EP0857200B1 - Washing-agent additive - Google Patents

Abstract

A detergent in agglomerate form is described, characterized by the fact that it contains at least one swellable layer silicate and at least one optical brightener in intimate contact with each other.

Description

The invention relates to a detergent additive, based of swellable layered silicates.

A related invention is disclosed in parallel EP-A-0 856 046 described and claimed.

FR-A-2 500 475 describes spray-dried detergent additives the 1 to 20% by weight bentonite and optical brighteners can contain. An aqueous slurry is used for the production made from the various components. Subsequently this slurry is spray dried.

DD-220325, 220326, 220327 and 220328 are washing aids known for whiteness enhancement. These contain optical Brightener and non-swellable layered silicates, e.g. the natural mineral magadiite.

Furthermore, the use is restricted from DE-A-35 26 405 swellable aluminosilicates in detergents that are also optical Brightener included, known.

Has been developing detergents since the mid-1980s a trend towards higher bulk weights. The motive for this is the possibility of saving unnecessary volume-increasing fillers and the saving of packaging material. Another advantage is there too see a lower volume in transportation and trade is required. The consumer has the advantage that Take less detergent packs in the shopping basket.

An essential step in the development of highly concentrated Detergent with a high bulk density consists of Omission of fillers or so-called adjusting agents, such as Sodium sulfate.

DE-C-3 424 987 describes the production of detergent concentrates high bulk density, which is not sodium sulfate included as a set. Here a basic powder is passed through Spray drying, which contains the usual detergent ingredients, such as surfactants, carboxymethyl cellulose (CMC), Sodium polyphosphate, zeolite A, water glass, optical brighteners et al contains. The base powder obtained with low bulk density, which is free of sodium sulfate will increase the bulk density is sprayed with further nonionic surfactant and with a separately produced granulate with high Bulk weight mixed dry. This product is the optical brighteners on contact, especially oxidation, exposed unprotected by other detergent ingredients.

Another major disadvantage of highly concentrated detergents with high bulk density is that the detergent ingredients in high individual concentrations without dilution with an actuator, come into contact with each other can. This was with detergent with low bulk density, which contained up to 25% sodium sulfate, not the Case. The active ingredients are in detergent concentrates of the detergent packed tightly in high concentration side by side. In the worst case, the detergent ingredients with hydrolysis or oxidation with each other react, which affects the function of the ingredients and the detergent can lead.

The incorporation of optical brighteners poses a problem in detergent concentrates with high bulk density Manufacture of detergent with low bulk density has been the optical brightener either processed in the spray product, or it was subsequently added to the tower product as a powder (Spray product) mixed. Is not the optical brightener through a coating created during production or by the presence of thinning, spatially separating and water adsorbing actuators, from the bleaches also contained in the detergent, such as sodium perborate, but especially sodium percarbonate, separated, so optical brighteners can be oxidized. That used up here Bleaching potential stands for the later bleaching effect no longer available in the wash liquor. Especially but the oxidation product of the optical brightener can turn yellow be colored, which gives the detergent a yellow tint shows, on the other hand, the yellow oxidation product of the brightener substantively on the washing textiles, what to an impairment of the aesthetic aspect, above all white laundry leads.

The formation preceding the oxidation of the optical brightener of active oxygen in the washing powder is due to a reaction of bleach contained in washing powder, especially when containing percarbonate as a bleach is. In the presence of tetraacetylethylenediamine (TAED) Peracetic acid is formed, from which active oxygen is released becomes. This problem is discussed in M. Husslein et al., 36. International Conference 1994, WFK - Research Institute for cleaning technology e.V., pages 82-85.

For detergents with low bulk density, which contain sodium sulfate contained, the problem was not serious because that water triggering the reaction through the formation of water of crystallization could be bound to the sodium sulfate. The problem turns out very clearly with detergents with high Bulk density. There was therefore a need to opt Brightener, especially of the stilbene type, before reacting with to protect the active oxygen generated in the washing powder.

Another, with the formulation of detergent concentrates accompanying problem is that the agglomerates with high bulk density in the wash liquor not fast enough dissolve and find yourself in the "wash liquor swamp". Since there insufficient mechanical stress on the agglomerates occurs, these only partially dissolve, causing the active components partially removed from the washing effect.

The detergent agglomerates of high bulk density generally have poor dispersibility; this can be improved by adding dispersing and disintegrating agents which swell in contact with water and blow up or loosen the agglomerates, which leads to improved solubility and availability of the active components. In the article by H. Führer, Seifen-Öle-Fette-Wachsen, 18 (1963), pp. 561-562, it is described that natural, water-swelling smectites can be used as disintegrants in compacted detergent tablets.

