EP0856046B1 - Washing-agent additive - Google Patents

Abstract

Described is a washing-agent additive in agglomerate form, the additive being characterized in that it contains at least one swellable layered silicate, an optical brightener and a surfa ctant.

Description

The invention relates to a detergent additive that at least a swellable layered silicate and other additional components contains.

A related invention is disclosed in parallel EP-A-0 857 200 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 made from the various components. Subsequently this slurry is spray dried.

DE-A-34 34 854 describes a process for the production a granular, free-flowing detergent component that inorganic carrier substances (especially sodium alumosili Zeolite A type cate) contains surfactants and optical brighteners. Zeolites are not swellable Phyllosilicates.

WO 94/05 761 describes a process for the production a detergent with a high bulk density and good solubility, with non-swellable silicates (e.g. zeolites), Surfactants and optical brighteners can be used.

WO 89/08 695 describes a stabilized particulate Composition for use in detergents, which optical Contains brighteners or enzymes. The particles are through one Bentonite coating protected. Contain separated particles Bleaches, surfactants or builders.

DE-A-35 26 405 describes layered silicates with limited Swelling capacity, as well as their use in detergents and cleaning agents, which also contain surfactants and optical brighteners. The layered silicates are synthetic aluminosilicates.

Detergents are also known from other references, which Na alumosilicates, such as zeolites, that is not swellable Silicates, as well as optical brighteners and surfactants.

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 with 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 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 components 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 debris weight 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 adjusting agents, of which likewise bleaches contained in the detergent, such as sodium perborate, but especially sodium percarbonate, separated, so optical Brighteners are oxidized. That used up here Bleaching potential stands for the later bleaching effect the wash liquor is no longer available. Above all, it can the oxidation product of the optical brightener is colored yellow be, causing the detergent on the one hand a yellow tint shows, on the other hand, the yellow oxidation product of the brightener Nouns on the laundry textiles, causing an impairment the aesthetic aspect, especially with whites Laundry performs.

The origin 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) arises Peracetic acid, from which active oxygen is released becomes. This problem is discussed in M. Husslein et al., 36th Internationale Conference 1994, WFK - Research Institute for Cleaning technology e.V., pages 82-85.

In detergents with low bulk density, which 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 Brighteners, 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 sump". Since there insufficient mechanical stress on the agglomerates occurs, these dissolve only partially, which means that 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 advertised in contact with the wash liquor, causing the optical brighteners homogeneously dissolved 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 whitening 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, which is characterized in that it has at least one swellable layered silicate, which is a natural or synthetic clay mineral, an optical brightener embedded between the layers of layered silicate and contains a surfactant.

The surfactant is believed to contribute to the optical Brightener at least partially homogeneous between the layers of the layered silicate because of the X-ray diffraction pattern of the dried product a layer expansion of from about 1.05 to 1.30 nm down to about 1.35 to 1.85 nm becomes.

Due to the presumed storage of the optical brightener between the layers of the layered silicate, this is the Oxidation processes during the storage of the detergent reliably withdrawn, and it becomes when using the detergent the "brightener spotting" avoided on the laundry.

The detergent additive preferably contains in addition to the swellable Layered silicate, the optical brightener and the surfactant an alkali carbonate.

a) etwa 5 bis 60 Gew.-% quellfähige(s) Schichtsilicat(e);

b) etwa 5 bis 35 Gew.-% Tensid(e);

c) etwa 5 bis 60 Gew.-% Alkalicarbonat(e);

d) etwa 1 bis 20 Gew.-% optische(n) Aufheller.

The detergent additive according to the invention preferably contains

a) about 5 to 60% by weight of swellable layered silicate (s);

b) about 5 to 35% by weight of surfactant (s);

c) about 5 to 60 wt% alkali carbonate (s);

d) about 1 to 20% by weight of optical brighteners.

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 used become. The layered silicate is preferably in one Amount of 10 to 50% by weight, in particular 30 to 50% by weight used.

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

The surfactant is preferably selected from the group consisting of anionic and selected nonionic surfactants, the nonionic Surfactant preferably a mixture of fatty alcohol ethoxylates represents different degrees of ethoxylation.

The fatty alcohol ethoxylates have the formula: RO- (EO) _y -H, where R is a hydrocarbon radical having 10 to 18, in particular 12 to 18 carbon atoms, EO is an ethylene oxide group and y is a number from 2 to 20, in particular from 3 to 10. Mixtures of fatty alcohol ethoxylates of various degrees of ethoxylation can also be produced in a targeted manner.

