NL8202044A - FRICTION GRANULATE BASED ON ALKALIMETALALUMINUM SILICATE WITH GOOD DISPERSIBILITY IN A WATER-CONTAINING BATH. - Google Patents

Description

N

S ’\ * JT.O. 30,966 1

Rub-on granules based on alkali metal aluminum silicate with good dispersibility in a water-containing bath.

The object of the invention is a rubbing real, free-flowing granulate based on water-insoluble alkali metal aluminum silicate with a good dispersibility and a high rate of disintegration in water bath, its preparation and the use in washing, rinsing and cleaning agents and for water softening.

10 Water-insoluble alkali metal aluminum silioate is recommended as a substitute for the polyphosphates in washing, rinsing and cleaning products: However, difficulties have been encountered in the application of this product. Alkali metal aluminum silicate is a very fine powdery product of a peeling character, which does not remain wetted in water for a very long time, so that the activity is delayed, and a poor washing result is achieved. Dusting also occurs when mixing with other formulation ingredients or when formulating, whereby higher dust contents are usually of equal significance with poor flushability from the dosing space.

To avoid lumps forming on the cleaning agents and to ensure good rinsing, the cleaning agents resp. the cleaning components are usually used in granulate form. Granules based on water-insoluble alkali metal silioate, however, can only be used if they readily disintegrate in water, disperse and return to the original distribution, i.e. the alkali metal aluminum silicate is present in the originally fine particles. Irreversible alkali metal aluminum silicate agglomerates should not be formed, which are difficult to wash out and settle in the tissues. In addition, the exchange power must be maintained.

Attempts have already been made to improve the deleterious properties of the alkali metal aluminum silioate. For example, it is known to increase the wettability of the alkali metal aluminum silicate. For this purpose, the alkali metal aluminum silicate is mixed with an aqueous solution of a hydrophilic agent, such as orthophosphoric or tartaric acid, and the solid hydrophilic agent is added to the moist alkali metal 8202044 i Λ 2 aluminum silicate, the mixture is dried and ground. Although the products thus obtained have a better wettability, they tend to form dust and often do not lead to satisfactory results when used in automatic washing and dishwashing machines.

Br therefore had the problem of producing stable, rubbing, non-dusting, free-flowing granules based on al-potassium aluminum silicate, which do not have the drawbacks outlined.

The object of the invention is a rubbing, free-flowing granulate with good dispersibility and high dispersion rate in aqueous solution, consisting of water-insoluble alkali metal aluminum silicate and at least 5 wt.% Of an amino polycarboxylic acid and / or an alkali metal salt thereof .

Aminopolycarboxylic acids resp. the preferred alkali metal salts according to the invention are nitri-lotri acetic acid, ethylenediamine tetraacetic acid and diethylene triamine pentaacetic acid.

Also aminopolycarboxylic acids resp. alkali metal salts thereof are suitable, wherein 1 or more of the carboxymethyl groups have been or have been replaced by another residue. For example, the following groups may be present in place of the carboxymethyl group: earboxyalkyl, for example 1-carboxy-ethyl, 1-oarboxypropyl, 2-hydroxyethyl, 2-mercaptoethyl, sulfomethyl, sulfoethyl, alkyl dicarboxylic acids such as, for example, sueoinyl, oapryl, adipyl, -carboxy -4 / -sulfoalkyl, for example aC-carboxy-8-sulfoethyl and others

The aminopolycarboxylic acid can also be a polyolefin with side-chain iminodiacetic acid groups. A mixture of some amino polycarboxylic acids and / or their alkali metal salts can also be used.

In addition, the granules of the invention may also contain a hydroxyl compound with at least 4 carbon atoms, at least one carboxyl, respectively. alkali metal carboxylate group and / or an aldehyde, keto or alcohol group, the sum of the number of hydroxyl groups and carboxyl, respectively. alkali metal boxylate groups and / or aldehyde or keto or alcohol group greater than or equal to 4 · 40 The hydroxyl compound may be a carboxylic acid and / or an alkali metal salt thereof. A preferred carboxylic acid is the gluconic acid (glucono-loton), sodium gluconate or the two fluids inoculate gluconic acid and gluconate-containing solutions.

Other hydroxycarboxylic acids, such as, for example, alkali metal salts of citric acid or tartaric acid, are also suitable.

Hydroxyl compounds according to the invention are further sugar, starch hydrolysis products, such as water-soluble starch, dextrin, polyalcohol, for example sorbitol, mannitol.