The presence of a disintegrating detergent agglomerate Disintegrant is also necessary to the so-called Avoid "brightener spotting". Lightening spotting arises through a long-term contact of unresolved, lightened agglomerate with the laundry. By the direct contact of locally over-concentrated optical brighteners If this is done at the contact point in unwanted, high concentrations locally transferred to the tissue. This is especially in the presence of UV light Form of slight stains visible and represents an impairment of the aesthetic aspect. The detergent agglomerates should therefore contain explosives so that they be blown into contact with the wash liquor, causing the optical brighteners dissolved homogeneously in the wash liquor and a direct contact of the detergent agglomerates with the laundry is avoided.

Are several in a production plant for detergents Detergent made different recipe, so result problems when lightening and brightener-free detergents are produced. Aufhellerfrei Formulated detergents are used in plants in which previously brightening detergents were made with residues of the optical brightener contaminated. Even with thorough The contamination cannot be cleaned beforehand be completely excluded.

There is therefore a need for a detergent additive in which avoiding the brightener component in a suitable manner of contact with the essential parts of a production plant for detergent can be mixed into the detergent can without affecting the function of the optical brightener becomes.

The invention had the object of adding a detergent to provide in agglomerate form (granulate form), which at least one swellable layered silicate and an optical one Brightener contains which with good mechanical stability decays well in water and in which the optical brightener is present in a homogeneous distribution and against oxidation by the Oxidizing agent contained in the detergent is protected.

The invention relates to a detergent additive in non-spray-dried agglomerate form according to claim 1.

Due to the close contact of the optical brightener with the Layered silicate is used during the oxidation processes Storage of the detergent is reliably removed and it will when using the detergent, the "brightener spotting" on the Avoid laundry. It is believed that the optical brightener at least partially between the layers of layered silicate is stored because the discrete Brightener particles in the detergent additive have largely disappeared and the layered silicate particles in the fluorescence microscope appear homogeneously colored by the brightener.

The weight ratio is preferably swellable Layered silicate (s): optical brightener about 200-7: 1, in particular 100-10: 1st

The swellable layered silicate is a natural one or synthetic clay mineral. The swellable clay mineral is preferably montmorillonite, beidellite, saponite or hectorite.

Montmorillonite can be in sodium or calcium form or in the form of a calcium montmorillonite ion-exchanged with soda be used. It can also be synthetically made Clay minerals from the above group be used. The layered silicate is preferably in an amount of 90 to 99 wt .-% used.

The swellable layered silicates have the property under intra-crystalline swelling polar agents between the Intercalate silicate lamellae, which can be seen at higher concentrations noticeable in an increase in the layer spacing makes.

The optical brightener is preferably a stilbene derivative But it can also benzoxazole, coumarin and pyrazoline derivatives be used. These products generally have an anionic dye residue, which is why it was surprising that they are between the negatively charged layers of the swellable Layered silicate can be stored.

Suitable optical brighteners are, for example

(a) Cyanursäurechlorid-Diaminostilben (CCDAS), worin R folgende Bedeutungen haben kann:

Typ: Tetraanilin
(Handelsbezeichnung Tinopal® TAS-X der Firma Ciba-Geicy)

Typ: Dimorpholin
(Handelsbezeichnung Tinopal® DMS-X H.C.)

Typ: Aminostilben
(Handelsbezeichnung Tinopal® 5 BMS-X)

(b)

Handelsbezeichnung: Tinopal® CBS-X

(c)

Handelsbezeichnung Tinopal® ELS-X

(a) Cyanuric acid chloride diaminostilbene (CCDAS), in which R can have the following meanings:

Type: tetraaniline
(Trade name Tinopal® TAS-X from Ciba-Geicy)

Type: dimorpholine
(Trade name Tinopal® DMS-X HC)

Type: amino style
(Trade name Tinopal® 5 BMS-X)

(B)

Trade name: Tinopal® CBS-X

(C)

Trade name Tinopal® ELS-X

Since agglomerates of natural layered silicates and optical brighteners can have a beige, gray or yellow appearance, the agglomerate particles of the detergent additive are preferably coated with synthetic zeolite or layered sodium silicate (preferably about 3 to 15% by weight), which increases the whiteness of the agglomerate is improved. Further preferred alternatives for concealing the intrinsic color of the agglomerates consist of dyeing with dyes customary in detergents, in particular pigment dyes, for example Unidisperse® blue BE (commercial product from Ciba-Geigy) (preferably about 0.01 to 0.5% by weight), or in the addition of colored active substances (preferably about 0.3 to 5% by weight), for example the photo bleach Tinolux® BB ⁵ (commercial product from Ciba-Geigy).

