EP0544670A1 - Spray-dried brightening additive for washing agents. - Google Patents

Spray-dried brightening additive for washing agents.

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Publication number
EP0544670A1
EP0544670A1 EP91906393A EP91906393A EP0544670A1 EP 0544670 A1 EP0544670 A1 EP 0544670A1 EP 91906393 A EP91906393 A EP 91906393A EP 91906393 A EP91906393 A EP 91906393A EP 0544670 A1 EP0544670 A1 EP 0544670A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
water
composition according
spray
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.)
Granted
Application number
EP91906393A
Other languages
German (de)
French (fr)
Other versions
EP0544670B1 (en
Inventor
Lothar Pioch
Wolfgang Seiter
Elmar Wilms
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication of EP0544670A1 publication Critical patent/EP0544670A1/en
Application granted granted Critical
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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
    • C11D3/02—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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to the production of a granular detergent additive which, due to its content of layered silicates, enhances, i.e. has fabric softening properties. Because of the high proportion of ingredients with builder properties, it also has detergent properties.
  • Detergent additives of the type mentioned are advantageously added to granular detergents in order to modify and improve their properties.
  • the agents according to the invention consist of easily soluble granules which are very resistant to abrasion and breakage and are therefore very suitable for further processing on detergent and cleaning agent mixtures. They have a pronounced adsorption capacity for liquid to pasty detergent constituents, which can be introduced into detergent granules without problems in this way without impairing their free-flowing properties.
  • EP-A 279 040 discloses laundry builders which contain 50 to 80% by weight of finely crystalline zeolite, 5 to 25% by weight of bentonite and 0.5 to 5% by weight of cellulose ether as binders. In addition, up to 5% by weight of sodium sulfate, up to 1% by weight of alkali and up to 5% by weight of nonionic surfactants can be present. The compositions are said to be produced by spray drying an aqueous slurry. None is said about the Aviva effect of the funds. If present at all, it can only be very small, since in practice (examples) the proportion of bentonite is comparatively low at a maximum of 8% by weight and special layered silicates with a finishing effect are not disclosed.
  • the object of the present invention is to provide means and a suitable method for their production, by means of which a sufficient active ingredient content and thus a good softening effect and favorable grain properties are achieved.
  • the invention relates to a spray-dried, aerating detergent additive containing
  • Suitable sheet silicates which belong to the group of smectites which swell with water are, for example, those of the general formulas 2
  • the layered silicates can contain hydrogen, alkali and alkaline earth ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and is dependent on the swelling state or on the type of processing.
  • the particle size is in the range from 0.05 to 25 ⁇ m, usually less than 10 ⁇ m.
  • Layered silicates are preferably used which, for example due to an alkali treatment, are largely free of strongly coloring iron ions and of calcium ions.
  • the layer silicate content of the agents is 12.5 to 20% by weight, preferably 14 to 20% by weight and in particular 15 to 20% by weight.
  • the constituent (B) which is present in proportions of 50 to 65% by weight, preferably 52 to 62% by weight, consists of synthetic sodium aluminosilicate of the zeolite A type containing bound water .
  • Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% of particles smaller than 10 ⁇ m.
  • Your 'calcium binding capacity which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g.
  • the sodium sulfate (C) improves the granulability of the starting mixtures and the dispersing and dissolving behavior of the granules in the wash water. Its content is preferably 3 to 7% by weight.
  • the proportions refer to anhydrous salt. However, this means that some of the moisture contained in the granules can be bound to this salt as water of hydration.
  • the component (-D) consists of a homopolymeric and / or copolymeric carboxylic acid in the form of the sodium salt.
  • Suitable homopolymers are polyacrylic acid and polymethacrylic acid.
  • Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid.
  • copolymers of acrylic acid or methacrylic acid with maleic acid such as are described, for example, in EP 25551 B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
  • the molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000.
  • the proportion of polyacid or its salts increases, the resistance of the grains to abrasion increases. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases.
  • Mixtures with 2 to 7% by weight of sodium salt of polyacid have optimal abrasion properties.
  • the polymers also do one improved builder effect of the mixtures when used.
  • the water content of the granules includes the water which is bound to the zeolite (18 to 22% by weight, based on zeolite) and is adsorbed by the layered silicate, and also the water of hydration of the salts. It is usually 10 to 25% by weight, in particular 12 to 20% by weight.
  • the agents can contain small amounts of compounds which can be added during the production and processing of the synthetic zeolites in order to increase the stability of the aqueous zeolite dispersions (master batch).
  • additives which can be introduced into the compositions with the zeolite, are described in document DE 25 27 388 cited above.
  • These can be nonionic surfactants containing polyglycol ether groups, for example primary alcohols with 12 to 18 carbon atoms reacted with 2 to 7 moles of ethylene oxide.
  • the proportion of stabilizers introduced into the composition via such zeolite dispersions can be, for example, 0.05 to 2% by weight, depending on the proportion of the zeolite. However, this component is not necessary for the desired properties of the granules.
  • Further optional constituents are dyes or colored pigments, which can be added to the agents in the granulation in proportions of, for example, 0.01 to 1% by weight in order to cover a possible gray or brownish intrinsic color of the layered silicates. After the granules have been mixed into a granular detergent, they give it a visually appealing, color-speckled appearance. In the same way, white Use pigments and optical brighteners if a white granulate and a uniform white mixed product are required.
  • Dyes which are degraded in the subsequent washing process are particularly suitable, so that there is no undesired dyeing of the textiles.
  • Examples include the dyes duasyn acid blue ( R ) and duasyn acid green.
  • the granules can be used to adsorb liquid or pasty detergent constituents and to incorporate them into detergent granules without loss of free-flowing properties.
  • these are fatty acid alkanols (which can bring about an additional softening effect or increase washing power) and, in particular, nonionic surfactants of the polyglycol ether derivative type.
  • nonionic surfactants of the polyglycol ether derivative type.
  • nonionic surfactants it is also possible to adsorb oily additives, such as perfumes or foam-suppressing substances from the class of paraffins, microparaffins, long-chain bisacyl diamines and silicones, and mixtures thereof, onto the grains.
  • oily additives such as perfumes or foam-suppressing substances from the class of paraffins, microparaffins, long-chain bisacyl diamines and silicones, and mixtures thereof, onto the grains.
  • the agents are produced by spray drying an aqueous, paste-like batch (slurry) of the constituents by means of heated gases (combustion gases) in conventional drying towers. Since the combustion air, which is widely used as a dry gas, contains comparatively high proportions of carbon dioxide, it can be particulate if small amounts of sodium hydroxide are added to the slurry before spraying, in order to counteract a pH reduction by a corresponding excess of alkali.
  • the recommended proportions of NaOH are usually between 0.1 and 1% by weight.
  • the aqueous batch contains 50 to 65% by weight of water-free ingredients. Its temperature is advantageously 50 to 90 ° C and its viscosity at this working temperature up to 25000 mPa-s, usually 12000 to 20,000 mPa-s.
  • the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar.
  • the drying gas which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent.
  • the inlet temperature measured in the ring channel (ie immediately before entering the lower part of the tower), is 180 to 300 ° C. preferably 220 to 280 ° C.
  • the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 110 ° C., preferably 60 to 100 ° C.
  • the granules produced in this way are notable for very good redispersibility in the aqueous wash liquor. With regard to their activating effect, they are largely identical with agents of the same type produced in another way.
  • the average grain size of the agent produced by spray drying is usually 0.2 to 1.2 mm.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.0 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 2% by weight .-%, in particular less than 1% by weight and the proportion of the grains above 1.5 mm is not more than 15% by weight, in particular not more than 10% by weight.
  • Larger proportions of fine grain favor the formation of dust when mixed with other powder components and should therefore be avoided.
  • Larger proportions of coarse grain cause a lower bulk density and make the product appear visually inconsistent, but are otherwise not disadvantageous.
  • the bulk density of the spray-dried compositions is 500 to 700 g / 1, mostly 550 to 650 g / 1.
  • the agent essentially consists of rounded grains which have a very good flow behavior. This very good flow behavior is still present even when the grains have been impregnated with larger proportions of liquid, semi-liquid or solid nonionic surfactants.
  • the proportion of these adsorbed constituents can be 5 to 30% by weight, preferably 10 to 25% by weight, based on the adsorbate.
  • the starting material was a suspension containing about 50% by weight of water and stabilized with the non-ionic surfactant.
  • the zeolite is calculated to be anhydrous, ie the water content attributable to the zeolite (approx. 20% based on zeolite) is listed under "water”.
  • (D) Copoly eres salt, acrylic acid-maleic acid copolymer, MG 70000, Na salt, product Sokalan ( R ) CP5 from BASF (DE),
  • TA5 means a tallow alcohol reacted with 5 moles of ethylene glycol, used as a dispersion stabilizer for the zeolite dispersion containing 50% by weight.
  • a dianilino-dimorpholino derivative of bis (triazinyl) -stilbene disulfonic acid Na salt) was used as the optical brightener.
  • Example 2 The formulation according to Example 2 was sprayable using stirrers with high torque and a high spray pressure.
  • the recipes according to Examples 1 and 3 could be prepared and spray-dried without special technical effort.
  • the drying gases conducted in countercurrent had an inlet temperature in the ring channel of 263 ° C. (examples 1 and 3) and 267 ° C. (example 2).
  • the temperature in the area of the tower outlet in front of the dust filters was 71 ° C to 72 ° C (Examples 1 and 3) and 76 ° C (Example 2).
  • the atomization pressure was 40 bar in Example 1 and 3 and 49 bar in Example 2.
  • the spray products obtained were free-flowing with an average particle size of 0.35 mm and a dust content (less than 0.05 mm) of less than 0.1% by weight. Grain fractions of over 2 mm were not present.
  • the bulk density was 590 g / 1 in Example 1, 550 g / 1 in Example 2 and 590 g / 1 in Example 3. All spray products were able to use 5 to 30% by weight (based on the end product) of liquid nonionic surfactants in a spray mixing apparatus (Coconut fatty alcohol + 5E0, Ci2-14-oxo alcohol + 7 E0) can be added, the bulk density increasing to 650 to 780 g / l. The flow behavior of the adsorbates thus obtained was unchanged compared to the granules used.
  • the granules were mixed with a granular detergent to give an agent of the following composition (in% by weight):