These fatty alcohol ethoxylates are getting eager between the Layer slats stored. The nonionic surfactants, in which the optical brighteners, especially of the stilbene type, are soluble, promote their transport between the slats of the swellable layered silicate. The optical brighteners are intercalated between the lamellae of the layered silicate and share with other detergents before the reaction protected.

Intercalated with surfactants and optical brighteners Layered silicates in granular form swell in water and give the surfactants and optical brighteners of the solution in water free. The optical brighteners and the surfactants are therefore in Washing process fully available. Due to the swelling effect of the layered silicate agglomerate in water Agglomerates blown up and dispersed in the water, causing the "Lightening spotting" is avoided.

The alkali carbonate, especially in the form of sodium carbonate is used for several functions:

If the layered silicate is agglomerated with the surfactant, it is obtained a soft, sticky with increasing content of surfactant Agglomerate that is not free-flowing and not capable of ensiling. Due to the presence of sodium carbonate, the mechanical Improved stability of the agglomerate and its stickiness reduced. There is also sodium carbonate in the detergent for adjusting the alkalinity and as a builder component he wishes. The alkali carbonate is preferably used in amounts of about 10 to 40% by weight, in particular about 12 to 30% by weight If the layered silicate is agglomerated with the surfactant, it is obtained a soft, sticky with increasing content of surfactant Agglomerate that is not free-flowing and not capable of ensiling. Due to the presence of sodium carbonate, the mechanical Improved stability of the agglomerate and its stickiness reduced. There is also sodium carbonate in the detergent for adjusting the alkalinity and as a builder component he wishes. The alkali carbonate is preferably used in amounts of about 10 to 40% by weight, in particular about 12 to 30% by weight used.

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.

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

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

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

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

Handelsbezeichnung: Tinopal® CBS-X

Handelsbezeichnung Tinopal® BLS-X

Suitable optical brighteners are, for example

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

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

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

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

Trade name: Tinopal® CBS-X

Trade name Tinopal® BLS-X

Since the surfactant is hygroscopic, the agglomerate particles are the detergent additive, preferably with synthetic zeolite envelops, resulting in the flowability of the agglomerate particles is improved. The coating with zeolite continues to improve the degree of whiteness of the agglomerate.

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 the detergent additive described above in agglomerate form, which is characterized in that (a) the optical brightener as an aqueous slurry at the same time with the surfactant (s) to the layered silicate (s) or (b) at least part of the optical brightener (s) previously dissolved in the surfactant (s) and the solution to the Layer silicates (s) are added.

The swellable layered silicate is preferably mixed before Add the optical brightener / surfactant with the alkali carbonate.

The powder components can, for example, in an intensive mixer, e.g. mixed together in an Eirich mixer. Subsequently, the optical brighteners (preferably as an aqueous dispersion) and that Surfactant sprayed through to the powder component. This forms an agglomerate, which is lower Mixing speed with which zeolite is powdered. The resulting Agglomerate is sieved and by adding more Zeolite (especially Zeolite P) in powder form on the surface to reduce stickiness and improve Whiteness 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 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, framework substances (builders), 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 powdered layered silicate and the powdered sodium carbonate are premixed intensively. Under intense The surfactant or a Solution of the surfactant added. At the same time, the optical Brightener or a mixture of different optical brighteners added as an aqueous dispersion (slurry). Alternatively, you can a solution of the optical brightener in a surfactant solution be given to the powder mixture.

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 screening 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 the again Agglomeration fed. Coarse grain that forms is also removed crushed with a roller crusher and again on the screening plant given.

Becomes part of the optical brightener together with the surfactant added to the powder mixture, the optical is first Brightener dissolved in powder form in the surfactant. The weight ratio between surfactant and optical brightener can be 15: 2 to 4:10, preferably 10: 3 to 10: 8. The solution or Dispersion of the optical brightener in the surfactant becomes more intense Whirling is added to the powder, at the same time further portions of the optical brightener in aqueous dispersion be added.

After a mixing time of about 2 to 5 minutes, it forms Agglomerate, which, however, due to the presence of the surfactant something is sticky and therefore prone to caking. By Add about 0.5 to 5% by weight of a synthetic zeolite during the last 30 seconds of the agglomeration process the stickiness of the agglomerate is reduced so far that the agglomerate is dried in a fluidized bed and as described, can be screened.