The agglomerate preferably has a bulk density of more than about 700 g / liter and is due to this high bulk density Compatible with highly concentrated, high density detergents.

The invention further relates to a method for the production of the detergent additive described above in Agglomerate form, which is characterized in that the optical brighteners as an aqueous slurry to the (the) Layered silicate (s) exist.

The layered silicate (s) can be, for example, in an intensive mixer, e.g. in an Eirich mixer (mixed together). Then the optical brightener (preferably as an aqueous dispersion) sprayed with swirling to the powder component. in this connection an agglomerate forms, which is sieved and added of powdered zeolite superficially to improve the Whiteness is coated.

The agglomerate obtained is readily dispersible in water. The optical brightener is protected from oxidation and after the dissolution of the agglomerate in the wash liquor is fully available. Due to the presence of the layer silicate swellable in water there is no "brightener spotting". The agglomerate can be manufactured in brightener-free production facilities Detergents are added subsequently, so that the systems not to be contaminated with brighteners.

The invention further relates to a detergent containing the detergent additive described above in addition to usual Detergent components such as anionic and nonionic Surfactants, builders (polymers), polymers (co-builders), Graying inhibitors, bleaching agents and bleach activators, Enzymes, foam inhibitors, fragrances and / or Dyes.

The preferred manufacturing process is explained below.

The powdery layered silicate becomes with intensive swirling the optical brightener or a mixture of different optical brightener as an aqueous dispersion (slurry) added.

If the optical brightener is added as an aqueous dispersion, the mixture agglomerates at a water content of approximately 20 to 30 wt .-%, based on the total mixture. After a Mixing time of about 2 to 5 minutes gives an agglomerate that in a suitable dryer, preferably in a Fluid bed dryer to a residual water content of about 2 to 15% by weight, preferably dried from about 5 to 10% by weight becomes. The agglomerate obtained is broken up with a sieving machine a particle size of about 0.2 to 2.5 mm, preferably of 0.5 to 1.7 mm, sieved. The fraction <0.2 mm becomes again Agglomeration fed. Coarse grain that forms is also removed crushed with a roller crusher and again on the screening plant given.

The sieved agglomerate is placed in a drum mixer (for Example in a drum mixer from Telschig) or one Given granulation plate. Then about 3 to 15 wt .-%, preferably about 5 to 10% by weight synthetic zeolite in fine-grained form added. The average particle size of this Powder should preferably be <20 μm, in particular approximately 3 to 10 µm. Store when mixing the agglomerate with the powder the latter on the outer surface of the agglomerate on. Since the powders used have a whiteness of> 90% (R 456, Elrepho), arises around the yellowish by the brightener colored agglomerate surface a white coating, so that the agglomerate obtained is white and the color of the detergent is indistinguishable.

The detergent additive produced by the process described also has the following advantages:

The bulk density is greater than 700 g / liter, so that it with Detergent with high bulk density is compatible. Through the Swelling effect of the layered silicate contained in the detergent additive the agglomerates quickly disintegrate in water. It won't Whitening spotting observed on the laundry. The optical brightener is fully available in the detergent. The agglomerate is mechanically stable. The agglomerate can be subsequently Mix in detergent, which makes up essential parts of the detergent production system not contaminated with optical brighteners become.

The invention is illustrated by the examples below.

example 1

A detergent additive was produced according to the following recipe: A Bentonite (Laundrosil® DGA, Süd-Chemie AG) 98% by weight B Optical brightener (Tinopal® DMS-X hc) 2% by weight

In an Eirich intensive mixer of the RO2 type, 1960 g Laundrosil® DGA powder presented. Then became more intense Whirling 74.4 g Tinopal® DMS-Slurry 36 (corresponding to 40 g Tinopal® DMS-X h.c.) added, followed by the addition of 450 g of water. A light gray agglomerate was obtained, which in a drying cabinet to a residual moisture of 10% by weight of water was dried. Then the grain fraction became 0.4 to 1.4 mm sieved.

5% by weight of the detergent additive was mixed into a brightener-free test detergent. At a wash liquor ratio of 1:20 and a temperature of 30 ° C, this detergent was allowed to act on pre-lightened cotton fabric for 1 min without mechanical movement. After rinsing, drying and ironing, the spotting was assessed visually as follows. In daylight very good Under UV light very good

10% by weight of the detergent additive was placed in an ECE test detergent, which contained 7% Na perborate monohydrate and 3% TAED, mixed.