The weight ratio of the amino polycarboxylic acid to the hydroxyl compound and / or its alkali metal salts may be from 9 * 1 to 1: 9, preferably 1: 1. The sum of the aminopolycarboxylic acid and the hydroxyl compound should be at least 5 gww.

As the water-soluble ion-exchange alkali metal-aluminum silicate, all silicates mentioned in German Offenle'gung-20 Nos. 2,412,837 and 2,510 * 741 are suitable, preferably alkali metal aluminum silicate such as zeolith of type A, X, I with a crystal water content of about 22 $. The alkali metal aluminum silicate is advantageously used in the form of the commercially available water-containing, about 4% nonionic surfactant stabilized, alkali metal aluminum silicate suspension (alumosilicate suspension), which has a water content (excluding the water of crystallization) of 45 - $ 49 possession.

It is of course also possible to use an unstabilized aluminosilicate suspension.

It has been found that granules consisting of 70-95 wt.% Water-insoluble alkali metal aluminum silicate and 3-5 wt.% Amino polycarboxylic acid, respectively. a mixture of aminopolycarboxylic acid and hydroxyl compound and / or its alkali metal salts have very good properties.

The granulates according to the invention are obtained by mixing the alkali metal aluminum silicate suspension with the aminopolycarboxylic acid or. the mixture of aminopolycar-40 carboxylic acid and hydroxyl compound and / or its alkali metal salts 8202044 4 and subjected to a spray drying treatment.

The alkali metal aluminum silicate suspension is mixed with at least 5 wt.% Amino polycarboxylic acid and / or an alkali metal salt thereof, respectively. a mixture of the hydroxyl compound (calculated on the basis of the alkali metal aluminum silicate content) thoroughly mixed. The amino polyarboxylic acid resp. the mixture with the hydroxyl compound is preferably added as a concentrated aqueous solution. The suspension obtained should have a clearly alkaline pH value '7' 9. If necessary, the pH value must be adjusted by adding alkali. The suspension is heated to 50 ° -70 ° C and subjected to a spray-drying treatment. Spray drying is carried out in a spray tower with a dust nozzle. It is also possible to carry out the spray drying on a spray tower with an atomizer disc or a dual-fabric nozzle.

The granules according to the invention have a high rub fastness. The advantageous rub fastness is obtained at a residual moisture content (excluding crystal water) of not more than 4 °.

In particular, the granules according to the invention are distinguished in that they decompose readily during dispersion in water and are again present in the original fine particles with a size of <25 µm with alkali metal aluminum silicate. Clumping of the silicate particles into irreversible agglomerates does not take place in the granulates according to the invention.

The granules according to the invention are preferably suitable for use in washing, cleaning and dishwashing detergents, textile laundry detergents or in washing aids, such as softening agents. They can be added to the other ingredients in cleaning agents with mixing without causing dust to form. The agents can be stored in a simple package for a long period of time. The flowability is maintained and no segregation takes place. Clumps do not form in the dosing chambers of the washing machines and dishwashers and good rinsability is ensured.

The invention is further elucidated on the basis of the following examples.

8202044 5

Yoorheelden I - 71 «

An aluminum silicate slurry (zeolite A 55 $ content) was mixed with the amino polycarboxylic acid or. mixture of aminopolycarboxylic acid and hydroxyl compound and / or its alkali metal salts well mixed and heated to 50 ~ 70 ° C. 100 kg of the suspension was sprayed per hour in a spray tower 18 m high with a diameter of 2.5 m with a nozzle for 1 substance under the conditions indicated in tahel A.

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To determine the rate of disintegration, 521 of an aqueous washing bath containing the granulate to be tested in an amount corresponding to 6 g of the alkali metal aluminum silicate contained therein and 14 g of tripolyphosphate were prepared. 500 ml of this bath were divided into 4 laun-10 derometer beakers per simulation of a washing process and each time 490 ml of tap water and 10 ml of a 2.5% Genapol T 110 solution were added. The beakers were then rotated at 35 ° C for 15 minutes. The reunited test solution was then passed through a pre-weighed window-tensioned test sieve (approximately 200 x 200 mm nylon fabric). The screen was dried after rinsing with water and alcohol at room temperature overnight and weighed back.

The residues concerned are indicated in percentages based on the alkali metal aluminum silicate (6 g) present in table B in 8202044 8

Table B

Example fo residue on the screen disintegration - 100 yum 63 yum 40 yum 25 yum speed 25 yum 5 Alkali metal aluminum silicate 9856

Example I 1.2 1.2 0.3 0.7 96.6 $

Example II 1.0 0.9 0.4 0.6 97.1 $

Example III 1.7 0.7 0.5 0.9 96.1 # 10 Example IV 1.3 0.8 0.1 0.4 97.4 $

Example V 2.0 0.5 0.9 1.5 95.156

Example VI 1.2 0.9 0.3 0.8 96.856

The fastness to rubbing of the granules according to the invention is shown in Table C.