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, Eirepho), is created 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 of 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 active components Surfactant and optical brightener are full in the detergent available. Due to the presence of layered silicate and alkali carbonate the agglomerate is mechanically stable. The agglomerate can be added to the detergent afterwards, whereby essential parts of the detergent production plant not be contaminated with optical brighteners.

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) 40% by weight B sodium 15.52% by weight C Non-ionic surfactant R- (O-CH ₂ -CH ₂ ) ₄ -OH (R = C ₁₄ / C ₁₅ ) 10.00% by weight D Optical brightener A (Tinopal® DMS, slurry in water with 36% active ingredient) 18.6% by weight e Optical brightener B (Tinopal® CBS, slurry in water with 30% solids content) 5.88% by weight F Zeolite P 10% by weight

In an Eirich intensive mixer type R02 (filling 3-5 Liters, power 2.7 kW) were 800 g of component A and 310.4 g of component B are introduced and mixed for 1 minute. Then Component C was added during mixing followed from the addition of components D and E. It turned yellow tinted agglomerate with a water content of 18% by weight receive. This agglomerate was placed on a drying cabinet Residual moisture of 6 wt .-% water dried. Then the Grain fraction sieved 0.2 to 1.7 mm.

Then the sieved agglomerate with 10 wt .-% zeolite P added and mixed in a granulating plate. there the surface of the agglomerate was coated with zeolite powder, whereby a white agglomerate was obtained.

20 Gew.-% Na-Percarbonat

5 Gew.-% TAED

6 Gew.-% Nichtionisches Tensid (Komponente C)

12 Gew.-% Fettalkholsulfat (ROSO₃Na; R=C16/C18)

2% by weight of the detergent additive was mixed into a new generation compact detergent produced by spray agglomeration with a bulk density of 850 g / liter. This detergent contained:

20% by weight Na percarbonate

5 wt% TAED

6% by weight nonionic surfactant (component C)

12% by weight fatty alcohol sulfate (ROSO ₃ Na; R = C16 / C18)

As a comparison, an equivalent amount of brightener A and brightener B was introduced into an identical detergent during the production of the spray agglomerate. Both detergent formulations were stored in a closed refill bag at 40 ° C for 4 weeks. The breakdown was calculated from the brightener content determined before and after the storage test by means of HPLC analysis. The optical aspect of the detergent was also assessed visually. The results are shown in Table I. Brighteners use Degradation after 4 weeks / 40 ° C optical aspect Brightener A Brightener B output 4 weeks / 40 ° C about detergent additive according to Example 1 20% 40% White White over spray agglomerate 40% 50% White yellow

When using the detergent additive, the brightener is degraded A and B significantly lower, and there is no annoying Yellow color of the detergent due to oxidation products.

Example 2

As an alternative to Example 1, components A and B in mixed in an Eirich mixer. A solution of 134 g was obtained Tinopal® DMS-X h.c. (Powder form) in 438 g of component C (Surfactant), which is added to the mixture during the mixing process is given from components A and B. Then was component E added as a slurry. It also became a Obtained yellow tinted agglomerate, which is processed as in Example 1 has been.

2% by weight of the detergent additive according to this example was again mixed into the detergent described in Example 1 and tested accordingly. The results are shown in Table II. Brighteners use Degradation after 4 weeks / 40 ° C optical aspect Brightener A Brightener B output 4 weeks / 40 ° C about detergent additive according to Example 2 20% 40% White White

The stabilization of brightener A occurs regardless of whether as a slurry in water (example 1) or in non-ionic Surfactant (Example 2) incorporated into the detergent additive has been.

Example 3

A detergent additive was produced according to the following recipe: A Bentonite (Laundrosil® DGA, Süd-Chemie AG) 42% by weight B sodium 21.2% by weight C Non-ionic surfactant R- (O-CH ₂ -CH ₂ ) ₄ -OH (R = C ₁₄ / C ₁₅ ) 9.0% by weight D Non-ionic surfactant R- (O-CH ₂ -CH ₂ ) ₈ -OH (R = C ₁₄ / C ₁₅ ) 9.0% by weight e Optical brightener A (Tinopal® DMS, slurry in water with 36% active ingredient) 7.0% by weight F Optical brightener B (Tinopal® CBS, slurry in water with 30% solids content) 1.8% by weight G Zeolite P 10% by weight

As in Example 1, 840 g were in an Eirich intensive mixer of component A and 424 g of component B for about one minute premixed. Then a mixture of components E (140 g) and F (36 g) added. Then 180 g of the component C and 180 g of component D (premixed) added.