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A granular additive for washing agents with brightening properties contains (A) 12.5 to 20 wt. % of a laminar silicate, (B) 52 to 65 wt. % of fine crystalline, synthetic zeolite (referred to the anhydrous substance), (C) 2 to 8 wt. % of sodium sulphate (referred to the anhydrous substance), (D) 1.5 to 8 wt. % of a sodium salt of a (meth)acrylic acid homopolymer or copolymer and (E) 0 to 30 wt. % of nonionic tensides from the class of polyglycol ethers, the difference from 100 % consisting of water.

Description

"Sprühgetrocknetes, avivierend wirkendes Waschmitteladditiv""Spray-dried, softening detergent additive"
Die vorliegende Erfindung betrifft die Herstellung eines granulä¬ ren Waschmitteladditivs, das aufgrund seines Gehaltes an Schicht¬ silikaten avivierende, d.h. textilweichmachende Eigenschaften auf¬ weist. Aufgrund des hohen Anteils an Inhaltsstoffen mit BuiIderei¬ genschaften besitzt es zusätzlich waschwirksame Eigenschaften. Waschmitteladditive der genannten Art werden mit Vorteil granu¬ lären Waschmitteln zugemischt, um deren Eigenschaften zu modifi¬ zieren und zu verbessern. Die erfindungsgemäßen Mittel bestehen aus leichtlöslichen Granulaten, die gegen Abrieb und Zerbrechen sehr beständig sind und sich daher sehr gut zur Weiterverarbeitung an Wasch- und Reinigungsmittelgemischen eignen. Sie besitzen ein ausgeprägtes Adsorptionsvermögen für flüssige bis pastöse Wasch¬ mittelbestandteile, die sich auf diese Weise problemlos in Wasch¬ mitteIgranulate einbringen lassen, ohne deren Rieselfähigkeit zu beeinträchtigen.The present invention relates to the production of a granular detergent additive which, due to its content of layered silicates, enhances, i.e. has fabric softening properties. Because of the high proportion of ingredients with builder properties, it also has detergent properties. Detergent additives of the type mentioned are advantageously added to granular detergents in order to modify and improve their properties. The agents according to the invention consist of easily soluble granules which are very resistant to abrasion and breakage and are therefore very suitable for further processing on detergent and cleaning agent mixtures. They have a pronounced adsorption capacity for liquid to pasty detergent constituents, which can be introduced into detergent granules without problems in this way without impairing their free-flowing properties.
Allgemeine Hinweise auf Schichtsilikat-Agglomerate finden sich in DE-A 24 39541 (US 3966629), doch ist diesem Dokument keine spe¬ zielle Lehre zur Herstellung von Granulaten der nachfolgend be¬ schriebenen Zusammensetzung zu entnehmen.General references to layered silicate agglomerates can be found in DE-A 24 39541 (US 3966629), but this document does not provide any specific teaching on the production of granules of the composition described below.
Aus DE-A 35 41 410 (US 4 582615, US 4609 473) sind textilweich- machende Agglomerate aus Bentonit und Natriumsulfat bekannt, ent- haltend 1 Gewichtsteil Natriumsulfat auf 3 bis 5 Gewichtsteile Bentonit. Das Natriumsulfat agiert in diesen Mitteln als Granu¬ lierhilfsmittel. Sein vergleichsweise hoher Anteil stellt einen erheblichen Nachteil dar, da es keine waschenden und reinigenden Eigenschaften aufweist und den Salzgehalt im Abwasser erhöht. Die Herstellung der Mittel- erfolgt durch Granulieren der Bestandteile unter gleichzeitigem Aufsprühen von Wasser, woran sich ein- Trock¬ nen der feuchten Granulate mittels heißer Luft, beispielsweise in einem Wirbelschicht-Trockner (fluid bed dryer) anschließt.DE-A 35 41 410 (US 4 582615, US 4609 473) discloses textile-softening agglomerates of bentonite and sodium sulfate, holding 1 part by weight of sodium sulfate to 3 to 5 parts by weight of bentonite. In these agents, the sodium sulfate acts as a granulating aid. Its comparatively high proportion is a considerable disadvantage since it has no washing and cleaning properties and increases the salt content in the waste water. The agents are produced by granulating the constituents with simultaneous spraying on of water, which is followed by drying of the moist granules by means of hot air, for example in a fluidized bed dryer (fluid bed dryer).
Aus EP-A 279 040 sind Wasch ittelbuilder bekannt, die 50 bis 80 Gew.-% feinkristallinen Zeolith, 5 bis 25 Gew.-% Bentonit und 0,5 bis 5 Gew.-% Celluloseether als Bindemittel enthalten. Zusätzlich können bis 5 Gew.-% Natriumsulfat, bis 1 Gew.-% Alkali und bis 5 Gew.-% nichtionische Tenside anwesend sein. Die Mittel sollen durch Sprühtrocknung einer wäßrigen Aufschlämmung hergestellt wer¬ den. Über eine Avivagewirkung der Mittel wird nichts gesagt. Sie kann, falls überhaupt vorhanden, nur sehr gering sein, da der Ben- tonit-Anteil in der Praxis (Beispiele) mit maximal 8 Gew.-% ver¬ gleichsweise gering ist und spezielle Schichtsilikate mit Avivage¬ wirkung nicht offenbart sind.EP-A 279 040 discloses laundry builders which contain 50 to 80% by weight of finely crystalline zeolite, 5 to 25% by weight of bentonite and 0.5 to 5% by weight of cellulose ether as binders. In addition, up to 5% by weight of sodium sulfate, up to 1% by weight of alkali and up to 5% by weight of nonionic surfactants can be present. The compositions are said to be produced by spray drying an aqueous slurry. Nothing is said about the Aviva effect of the funds. If present at all, it can only be very small, since in practice (examples) the proportion of bentonite is comparatively low at a maximum of 8% by weight and special layered silicates with a finishing effect are not disclosed.
Eine Überprüfung der Angaben hat zudem gezeigt, daß bei einem Ge¬ halt von mehr als 12 bis 15 Gew.-% an avivierend wirkenden Bento- niten eine Sprühtrocknung auf erhebliche technische Probleme stößt. Die Bentonite verursachen zusammen mit den Celluloseethern durch QuellVorgänge einen sehr starken Viskositätsanstieg im Slurry. Der Slurry muß daher, um noch versprühbar zu sein, sehr stark verdünnt werden, beispielsweise auf Wassergehalte von 60 und mehr Gewichtsprozent. Das führt nicht nur zu erhöhtem Energiever¬ brauch, sondern auch zu nachteiligen Produkteigenschaften, da die gesprühten Teilchen während der üblichen Verweilzeit im Turm nicht mehr hinreichend entwässert werden können. Aus den genannten Grün¬ den finden sich in dem zitierten Dokument EP-A 279 040 keine Bei¬ spiele, in denen die Sprühprodukte mehr als 8 Gew.-% Bentonit und mehr als 1 % Celluloseether enthalten. Die beanspruchten Höchst¬ mengen von 25 % Bentonit und 5 % Celluloseether sind daher völlig unrealistisch. Schon weitaus geringere Gehalte erweisen sich als unpraktikabel.A review of the data also showed that spray drying encounters considerable technical problems with a content of more than 12 to 15 wt. Together with the cellulose ethers, the bentonites cause a very strong increase in viscosity in the slurry due to swelling processes. In order to be sprayable, the slurry must therefore be diluted very strongly, for example to water contents of 60 and more percent by weight. This not only leads to increased energy consumption, but also to disadvantageous product properties, since the sprayed particles can no longer be adequately dewatered during the usual dwell time in the tower. For the reasons mentioned, there are no examples in the cited document EP-A 279 040 in which the spray products contain more than 8% by weight of bentonite and more than 1% of cellulose ether. The claimed maximum amounts of 25% bentonite and 5% cellulose ether are therefore completely unrealistic. Far lower salaries prove to be impractical.