For comparison, an equivalent amount of brightener, 0.2 % By weight Tinopal® DMS-X h.c., in an identical detergent about the slurry already during the production of the spray product brought in.

Both detergent samples were opened in a climate cabinet 8 Weeks at 30 ° C and 70% rel. Humidity stored.

The loss in% was calculated from the brightener content determined before and after the storage test by means of HPLC analysis. The results are shown in Table I. Brighteners use Loss in% after 8 weeks about detergent additive 23% about spray product 55%

The decrease in the brightener content due to oxidative degradation is when using the detergent additive according to Example 1 clearly smaller compared to a detergent of the same gross composition, where the brightener is included in the spray product is.

Example 2

A detergent additive was produced according to the following recipe: A Bentonite (Laundrosil® DGA, Süd-Chemie AG) 99% by weight B Optical brightener (Tinopal® -CBS-X) 1% by weight

1980 g

Laundrosil® DGA Pulver

60 g

Tinopal® CBS Slurry 33 (entsprechend 20 g Tinopal® CBS-X)

440 g

Wasser

The manufacturing process corresponds to Example 1, with the following weights being selected:

1980 g

Laundrosil® DGA powder

60 g

Tinopal® CBS Slurry 33 (equivalent to 20 g Tinopal® CBS-X)

440 g

water

Then 90 parts by weight of the sieved to 0.4 to 1.4 mm light beige agglomerate with 10 parts by weight of zeolite A added, and mixed in a granulating plate. It was the surface of the agglomerate is coated with zeolite powder, whereby a white agglomerate was obtained.

The detergent additive was subjected to a spotting test on pre-lightened cotton fabric as described in Example 1. The evaluation is as follows: In daylight very good Under UV light acceptable.

10% by weight of the detergent additive was added to that in Example 1 Test detergent described mixed.

In the comparison sample, 0.1% Tinopal® CBS-X was over the Slurry introduced into the spray product.

A storage stability test as described in Example 1 was then carried out. The results are shown in Table II. Brighteners use Loss in% after 8 weeks about detergent additive 27% about spray product 37%

When using the detergent additive, the brighteners are broken down less than in a detergent of the same gross composition, where the brightener is included in the spray product is.

Claims (12)

1. Detergent additive in agglomerate form, characterized in that it contains at least one swellable layer silicate, which represents a natural swellable clay mineral, and at least one optical brightener in intimate contact with each other, the optical brightener being at least partially deposited between the layers of the layer silicate.
2. Detergent additive according to Claim 1, characterized in that the weight ratio of swellable layer silicate(s) to optical brightener(s) is about 200-7:1, preferably about 100-10:1.
3. Detergent additive according to Claim 1, characterized in that the swellable clay mineral is montmorillonite, beidellite, saponite or hectorite.
4. Detergent additive according to any one of Claims 1 to 3, characterized by the fact that the optical brightener is a stilbene derivative.
5. Detergent additive according to any one of Claims 1 to 4, characterized in that the agglomerate particles are enrobed with synthetic zeolite or with a layered sodium silicate.
6. Detergent additive according to any one of Claims 1 to 4, characterized in that the agglomerate particles are coloured with a dye, preferably a pigment dye.
7. Detergent additive according to any one of Claims 1 to 4, characterized in that it contains an active substance, preferably a photobleaching agent in addition to the swellable layer silicate and the optical brightener.
8. Detergent additive according to any one of Claims 1 to 7 characterized in that the agglomerate has a bulk density of more than about 700 g/Liter.
9. Process for the production of a detergent additive in the form of an agglomerate, according to any one of Claims 1 to 8, characterized in that the optical brightener(s) is(are) added as an aqueous slurry to the layer silicate(s).
10. Process according to Claim 9, characterized in that an agglomerate with a particle size of about 0.2 to 2.5 mm and a residual water content of 2 to 15 wt.% is formed.
11. Process according to Claims 9 or 10, characterized in that the obtained agglomerate is(are) enrobed with about 3 to 15 wt.% of a synthetic zeolite, (b) coloured with about 0.01 to 0.5 wt.% of a dye, especially a pigment dye, or (c) treated with about 0.3 to 5 wt.% of a coloured active substance, preferably a photobleaching agent.
12. Detergent containing a detergent additive according to any one of Claims 1 to 8 or produced according to any one of Claims 9 to 11, in addition to ordinary detergent components.