It became a slightly yellowish, slightly sticky Obtained agglomerate. Have been used to reduce stickiness 5% zeolite P was added and mixed for about 20 seconds.

The agglomerate obtained was to a grain size of 0.2 mm sieved to 2.0 mm.

The sieved agglomerate was then again with 5 % By weight of zeolite P, and mixed in a granulating plate, the agglomerate on the surface with zeolite powder was coated, thereby obtaining a white agglomerate has been.

14% Na-Perborat-Monohydrat

5% TAED

6% Nichtionisches Tensid C+D = 1:1

12% Fettalkholsulfate (RO-SO₃Na; R = C₁₆/C₁₈)

5% by weight of the detergent additive according to this example was mixed into a compact detergent produced by spray drying with a bulk density of 700 g / liter. This detergent contains:

14% Na perborate monohydrate

5% TAED

6% non-ionic surfactant C + D = 1: 1

12% fatty alcohol sulfates (RO-SO ₃ Na; R = C ₁₆ / C ₁₈ )

For comparison, an equivalent amount of brightener A and Brightener B in an identical detergent already at the Manufacture of the spray product introduced.

A position stability test as described in Example 1 was then carried out. The results are shown in Table III. Brighteners use Degradation after 4 weeks / 40 ° C optical aspect Brightener A Brightener B output 4 weeks / 40 ° C about detergent additive according to Example 1 7% 0% White White about spray product 24% 0% White yellow

Brightener A becomes when using the detergent additive degrades much more slowly than when used in a spray product. The detergent remains white.

Claims (13)

1. Detergent additive in non-spray-dried agglomerate form, characterised in that it contains at least one swellable sheet silicate which is a natural or synthetic clay mineral, an optical brightener stored between the sheets of the sheet silicate and surfactant stored between the sheets of the sheet silicate, and has a bulk density of more than 700 g/l.
2. Detergent additive according to claim 1, characterised in that in addition to the swellable sheet silicate, the optical brightener and the surfactant, it contains an alkali carbonate.
3. Detergent additive according to claim 1, characterised in that it contains:

   a) about 5 to 60 wt.% swellable sheet silicate(s)

   b) about 5 to 35 wt.% surfactant(s),

   c) about 5 to 60 wt.% alkali carbonate(s),

   d) about 1 to 20 wt.% optical brightener(s).
4. Detergent additive according to claim 1, characterised in that the swellable clay mineral is montmorillonite, beidellite, saponite or hectorite.
5. Detergent additive according to any one of claims 1 to 4, characterised in that the surfactant is selected from the groups of anionic or non-ionic surfactants.
6. Detergent additive according to claim 5, characterised in that the non-ionic surfactant is a mixture of fatty alcohol ethoxylates with different degrees of ethoxylation.
7. Detergent additive according to any one of claims 1 to 6, characterised in that the optical brightener is a stilbene deriyative.
8. Detergent additive according to any one of claims 1 to 6, characterised in that the agglomerate particles are enclosed with synthetic zeolite, preferably zeolite P.
9. Method for producing a detergent additive in the form of an agglomerate according to any one of claims 1 to 8, characterised in that (a) the optical brightener(s) is/are added as aqueous slurry to the sheet silicate(s) simultaneously with the surfactant(s) or (b) at least part of the optical brightener(s) is dissolved in the surfactant(s) in advance and the solution is then added to the sheet silicate(s).
10. Method according to claim 9, characterised in that the swellable sheet silicate is mixed with the alkali carbonate before the optical brightener/surfactant is added.
11. Method according to claim 9 or 10, characterised in that an agglomerate is formed with a particle size of about 0.2 to 2.5 mm and a residual water content of 2 to 15 wt.%.
12. Method according to any one of claims 9 to 11, characterised in that the agglomerate obtained is enclosed with 3 to 15 wt.% of a synthetic zeolite, preferably zeolite P.
13. Detergent containing a detergent additive according to any one of claims 1 to 8 or produced according to any one of claims 9 to 12, in addition to conventional detergent components.