Durch die vorliegende Erfindung wird die Aufgabe gelöst, Mittel sowie ein geeignetes Verfahren zu deren Herstellung bereitzustel¬ len, mit denen ein ausreichender Wirkstoffgehalt und somit eine gute avivierende Wirkung sowie günstige Korneigenschaften erzielt werden.The object of the present invention is to provide means and a suitable method for their production, by means of which a sufficient active ingredient content and thus a good softening effect and favorable grain properties are achieved.
Gegenstand der Erfindung ist ein sprühgetrocknetes, avivierend wirkendes Waschmitteladditiv, enthaltendThe invention relates to a spray-dried, aerating detergent additive containing
(A) 12,5 bis 20 Gew.-% eines Schichtsilikates,(A) 12.5 to 20% by weight of a layered silicate,
(B) 50 bis 65 Gew.-% feinkristallinen, synthetischen Zeolith (Anteil auf wasserfreie Substanz bezogen),(B) 50 to 65% by weight of finely crystalline, synthetic zeolite (proportion based on anhydrous substance),
(C) 2 bis 8 Gew.-% Natriumsulfat (Anteil auf wasserfreie Substanz bezogen),(C) 2 to 8% by weight of sodium sulfate (proportion based on anhydrous substance),
(D) 1,5 bis 8 Gew.-% des Natriumsalzes einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure,(D) 1.5 to 8% by weight of the sodium salt of a homopolymeric or copolymeric (meth) acrylic acid,
(E) 0 bis 30 Gew.-% an nichtionischen Tensiden aus der Klasse Polyglykolether,(E) 0 to 30% by weight of nonionic surfactants from the class polyglycol ether,
Rest Wasser.Rest of water.
Geeignete Schichtsilikate (Bestandteil ), die zur Gruppe der mit Wasser quellfähigen Smectite zählen, sind z.B. solche der allge¬ meinen Formeln 2Suitable sheet silicates (constituent) which belong to the group of smectites which swell with water are, for example, those of the general formulas 2
- 4 -- 4 -
(0H)4 Si'β-y Aly (MgxAl4.x)020(0H) 4 Si ' β-y Al y (M gx Al 4. X ) 020
Montmorrilon t (0H)4 Si8-y Aly (Mg6.zLiz)020 Montmorrilon t (0H) 4 Si 8 -y Al y (M g6 . Z Li z ) 0 20
Hectorit (0H)4 Si8.y Aly (Mg6.zAlz)020Hectorite (0H) 4 Si 8 . y Al y (M g6 . z Al z ) 0 2 0
Saponit mit x = 0 bis 4, y = 0 bis 2, z = 0 bis 6.Saponite with x = 0 to 4, y = 0 to 2, z = 0 to 6.
Zusätzlich kann in das Kristallgitter der Schichtsilikate gemäß vorstehenden Formeln geringe Mengen Eisen eingebaut sein. Ferner können die Schichtsilikate aufgrund ihrer ionenaustauschenden Ei¬ genschaften Wasserstoff-, Alkali und Erdalkal -Ionen, insbesondere Na+ und Ca++ enthalten. Die Hydratwassermenge liegt meist im Be¬ reich von 8 bis 20 Gew.- und ist vom Quellungszustand bzw. von der Art der Bearbeitung abhängig. Die Teilchengröße liegt im Be¬ reich von 0,05 bis 25 μm, meist unter 10 μm. Vorzugsweise werden Schichtsilikate verwendet, die, beispielsweise aufgrund einer Al- kalibehandlung, weitgehend frei von stark färbenden Eisenionen sowie von Calciumionen sind.In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali and alkaline earth ions, in particular Na + and Ca ++ . The amount of water of hydration is usually in the range from 8 to 20% by weight and is dependent on the swelling state or on the type of processing. The particle size is in the range from 0.05 to 25 μm, usually less than 10 μm. Layered silicates are preferably used which, for example due to an alkali treatment, are largely free of strongly coloring iron ions and of calcium ions.
Der Gehalt der Mittel an Schichtsilikaten beträgt 12,5 bis 20 Gew.-%, vorzugsweise 14 bis 20 Gew.- und insbesondere 15 bis 20 Gew.-%.The layer silicate content of the agents is 12.5 to 20% by weight, preferably 14 to 20% by weight and in particular 15 to 20% by weight.
Der Bestandteil (B), der in Anteilen von 50 bis 65 Gew.-%, vor¬ zugsweise 52 bis 62 Gew.-% anwesend ist, besteht aus syntheti¬ schem, gebundenes Wasser enthaltendem Natriu alu osilikat vom Zeo- lith A-Typ. Geeignete Zeolithe weisen keine Teilchen mit einer Größe über 30 μm auf und bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 μm. Ihr' Calciumbindevermögen, das nach den Angaben der DE 24 12837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g.The constituent (B), which is present in proportions of 50 to 65% by weight, preferably 52 to 62% by weight, consists of synthetic sodium aluminosilicate of the zeolite A type containing bound water . Suitable zeolites have no particles larger than 30 μm and consist of at least 80% of particles smaller than 10 μm. Your 'calcium binding capacity, which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g.
Das Natriumsulfat (C) verbessert die Granulierbarkeit der Aus¬ gangsgemische und das Dispergier- und Lösungsverhalten der Granu¬ late im Waschwasser. Vorzugsweise beträgt sein Gehalt 3 bis 7 Gew.-%. Die Anteile beziehen sich auf wasserfreies Salz. Dies schließt jedoch ein, daß ein Teil der in den Granulaten enthalte¬ nen Feuchtigkeit als Hydratwasser an dieses Salz gebunden sein kann.The sodium sulfate (C) improves the granulability of the starting mixtures and the dispersing and dissolving behavior of the granules in the wash water. Its content is preferably 3 to 7% by weight. The proportions refer to anhydrous salt. However, this means that some of the moisture contained in the granules can be bound to this salt as water of hydration.
