuten im Mixer gut gemischt, wobei es sich stark erwärmt. Jetzt gibt mana 15% solution of triclosan in nonylphenyl ethoxylate with 6.5 ethylene oxide units. The partly granular mixture is mixed well in the mixer for approx. 1.5 minutes, during which it heats up considerably. Now you give 5,4 g5.4 g deionisiertes Wasser tropfenweise über das Loch im Mixerglas hinzu und vermengt die Masse gut. Es entsteht ein gräuliches Granulat.Deionized water is added dropwise through the hole in the blender glass and mixes the mass well. A grayish granulate is formed.

    Das Muster wird 4 Stunden bei 65°C im Vakuum getrocknet und anschliessend über 3 Siebe mit Maschenweiten von 2, 1 und 0,5 mm gesiebt.The sample is dried for 4 hours at 65 ° C in a vacuum and then over 3 sieves sieved with mesh sizes of 2, 1 and 0.5 mm.

    Beispiele 5 bis 10: Man verfährt wie in den Beispielen 1 bis 4 beschreiben, verwendet aber anstelle von Triclosan die folgenden Verbindungen: Beispiel antimikrobielle Wirksubstanz 5 Diclosan (Verbindung der Formel (6)) 6 Dichlorophen Examples 5 to 10: The procedure is as described in Examples 1 to 4, but the following compounds are used instead of triclosan: example antimicrobial active substance 5 Diclosan (compound of formula (6)) 6 dichlorophen

    Beispiel 7: Bestimmung der Oxidationsstabilität von Triclosan in verschiedenen Triclosan-Bentonit-Compound/WaschmittelmischungenExample 7: Determination of the oxidation stability of triclosan in various triclosan-bentonite compound / detergent mixtures

    Durchführung: Zur Herstellung einer Waschmittelformulierung werden die in den Beispielen 1 bis 4 hergestellten Waschmittelzusätze eingesetzt. Implementation : The detergent additives prepared in Examples 1 to 4 are used to prepare a detergent formulation.

    Die einzelnen Waschmittelzusätze werden trocken mit einer Standard-Waschmittelmischung gemischt, ebenso wird eine Referenzmischung Triclosan/Standardwaschmittel hergestellt. Die so hergestellten Waschmittel haben folgende Zusammensetzung:

    x %
    Waschmittelzusatz
    12 %
    Na-Perborat x 1 H2O
    3 %
    TAED
    ad 100% ECE (= Standardwaschmittel der Firma Henkel)The individual detergent additives are dry mixed with a standard detergent mixture, as well as a reference mixture Triclosan / standard detergent. The detergents thus produced have the following composition:
    x%
    detergent additive
    12%
    Na perborate x 1 H 2 O
    3%
    TAED
    ad 100% ECE (= standard detergent from Henkel)

    Dieses Waschmittel hat folgende Zusammensetzung (%): Lineares Na-alkylbenzolsulfonat 8,0 Mg-silikat 1,9 Talgalkohol-tetradekan-ethylenglykolether 2,9 Carboxymethylcellulose 1,2 Na-Seife 3,5 EDTA 0,2 Na-triphosphat 43,8 Na-sulfat 21,2 Na-silikat 7,5 Wasser 9,8 This detergent has the following composition (%): Linear Na alkyl benzene sulfonate 8.0 Mg silicate 1.9 Tallow tetra-ethylene glycol ether dean 2.9 carboxymethylcellulose 1.2 Na-soap 3.5 EDTA 0.2 Na-triphosphate 43.8 Na sulphate 21.2 Na-silicate 7.5 water 9.8

    Die Referenzmischung hat folgende Zusammensetzung 0.15 % Triclosan 12 % Na-Perborat x 1 H2O 3 % TAED ECE ad 100%. The reference mixture has the following composition 0.15% triclosan 12% Na perborate x 1 H 2 O 3% TAED ECE ad 100%.

    Der Sollgehalt an Triclosan in den Waschmittelzusammensetzungen wurde vor Testbeginn analytisch bestimmt. Waschmittelzusatz gem Beispiel Menge [%] Triclosan-Startwert [%] Triclosan nach 4 Wochen/60°C [%] 1 5,8 0,16 0,07 2 6,2 0,17 0,08 3 7,3 0,20 0,13 4 8,1 0,21 0,13 Referenz -- 0,15 0,006 The target content of triclosan in the detergent compositions was determined analytically before the start of the test. Detergent additive according to the example Quantity [%] Triclosan starting value [%] Triclosan after 4 weeks / 60 ° C [%] 1 5.8 0.16 0.07 2 6.2 0.17 0.08 3 7.3 0.20 0.13 4 8.1 0.21 0.13 reference - 0.15 0,006

    Die Ergebnisse zeigen, dass die den erfindungsgemässen Waschmittelzusatz enthaltenden Waschmittel signifikant höhere Konzentrationen an antimikrobieller Wirksubstanz (Triclosan) aufweisen und damit wesentlich lagerstabiler sind als Waschmittel, die die antimikrobielle Wirksubstanz tel. quel. enthalten.The results show that those containing the detergent additive according to the invention Detergent significantly higher concentrations of antimicrobial active substance (triclosan) have and are therefore much more stable than detergents that the antimicrobial Active substance tel. quel. contain.