The fastness to rubbing results from the determination of the grain size distribution before and after treatment of the granules with an increased mechanical rubbing during the sieving process (loading of free-moving nylon brushes on the individual sieves).

20 1. Rub fastness I. Investigation of the grain-size distribution of the granulates by sieve analysis.

100 g of the sample were accurately weighed and placed on a sieve with the largest mesh size 25 (1000 yum) of a standardized test sieve arrangement DIN 4188. After a sieve duration of 5 minutes on a vibrating machine (type JEL) with a force-controlled, three-dimensional sieve movement, the sieve fractions were weighed. The residues of the samples on the sieve were weighed cumulated, i.e. the respective sieve residue is only weighed after association with the next finer residue.

II. Rub fastness.

After completion of the sieve analysis, the total sample was sieved once more with the addition of free nylon brushes on all seven. The fastness to rubbing follows from the direct comparison of the first with the second sieve analysis.

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8202044

Claims (14)

1. Free flowing and rub real granules based on "water insoluble alkali metal aluminum silicate with good dispersibility and high disintegration rate in water containing bath, characterized * that the granulate consists of water insoluble alkali metal aluminum silicate and at least 5 gsw. $ Of an amino polyarboxylic acid and / or an alkali metal salt thereof. Granules according to claim 1, characterized in that the aminopolyarboxylic acid is nitrilotriacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, N- (2-hydroxyethyl) ethylenediamine triacetic acid and / or an alkali metal salt thereof. Granulate according to claims 1 and 2, characterized in that the granulate contains mixtures of amino polyarboxylic acids and / or their alkali metal salts. Granulate according to claims 1 to 3, characterized in that that the granulate additionally has a hydroxyl compound with at least 4 carbon atoms, at least one ear-20 boxyl resp. alkali metal carboxylate group and / or aldehyde. contains keto or alcohol group, wherein the sum of the number of hydroxyl groups and carboxyl reap, alkali metal carboxylate group and / or aldehyde or keto or alcohol group is greater than or equal to 4. 25 Granulate according to claim 4, characterized in that the hydroxyl bond is a carboxylic acid, for example gluconic acid, citric acid, tartaric acid and / or an alkali metal salt thereof. Granulate according to claims 1 to 5, characterized in that a weight ratio of the aminopolycarboxylic acid and / or its alkali metal salt to the hydroxyl compound is 9 s 1 to 1: 9, preferably 1 s 1 and the sum of aminopolyo-carboxylic acid and / or alkali metal salt and hydroxyl compound is at least 5% by weight. 35 Granulate according to claims 1 to 6, characterized in that the granulate contains a residual moisture content (excluding crystal water) of not more than 4 fo. Granulate according to claims 1 to 7, characterized in that. that the granulate consists of 70-95 wt.% water insoluble 8202044 alk alkali metal aluminum silioate and 30-5 wt. 9 * Process for the preparation of granules based on water-insoluble alkali metal aluminum silioate, characterized in that an alkali metal aluminum silicate suspension with an aminopolyo-carboxylic acid or. mixing a mixture of amino polycarboxylic acid and hydroxyl compound and / or its alkali metal salts according to claims 1-8 and subjecting to a spray drying treatment. Process for the preparation of granules according to claim 9, characterized in that the alkali metal aluminum silicate is used as a suspension with a moisture content of 45 - 49% with at least 5% by weight (calculated on the alkali metal aluminum silicate content) of an aminopolyoarboxylic acid or. mixture of aminopolyocarboxylic acid and hydroxyl compound and / or its alkali metal salts, heating the mixture to 50-70 ° C and subjecting to a spray drying treatment. Process for preparing granules according to claims 9 and 10, characterized in that the aminopolycarboxylic acid or. mixture of aminopolyocarboxylic acid and hydroxyl compound and / or its alkali metal salts as a concentrated aqueous solution. Process for preparing the granules according to claims 9 to 11, characterized in that the suspension mixture is adjusted to a pH value of 79 with alkali if necessary. Method according to claims 9 to 12, characterized in that the spray drying is carried out in a spray tower with a one-piece nozzle. Use of the granulate according to claims 1 to 13 as a builder in detergents and cleaning agents, dishwashing detergents, laundry detergents and for the softening of water. 8202044