Der Bestandteil (-D) besteht aus einer homopolymeren und/oder copo¬ lymeren Carbonsäure in Form des Natriumsalzes. Geeignete Homopo- lymere sind Polyacrylsäure und Polymethacrylsäure. Geeignete Co- polymere sind solche der Acrylsäure bzw. der Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich neben homopolymerem Acrylat Copolymere der Acrylsäure bzw. Methacrylsäure mit Malein¬ säure erwiesen, wie sie beispielsweise in EP 25551 Bl beschrieben sind. Es handelt sich dabei um Copolymerisate, die 40 bis 90 Gew.-% Acrylsäure bzw. Methacrylsäure und 60 bis 10 Gew.-% Malein¬ säure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 45 bis 85 Gew.-% Acrylsäure und 55 bis 15 Gew.-% Maleinsäure anwesend sind. Das Molekulargewicht der Homo- bzw. Copolymeren beträgt im allgemeinen 1 000 bis 150 000, vorzugsweise 1 500 bis 100 000. Mit steigendem Anteil an Polysäure bzw. deren Salzen nimmt die Beständigkeit der Körner gegen Abrieb zu. Bei einem An¬ teil ab 1,5 Gew.-% wird bereits eine für viele Fälle hinreichende Abriebfestigkeit erzielt. Optimale Abriebeigenschaften weisen Ge¬ mische mit 2 bis 7 Gew.- an Natriumsalz der Polysäure auf. Außer der Verbesserung der Kornstruktur bewirken die Polymeren auch eine verbesserte Builderwirkung der Gemische bei der Anwendung.The component (-D) consists of a homopolymeric and / or copolymeric carboxylic acid in the form of the sodium salt. Suitable homopolymers are polyacrylic acid and polymethacrylic acid. Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid. In addition to homopolymeric acrylate, copolymers of acrylic acid or methacrylic acid with maleic acid, such as are described, for example, in EP 25551 B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred. The molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000. As the proportion of polyacid or its salts increases, the resistance of the grains to abrasion increases. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 7% by weight of sodium salt of polyacid have optimal abrasion properties. In addition to improving the grain structure, the polymers also do one improved builder effect of the mixtures when used.
Der Wassergehalt der Granulate schließt definitionsgemäß das Was¬ ser ein, das an den Zeolith gebunden (18 bis 22 Gew.-%, bezogen auf Zeolith), sowie vom Schichtsilikat adsorbiert ist, ferner das Hydratwasser der Salze. Üblicherweise liegt er bei 10 bis 25 Gew.-%, insbesondere bei 12 bis 20 Gew.-%.By definition, the water content of the granules includes the water which is bound to the zeolite (18 to 22% by weight, based on zeolite) and is adsorbed by the layered silicate, and also the water of hydration of the salts. It is usually 10 to 25% by weight, in particular 12 to 20% by weight.
Als fakultativen Bestandteil können die Mittel in geringer Menge Verbindungen enthalten, welche bei der Herstellung und Verarbei¬ tung der synthetischen Zeolithe zugesetzt werden können, um die Stabilität der wäßrigen Zeolith-Dispersionen (master batch) zu erhöhen. Derartige Zusätze, die mit dem Zeolith in die Mittel ein¬ gebracht werden können, sind im vorstehend zitierten Dokument DE 25 27 388 beschrieben. Es kann sich dabei um nichtionische, Poly- glykolethergruppen aufweisende Tenside, beispielsweise primäre, mit 2 bis 7 Mol Ethylenoxid umgesetzte Alkohole mit 12 bis 18 C- Ato en handeln. Der über derartige Zeolith-Dispersionen in das Mittel eingebrachte Anteil an Stabilisatoren kann, je nach Anteil des Zeoliths, beispielsweise 0,05 bis 2 Gew.-% betragen. Notwendig für die gewünschten Eigenschaften der Granulate ist dieser Be¬ standteil jedoch nicht.As an optional constituent, the agents can contain small amounts of compounds which can be added during the production and processing of the synthetic zeolites in order to increase the stability of the aqueous zeolite dispersions (master batch). Such additives, which can be introduced into the compositions with the zeolite, are described in document DE 25 27 388 cited above. These can be nonionic surfactants containing polyglycol ether groups, for example primary alcohols with 12 to 18 carbon atoms reacted with 2 to 7 moles of ethylene oxide. The proportion of stabilizers introduced into the composition via such zeolite dispersions can be, for example, 0.05 to 2% by weight, depending on the proportion of the zeolite. However, this component is not necessary for the desired properties of the granules.
Weitere fakultative Bestandteile sind Farbstoffe bzw. Farbpigmen¬ te, die den Mitteln bei der Granulation in Anteilen von beispiels¬ weise 0,01 bis 1 Gew.-% zugesetzt werden können, um eine mögliche graue oder bräunliche Eigenfarbe der Schichtsilikate zu über¬ decken. Nach dem Zumischen der Granulate zu einem granulären Wasch¬ mittel verleihen sie diesem ein optisch ansprechendes, farblich gesprenkeltes Aussehen. In gleicher Weise lassen sich auch Weiß- pigmente und optische Aufheller einsetzen, wenn ein weißes Granu¬ lat und ein einheitliches weißes Mischprodukt gewünscht wird.Further optional constituents are dyes or colored pigments, which can be added to the agents in the granulation in proportions of, for example, 0.01 to 1% by weight in order to cover a possible gray or brownish intrinsic color of the layered silicates. After the granules have been mixed into a granular detergent, they give it a visually appealing, color-speckled appearance. In the same way, white Use pigments and optical brighteners if a white granulate and a uniform white mixed product are required.
Besonders geeignet sind solche Farbstoffe, die im nachfolgenden Waschprozeß abgebaut werden, so daß es nicht zu einem unerwünsch¬ ten Anfärben der Textilien kommt. Beispiele hierfür sind z.B. die Farbstoffe Duasynsäureblau(R) und DuasynsäuregrünW.Dyes which are degraded in the subsequent washing process are particularly suitable, so that there is no undesired dyeing of the textiles. Examples include the dyes duasyn acid blue ( R ) and duasyn acid green.
Schließlich lassen sich die Granulate aufgrund ihrer guten Saug¬ fähigkeit dazu verwenden, um flüssige bzw. pastöse Waschmittεlbe- standteile zu adsorbieren und ohne Einbuße an Rieselfähigkeit in Waschmittelgranulate einzuarbeiten. Beispiele hierfür sind Fett- säurealkanola ide (die einen zusätzlichen Avivageeffekt bzw. eine Waschkraftverstärkung bewirken können) und insbesondere nichtio¬ nische Tenside vom Typ der Polyglykoletherderivate. Hinsichtlich der Art und der aufzubringenden Mengen an derartigen Zusatzstoffen wird auf die Patentanmeldung P 3936405.4 (D 8720) vom 02.11.1989 verwiesen, auf die hier ausdrücklich Bezug genommen wird. Der An¬ teil an nichtionischen Tensiden, bezogen auf das Adsorbat, kann bis 30 Gew.-% betragen. Anstelle der nichtionischen Tenside oder zusammen mit diesen können auch ölartige Zusatzstoffe, wie Parfüms oder schaumdämpfende Stoffe aus der Klasse der Paraffine, Mikro- paraffine, langkettigen Bisacyldiamine und Silikone sowie deren Gemische an den Körnern adsorbiert werden.Finally, due to their good absorbency, the granules can be used to adsorb liquid or pasty detergent constituents and to incorporate them into detergent granules without loss of free-flowing properties. Examples of these are fatty acid alkanols (which can bring about an additional softening effect or increase washing power) and, in particular, nonionic surfactants of the polyglycol ether derivative type. With regard to the type and the amounts of such additives to be applied, reference is made to patent application P 3936405.4 (D 8720) dated November 2, 1989, to which reference is expressly made here. The proportion of nonionic surfactants, based on the adsorbate, can be up to 30% by weight. Instead of, or together with, the nonionic surfactants, it is also possible to adsorb oily additives, such as perfumes or foam-suppressing substances from the class of paraffins, microparaffins, long-chain bisacyl diamines and silicones, and mixtures thereof, onto the grains.