    Claims (14)

    1. Laundry detergent additive in agglomerate form, characterized in that it comprises at least one swellable phyllosilicate, an active antimicrobial substance of the formula
      Figure 00190001
      in which
      X
      is oxygen, sulphur or -CH2-,
      Y
      is chloro or bromo,
      Z
      is SO2H, NO2 or C1-C4 alkyl,
      r
      is 0 to 3,
      o
      is 0 to 3,
      p
      is 0 or 1,
      m
      is 0 or 1 and
      n
      is 0 or 1,
      and a surfactant.
    2. Laundry detergent additive according to Claim 1, characterized in that it further comprises an alkali metal salt.
    3. Laundry detergent additive according to Claim 1 or 2, characterized in that it contains
      (a) from 5 to 60% by weight of swellable phyllosilicate;
      (b) from 5 to 35% by weight of surfactant;
      (c) from 0.1 to 20% by weight of an active antimicrobial substance; and
      (d) from 0 to 60% by weight of alkali metal salt.
    4. Laundry detergent additive according to one of Claims 1 to 3, characterized in that as swellable phyllosilicate it comprises a natural or synthetic clay mineral or a synthetic layered sodium silicate.
    5. Laundry detergent additive according to one of Claims 1 to 4, characterized in that the phyllosilicate is used in an amount of from 10 to 50% by weight.
    6. Laundry detergent additive according to one of Claims 1 to 5, characterized in that the surfactant is selected from the group of anionic and nonionic surfactants.
    7. Laundry detergent additive according to one of Claims 1 to 6, characterized in that suitable nonionic surfactants include fatty alcohol ethoxylates of the formula (2)   R-O-(EO)y-H, in which
      R
      is a hydrocarbon radical of from 10 to 18, in particular from 12 to 18, carbon atoms; or is a radical of the formula (2a)
      Figure 00210001
      EO
      is an ethylene oxide group;
      Y1
      is C1-C12 alkyl or is aryl or aralkyl;
      m1
      is 1 to 4;
      and
      y
      is a number from 2 to 20, in particular from 3 to 10.
    8. Laundry detergent additive according to Claim 7, characterized in that as nonionic surfactant a compound of the formula (2) is used in which
      R
      is C12-C15 alkyl; or is a radical of the formula (2a); and
      y
      is 3 to 10.
    9. Laundry detergent additive according to Claim 8, characterized in that as active antimicrobial substance the compound of the formula (3) is used in which
      X
      is oxygen, sulphur or -CH2- and
      Y
      is chloro or bromo,
      m
      is 0,
      n
      is 0 or 1,
      o
      is 1 or 2,
      r
      is 1 or 2 and
      p
      is 0.
    10. Laundry detergent additive according to Claim 1, characterized in that as active antimicrobial substance the compound of the formula
      Figure 00210002
      is used in which
      X
      is -O- or -CH2-;
      m
      is 1 to 3; and
      n
      is 1 or 2.
    11. Laundry detergent additive according to Claim 10, characterized in that the compound of the formula
      Figure 00220001
      is used.
    12. Laundry detergent additive according to Claim 10, characterized in that the compound of the formula
      Figure 00220002
      is used.
    13. Laundry detergent additive according to one of Claims 1 to 12, characterized in that it comprises alkali metal sulphate as an alkali metal salt.
    14. Process for preparing the laundry detergent additive according to Claim 1, characterized in that
      (a) the active antimicrobial substance is added as an aqueous dispersion simultaneously with the surfactant to the phyllosilicate or
      (b) at least part of the active antimicrobial substance is dissolved beforehand in the surfactant and the solution is added to the phyllosilicate.
    EP19980810888 1997-09-17 1998-09-08 Antimicrobial additive for washing agents Expired - Lifetime EP0903401B1 (en)

    Priority Applications (1)

    Application Number Priority Date Filing Date Title
    EP19980810888 EP0903401B1 (en) 1997-09-17 1998-09-08 Antimicrobial additive for washing agents

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    EP97810672 1997-09-17
    EP97810672 1997-09-17
    EP19980810888 EP0903401B1 (en) 1997-09-17 1998-09-08 Antimicrobial additive for washing agents

    Publications (2)

    Publication Number Publication Date
    EP0903401A1 EP0903401A1 (en) 1999-03-24
    EP0903401B1 true EP0903401B1 (en) 2003-08-06

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    Families Citing this family (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    AU2002229627B2 (en) * 2000-12-14 2006-11-23 Ciba Specialty Chemicals Holding Inc. Surface-active compositions
    CN1949971A (en) * 2004-03-23 2007-04-18 西巴特殊化学制品控股公司 Fungicidal detergent compositions
    WO2006097238A1 (en) * 2005-03-16 2006-09-21 Unilever Plc A soap composition
    EP1987120B2 (en) † 2006-02-24 2013-09-11 Unilever PLC Fast release granules

    Family Cites Families (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB2182051A (en) * 1985-09-10 1987-05-07 Interox Chemicals Ltd Stabilisation of peroxyacids in detergent compositions containing nonionic surfactant
    DE3822479A1 (en) * 1988-07-02 1990-02-08 Henkel Kgaa DETERGENT ADDITIVES WITH IMPROVED SPILLING BEHAVIOR
    GB8823008D0 (en) * 1988-09-30 1988-11-09 Unilever Plc Composition for softening fabrics
    DE4009618A1 (en) * 1990-03-26 1991-10-02 Henkel Kgaa SPRAY-DRIED, AVIVATING DETERGENT ADDITIVE
    SK24497A3 (en) * 1994-08-25 1997-07-09 Ciba Geigy Ag Surface-active formulations
    DE19538028A1 (en) * 1995-10-12 1997-04-17 Sued Chemie Ag detergent additive
    JPH09194899A (en) * 1996-01-22 1997-07-29 Lion Corp Particulate nonionic detergent composition and its production

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