Die Herstellung der Mittel erfolgt durch Sprühtrocknen eines wä߬ rigen, pastenförmigen Ansatzes (Slurry) der Bestandteile mittels erhitzter Gase (Verbrennungsgase) in üblichen Trockentürmen. Da die als Trockengas vielfach verwendete Verbrennungsluft ver¬ gleichsweise hohe Anteile an Kohlendioxid enthält, kann es vor- teilhaft sein, wenn man dem Slurry vor dem Versprühen geringe Men¬ gen an Natriumhydroxid zusetzt, um einer pH-Erniedrigung durch einen entsprechenden Alkaliüberschuß zu begegnen. Die empfohlenen Anteile an NaOH liegen meist zwischen 0,1 bis 1 Gew.-%.The agents are produced by spray drying an aqueous, paste-like batch (slurry) of the constituents by means of heated gases (combustion gases) in conventional drying towers. Since the combustion air, which is widely used as a dry gas, contains comparatively high proportions of carbon dioxide, it can be particulate if small amounts of sodium hydroxide are added to the slurry before spraying, in order to counteract a pH reduction by a corresponding excess of alkali. The recommended proportions of NaOH are usually between 0.1 and 1% by weight.
Im allgemeinen beträgt, der Gehalt des wäßrigen Ansatzes an wasser¬ freien Inhaltsstoffen 50 bis 65 Gew.-%. Seine Temperatur beträgt zweckmäßigerweise 50 bis 90 °C und seine Viskosität bei dieser Arbeitstemperatur bis 25000 mPa-s, meist 12000 bis 20000 mPa-s. Der Zerstäubungsdruck liegt meist bei 20 bis 120 bar, vorzugsweise 30 bis 80 bar. Das Trocknungsgas, das im allgemeinen durch Ver¬ brennen von Heizgas oder Heizöl erhalten wird, wird vorzugsweise im Gegenstrom geführt. Bei Verwendung von Trockentürmen, in welche der wäßrige Ansatz im oberen Teil über mehrere Hochdruckdüsen ein¬ gesprüht wird, beträgt die Eingangstemperatur, gemessen im Ring¬ kanal (d.h. unmittelbar vor Eintritt in den unteren Teil des Tur¬ mes) 180 bis 300 °C, vorzugsweise 220 bis 280 °C. Das den Turm verlassende, mit Feuchtigkeit beladene Abgas weist üblicherweise eine Temperatur von 50 bis 110 °C, vorzugsweise 60 bis 100 °C auf.In general, the aqueous batch contains 50 to 65% by weight of water-free ingredients. Its temperature is advantageously 50 to 90 ° C and its viscosity at this working temperature up to 25000 mPa-s, usually 12000 to 20,000 mPa-s. The atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar. The drying gas, which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent. When using drying towers, into which the aqueous batch is sprayed in the upper part via several high-pressure nozzles, the inlet temperature, measured in the ring channel (ie immediately before entering the lower part of the tower), is 180 to 300 ° C. preferably 220 to 280 ° C. The exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 110 ° C., preferably 60 to 100 ° C.
Die auf diese Weise hergestellten Granulate zeichnen sich durch eine sehr gute Redispergierbarkeit in der wäßrigen Waschflotte aus. Hinsichtlich ihrer avivierenden Wirkung sind sie mit auf an¬ dere Weise hergestellten Mitteln der gleichen Art weitgehend iden¬ tisch.The granules produced in this way are notable for very good redispersibility in the aqueous wash liquor. With regard to their activating effect, they are largely identical with agents of the same type produced in another way.
Die mittlere Korngröße des durch Sprühtrocknung hergestellten Mit¬ tels beträgt üblicherweise 0,2 bis 1,2 mm. Vorzugsweise weisen mindestens 80 Gew.-%, insbesondere mindestens 90 Gew.-% der Körner eine Größe von 0,2 bis 1,0 mm auf, wobei der Anteil der Körner zwischen 0,1 und 0,05 mm nicht mehr als 2 Gew.-%, insbesondere weniger als 1 Gew.-% und der Anteil der Körner oberhalb 1,5 mm nicht mehr als 15 Gew.-%, insbesondere nicht mehr als 10 Gew.-% beträgt. Größere Anteile an Feinkorn begünstigen die Staubbildung beim Mischen mit anderen Pulverkomponenten und sollten daher ver¬ mieden werden. Größere Ante le an Grobkorn bedingen ein geringeres Schüttgewicht und lassen das Produkt visuell uneinheitlich er¬ scheinen, sind im übrigen aber nicht nachteilig.The average grain size of the agent produced by spray drying is usually 0.2 to 1.2 mm. Preferably, at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.0 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 2% by weight .-%, in particular less than 1% by weight and the proportion of the grains above 1.5 mm is not more than 15% by weight, in particular not more than 10% by weight. Larger proportions of fine grain favor the formation of dust when mixed with other powder components and should therefore be avoided. Larger proportions of coarse grain cause a lower bulk density and make the product appear visually inconsistent, but are otherwise not disadvantageous.
Das Schüttgewicht der sprühgetrockneten Mittel beträgt 500 bis 700 g/1, meist 550 bis 650 g/1. Das Mittel besteht im wesentlichen aus abgerundeten Körnern, die ein sehr gutes Rieselverhalten aufwei¬ sen. Dieses sehr gute Rieselverhalten ist auch dann noch vorhan¬ den, wenn die Körner mit größeren Anteilen an flüssigen bzw. halb¬ flüssigen oder festen nichtionischen Tensiden imprägniert worden sind. Der Anteile dieser adsorbierten Bestandteile kann 5 bis 30 Gew.- , bevorzugt 10 bis 25 Gew.- , bezogen auf das Adsorbat, be¬ tragen. The bulk density of the spray-dried compositions is 500 to 700 g / 1, mostly 550 to 650 g / 1. The agent essentially consists of rounded grains which have a very good flow behavior. This very good flow behavior is still present even when the grains have been impregnated with larger proportions of liquid, semi-liquid or solid nonionic surfactants. The proportion of these adsorbed constituents can be 5 to 30% by weight, preferably 10 to 25% by weight, based on the adsorbate.
B e s p i e l eB e s p i e l e
Die in den folgenden Beispielen verwendeten Rohstoffe wiesen fol¬ gende Charakteristika auf:The raw materials used in the following examples had the following characteristics:
(A) Schichtsilikat, Produkt "Laundrosil DG-A" der Firma Süd-Che¬ mie (DE), windgesichtet, mit Sodalösung behandelt und im we¬ sentlichen frei von Erdalkaliionen (Teilchengröße der Schichtsilikate 99 Gew.-% unter 25 μm),(A) layered silicate, product "Laundrosil DG-A" from Süd-Chemie (DE), wind-sighted, treated with soda solution and essentially free of alkaline earth metal ions (particle size of the layered silicates 99% by weight below 25 μm),
(B) Zeolith NaA, Calciumbindevermögen 165 mg CaO/g, mittlere(B) Zeolite NaA, calcium binding capacity 165 mg CaO / g, medium
Korngröße 3 μm (keine Anteile über 20 μm). Ausgangsmaterial war eine ca. 50 Gew.-% Wasser enthaltende und mit dem nicht¬ ionischen Tensid stabilisierte Suspension. In den Beispielen ist der Zeolith wasserfrei gerechnet, d.h. der auf den Zeo¬ lith entfallende Wassergehalt (ca. 20 % bezogen auf Zeolith) ist unter "Wasser" aufgeführt. (D) Copoly eres Salz, Acrylsäure-Maleinsäure-Copolymer, MG 70000, Na-Salz, Produkt Sokalan(R) CP5 der Firma BASF (DE),Grain size 3 μm (no proportions over 20 μm). The starting material was a suspension containing about 50% by weight of water and stabilized with the non-ionic surfactant. In the examples, the zeolite is calculated to be anhydrous, ie the water content attributable to the zeolite (approx. 20% based on zeolite) is listed under "water". (D) Copoly eres salt, acrylic acid-maleic acid copolymer, MG 70000, Na salt, product Sokalan ( R ) CP5 from BASF (DE),
TA5 bedeutet ein mit 5 Mol Ethylenglykol umgesetzter Talgalkohol, eingesetzt als Dispersionsstabilisator für die 50 Gew.-% enthal¬ tende Zeolithdispersion. Als optischer Aufheller wurde ein Diani- lino-dimorpholino-Derivat der Bis-(triazinyl)-stilbendisulfonsäure Na-Salz) eingesetzt. TA5 means a tallow alcohol reacted with 5 moles of ethylene glycol, used as a dispersion stabilizer for the zeolite dispersion containing 50% by weight. A dianilino-dimorpholino derivative of bis (triazinyl) -stilbene disulfonic acid Na salt) was used as the optical brightener.
- 11- 11
Die Viskosität der Aufschlämmungen (Slurry) betrug, jeweils bei der Arbeitstemperatur von 80 °C gemessen, imThe viscosity of the slurries (slurry), measured in each case at the working temperature of 80 ° C., was in
1. Beispiel 10000 mPa-s, Slurry-Konzentration 55 Gew.-%1st example 10000 mPa-s, slurry concentration 55% by weight
2. Beispiel 24000 mPa«s, Slurry-Konzentration 50 Gew.-%2. Example 24000 mPa 's, the slurry concentration of 50 wt .-%
3. Beispiel 12300 mPa»s, Slurry-Konzentration 50 Gew.-%3. Example 12300 mPa 's, the slurry concentration of 50 wt .-%
Die Rezeptur gemäß Beispiel 2 war unter Anwendung von Rührwerken mit hohem Drehmoment und eines hohen Sprühdrucks versprühbar. Die Rezepturen gemäß Beispiel 1 und 3 ließen sich ohne besonderen technischen Aufwand ansetzen und sprühtrockneπ.The formulation according to Example 2 was sprayable using stirrers with high torque and a high spray pressure. The recipes according to Examples 1 and 3 could be prepared and spray-dried without special technical effort.
Die im Gegenstrom geführten Trocknungsgase wiesen eine Eingangs¬ temperatur im Ringkanal von 263 °C (Beispiel 1 und 3) bzw. 267 °C (Beispiel 2) auf. Die Temperatur im Bereich des Turmaustritts vor den Staubfiltern betrug 71 °C bis 72 °C (Beispiel 1 und 3) bzw. 76 °C (Beispiel 2). Der Zerstäubungsdruck betrug 40 bar in Beispiel 1 und 3 und 49 bar in Beispiel 2. Die erhaltenen Sprühprodukte waren einwandfrei rieselfähig bei einer mittleren Korngröße von 0,35 mm und einem Staubanteil (unter 0,05 mm) von weniger als 0,1 Gew.-%. Kornanteile von über 2 mm wa¬ ren nicht vorhanden. Das Schüttgewicht betrug 590 g/1 in Beispiel 1, 550 g/1 in Beispiel 2 und 590 g/1 in Beispiel 3. Sämtliche Sprühprodukte konnten in einer Sprühmischapparatur mit 5 bis 30 Gew.- (bezogen auf das Endprodukt) an flüssigen nichtionischen Tensiden (Cocosfettalkohol + 5E0, Ci2-14-Oxoalkohol + 7 E0) be¬ aufschlagt werden, wobei das Schüttgewicht auf 650 bis 780 g/1 anstieg. Das Rieselverhalten der so erhaltenen Adsorbate war ge¬ genüber den eingesetzten Granulaten unverändert gut.The drying gases conducted in countercurrent had an inlet temperature in the ring channel of 263 ° C. (examples 1 and 3) and 267 ° C. (example 2). The temperature in the area of the tower outlet in front of the dust filters was 71 ° C to 72 ° C (Examples 1 and 3) and 76 ° C (Example 2). The atomization pressure was 40 bar in Example 1 and 3 and 49 bar in Example 2. The spray products obtained were free-flowing with an average particle size of 0.35 mm and a dust content (less than 0.05 mm) of less than 0.1% by weight. Grain fractions of over 2 mm were not present. The bulk density was 590 g / 1 in Example 1, 550 g / 1 in Example 2 and 590 g / 1 in Example 3. All spray products were able to use 5 to 30% by weight (based on the end product) of liquid nonionic surfactants in a spray mixing apparatus (Coconut fatty alcohol + 5E0, Ci2-14-oxo alcohol + 7 E0) can be added, the bulk density increasing to 650 to 780 g / l. The flow behavior of the adsorbates thus obtained was unchanged compared to the granules used.
Die Granulate wurden mit einem körnigen Waschmittel zu einem Mit¬ tel folgender Zusammensetzung vermischt (in Gew.-%):The granules were mixed with a granular detergent to give an agent of the following composition (in% by weight):
7,2 % Natriumdodecylbenzolsulfonat7.2% sodium dodecylbenzenesulfonate
4,8 % Cχ2.i8-Fettalkohol + 7E04.8% Cχ2.i8 fatty alcohol + 7E0
1,5 % Talgseife (Na-Salz) 10,5 % Zeolith (wasserfrei)1.5% tallow soap (Na salt) 10.5% zeolite (anhydrous)
7,0 % Natriumkarbonat7.0% sodium carbonate
2,5 % Hydroxyethandiphosphonat (Na-Salz)2.5% hydroxyethane diphosphonate (Na salt)
2.2 % Copolymer entsprechend (D)2.2% copolymer corresponding to (D)
1.3 % Na-Carboxymethylcellulose1.3% Na carboxymethyl cellulose
2.5 % Natriumsilikat (1 : 3,3) 0,3 % optische Aufheller2.5% sodium silicate (1: 3.3) 0.3% optical brightener
10,5 % Natriumperborat-monohydrat10.5% sodium perborate monohydrate
2.6 % Tetraacetyethylendiamin2.6% tetraacetyethylene diamine
1,5 % Enzymgranulat (Enzymanteil 0,7 %)1.5% enzyme granulate (enzyme content 0.7%)
0,1 % Duftstoff0.1% fragrance
35,0 % Granulat gemäß Beispiel 1 - 3 Rest Wasser Die an 1. bis 10. Stelle aufgeführten Bestandteile sowie das Was¬ ser (an Zeolith gebunden, Kristallwasser, Produktfeuchte) lagen als sprühgetrocknete Granulate vor. Die übrigen Bestandteile be¬ standen jeweils aus getrennt hergestellten Granulaten. Der Duft¬ stoff war an dem Perborat adsorbiert.35.0% of granules according to Example 1-3 rest of water The constituents listed at the 1st to 10th place and the water (bound to zeolite, water of crystallization, product moisture) were present as spray-dried granules. The remaining constituents each consisted of separately produced granules. The fragrance was adsorbed on the perborate.
Mit den Mitteln wurden Baumwolltextilien bei einer Waschmittel¬ konzentration von 9 g/1 bei 60 °C gewaschen. Das Trocknen erfolgte freihängend. Die Vergleichsversuche wurden mit einem Waschmittel durchgeführt, in denen das erfindungsgemäße Granulat durch ein anderes Granulat ersetzt worden war. In diesem Vergleichsgranulat war bei sonst unveränderter Zusammensetzung das Schichtsilikat durch Natriumsulfat ersetzt worden. Gegenüber den Vergleichsproben wiesen die Textilien, die mit dem erfindungsgemäßen Mittel, gemäß Beispiel 2 und 3, gewaschen worden waren, einen deutlich weicheren Griff auf, wobei die Avivagewirkung von den Testpersonen bei Ver¬ wendung der Granulate gemäß Beispiel 2 und 3 als "gut bis befrie¬ digend" und gemäß Beispiel 1 als "noch befriedigend" beurteilt wurde.Cotton fabrics were washed with the detergents at a detergent concentration of 9 g / l at 60 ° C. Drying was free hanging. The comparative experiments were carried out with a detergent in which the granules according to the invention had been replaced by another granulate. In this comparative granulate, the sheet silicate had been replaced by sodium sulfate with an otherwise unchanged composition. Compared to the comparative samples, the textiles which had been washed with the agent according to the invention, according to Examples 2 and 3, had a significantly softer feel, the softening effect of the test subjects using the granules according to Examples 2 and 3 as "good to satisfactory "and was assessed as" still satisfactory "according to Example 1.
Bei Verwendung von Weichwasser (8 °dH entsprechend 80 mg Ca0/1) war die Reinigungswirkung der erfindungsgemäßen Mittel und der Vergleichsproben annähernd gleich. Bei einer Erniedrigung der Waschmittelkonzentration auf 6 g/1 und ebenso bei Verwendung von Hartwasser (20 °dH) bei unveränderter Konzentration von 9 g/1 wie¬ sen die mit den erfindungsgemäßen Mitteln gewaschenen Proben ein deutlich verbessertes Waschergebnis und nach jeweils 10 Wäschen eine geringere Vergrauung sowie einen geringeren Aschegehalt auf. When using soft water (8 ° dH corresponding to 80 mg Ca0 / 1), the cleaning effect of the agents according to the invention and the comparative samples was approximately the same. When the detergent concentration is reduced to 6 g / 1 and likewise when using hard water (20 ° dH) at an unchanged concentration of 9 g / 1, the samples washed with the detergents according to the invention have a significantly improved washing result and after 10 washes a lower one Graying and a lower ash content.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Avivierend wirkendes, granuläres Waschmitteladditiv, enthal¬ tend1. Granulating detergent additive, which acts as an aerating agent
(A) 12,5 bis 20 Gew.-% eines Schichtsilikates,(A) 12.5 to 20% by weight of a layered silicate,
(B) 52 bis 65 Gew.-% feinkristallinen, synthetischen Zeolith (Anteil auf wasserfreie Substanz bezogen),(B) 52 to 65% by weight of finely crystalline, synthetic zeolite (proportion based on anhydrous substance),
(C) 2 bis 8 Gew.-% Natriumsulfat (Anteil auf wasserfreie Substanz bezogen),(C) 2 to 8% by weight of sodium sulfate (proportion based on anhydrous substance),
(D) 1,5 bis 8 Gew.- des Natriumsalzes einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure,(D) 1.5 to 8% by weight of the sodium salt of a homopolymeric or copolymeric (meth) acrylic acid,
(E) 0 bis 30 Gew.-% an nichtionischen Tensiden aus der Klasse der Polyglykolether,(E) 0 to 30% by weight of nonionic surfactants from the class of the polyglycol ethers,
Rest Wasser.Rest of water.
2. Mittel nach Anspruch 1, worin der Bestandteil (A) aus Montmor- rilonit, Hectorit oder Saponit besteht und in Anteilen von 14 bis 20 Gew.-% vorliegt.2. Composition according to claim 1, wherein the component (A) consists of montmorrilonite, hectorite or saponite and is present in proportions of 14 to 20 wt .-%.
3. Mittel nach Anspruch 1 oder 2, enthaltend 52 bis 62 Gew.-% des Bestandteils (B).3. Composition according to claim 1 or 2, containing 52 to 62 wt .-% of component (B).
4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, ent¬ haltend 3 bis 7 Gew.-% des Bestandteils (C).4. Composition according to one or more of claims 1 to 3, containing 3 to 7% by weight of component (C).
5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, worin der Bestandteil (D) aus dem Natriumsalz der homopolymeren Acrylsäure und/oder deren Copolymeren mit Maleinsäure besteht.5. Composition according to one or more of claims 1 to 4, wherein the component (D) consists of the sodium salt of homopolymeric acrylic acid and / or its copolymers with maleic acid.
6. Mittel nach Anspruch 1 und 5, worin der Anteil des Bestand¬ teils (D) 2 bis 7 Gew.-% beträgt. 6. Composition according to claim 1 and 5, wherein the proportion of component (D) is 2 to 7 wt .-%.
7. Verfahren zur Herstellung der Mittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man einen 45 bis 60 Gew.- Wasser enthaltenden Ansatz der Bestandteile mittels strömender Gase, die eine Eingangstemperatur von 180 bis 300 °C und eine Austrittstemperatur von 60 bis 110 °C auf¬ weisen, sprühtrocknet.7. A process for the preparation of the agent according to one or more of claims 1 to 6, characterized in that a 45 to 60 wt .-% water-containing batch of the components by means of flowing gases having an inlet temperature of 180 to 300 ° C and an outlet temperature have from 60 to 110 ° C, spray dried.
8. Verwendung eines Mittels nach einem oder mehreren der Ansprü¬ che 1 bis 6 als Adsorptionsmittel für flüssige bzw. pastöse Waschmittelbestandteile, insbesondere nichtionische Tenside.8. Use of an agent according to one or more of claims 1 to 6 as an adsorbent for liquid or pasty detergent components, in particular nonionic surfactants.
9. Verwendung eines Mittels nach einem oder mehreren der Ansprü¬ che 1 bis 6 und 8 als Mischungsbestandteil in granulären Wasch¬ mitteln. 9. Use of an agent according to one or more of claims 1 to 6 and 8 as a constituent of the mixture in granular detergents.
EP91906393A 1990-03-26 1991-03-18 Spray-dried brightening additive for washing agents Expired - Lifetime EP0544670B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4009618 1990-03-26
DE4009618A DE4009618A1 (en) 1990-03-26 1990-03-26 SPRAY-DRIED, AVIVATING DETERGENT ADDITIVE
PCT/EP1991/000514 WO1991014762A1 (en) 1990-03-26 1991-03-18 Spray-dried brightening additive for washing agents

Publications (2)

Publication Number Publication Date
EP0544670A1 true EP0544670A1 (en) 1993-06-09
EP0544670B1 EP0544670B1 (en) 1994-07-20

Family

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Application Number Title Priority Date Filing Date
EP91906393A Expired - Lifetime EP0544670B1 (en) 1990-03-26 1991-03-18 Spray-dried brightening additive for washing agents

Country Status (5)

Country Link
EP (1) EP0544670B1 (en)
AT (1) ATE108823T1 (en)
DE (2) DE4009618A1 (en)
ES (1) ES2056643T3 (en)
WO (1) WO1991014762A1 (en)

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US5962401A (en) * 1994-12-15 1999-10-05 Nippon Shokubai Co., Ltd. Detergent builder process of manufacturing same and detergent composition containing same
GB2297977A (en) * 1995-02-07 1996-08-21 Procter & Gamble Detergent composition containing Zeolite MAP
DE19538029A1 (en) * 1995-10-12 1997-04-17 Sued Chemie Ag detergent additive
DE19538028A1 (en) * 1995-10-12 1997-04-17 Sued Chemie Ag detergent additive
EP0903401B1 (en) * 1997-09-17 2003-08-06 Ciba SC Holding AG Antimicrobial additive for washing agents
DE59809191D1 (en) 1997-09-17 2003-09-11 Ciba Sc Holding Ag Antimicrobial detergent additive
DE19756696A1 (en) 1997-12-19 1999-07-01 Clariant Gmbh Detergent and cleaning agent components containing layered silicate
DE19819187A1 (en) * 1998-04-30 1999-11-11 Henkel Kgaa Solid dishwasher detergent with phosphate and crystalline layered silicates
GB0102736D0 (en) * 2001-02-05 2001-03-21 Crosfield Joseph & Sons Disintegrants and a process for their manufacture
ES2953916T3 (en) 2016-11-04 2023-11-17 Sa Minera Catalano Aragonesa Colored particles for detergents and their production procedure

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DE3444960A1 (en) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf GRAINY ADSORPTION
DE3702764A1 (en) * 1987-01-30 1988-08-11 Degussa DETERGENT PICTURES
DE3931871A1 (en) * 1989-09-23 1991-04-04 Henkel Kgaa GRANULAR, PHOSPHATE-FREE WATER DISINFECTANT
DE3936405A1 (en) * 1989-11-02 1991-05-08 Henkel Kgaa GRINNY, NON-ionic surfactant-containing detergent for detergents and cleaning agents with improved induction behavior
GB0104383D0 (en) * 2001-02-22 2001-04-11 Psimedica Ltd Cancer Treatment

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Also Published As

Publication number Publication date
ES2056643T3 (en) 1994-10-01
DE4009618A1 (en) 1991-10-02
WO1991014762A1 (en) 1991-10-03
DE59102283D1 (en) 1994-08-25
EP0544670B1 (en) 1994-07-20
ATE108823T1 (en) 1994-08-15

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