DE3316513A1 - Abrasion resistant granular materials based on alkali metal aluminium silicate - Google Patents

Abstract

A proportion of at least 5% by weight of a homo- or copolymeric polycarboxylic acid and/or its alkali metal salt makes it possible to obviate detrimental properties of the alkali metal aluminium silicate in cleaning agents.

Description

Joh. A. Benckiser GmbH, "April 12, 1983

6 700 Ludwigshafen jab 2571

WZ / g

Abrasion-resistant granules based on alkali aluminum silicate

The invention relates to an abrasion-resistant, free-flowing granulate based on water-insoluble alkali aluminum silicate with good dispersibility and high disintegration rate in aqueous liquor, its production and use in washing, Dishwashing and cleaning agents and for water softening.

Water-insoluble alkali aluminum silicate is recommended as a replacement for polyphosphates in detergents, dishwashing detergents and cleaning agents. However, difficulties have arisen in using this product. Alkali aluminum silicate is a very finely powdered product with a flour-like character that is immersed in water remains unwetted for a very long time, "whereby the effectiveness occurs with a delay and thus a poor washing result is achieved will. When mixing with other recipe

T *

constituent parts or dust formation during assembly, whereby higher levels of dust are usually synonymous with poor flushability from the dosing chamber.

To avoid clumping of the cleaner and easy rinsing To ensure that the cleaning agents or cleaning components are mostly used in granulate form. However, granules based on water-insoluble alkali metal aluminum silicate can only be used if they are in water easily disintegrate, disperse and return to the original distribution, i.e. the alkali aluminum silicate in the originally fine particles. There must be no irreversible alkali aluminum silicate agglomerates, that are difficult to rinse out and lodge in the tissues. In addition, the exchange capacity must be preserved.

Attempts have already been made to improve the disadvantageous properties of the alkali aluminum silicate. So it is known that To increase the wettability of the alkali aluminum silicate. For this purpose, the alkali aluminum silicate is mixed with an aqueous solution a hydrophilizing agent such as orthophosphoric acid or tartaric acid mixed or the solid hydrophilizing agent Damp alkali aluminum silicate added, the mixture dried and ground. The products thus obtained are sit better wettability, but they tend to form dust and lead when used in automatic washing and ship winding machines often produce unsatisfactory results.

The task was therefore to produce stable, abrasion-resistant, non-dusting, free-flowing granules based on alkali aluminum

BATH ORIGINAL .

DO IO

Produce silicate that does not have the disadvantages outlined above exhibit.

The invention therefore relates to abrasion-resistant, free-flowing granules with good dispersibility and a high rate of disintegration in aqueous solution / consisting of water-insoluble Alkali aluminum silicate and at least 5% by weight of a homo- or copolymeric polycarboxylic acid and / or its alkali salt.

Preferred homo- or copolymeric polycarboxylic acids or their alkali metal salts are acids with a average molecular weight of 1000 - 1.5 million preferred but 12,000 - 500,000.

■ The polycarboxylic acids to be used according to the invention have the general formula

- X

C -

Z I

.COOH

where X, Y and Z, hydrogen ,. Methyl, acrylic, aryl, Can be carboxyl, hydroxy and carboxymethyl groups.

The following can occur as monomeric units:

ORIGINAL COPY

where R _{1 is} an alkyl group with C ₁ to C ₁₂ or a C ₁ to C ₁₂ acyl group, optionally hydroxy-substituted.

CH.

COOR.

R ₂ = H or CH ₃ R = H or C

and

. to C ₁₀ alkyl groups can be hydroxy-substituted.

- ι ⁴

-.C

R-

where R. to R _{7 are} hydrogen or alkyl groups and up to R ₇ together 1 - 20 carbon can be hydroxy-substituted,

to R ₇ together have 1 - 20 carbon atoms. R ₄ to R ₇

Polycarboxylic acids to be used with preference are polyacrylic acids and copolymers of maleic acid or of maleic anhydride, the copolymers of maleic acid or of maleic anhydride with methyl vinyl ether, ethyl vinyl ether, or acrylic acid have an average molecular weight of 12,000 to 500,000. '

Ö IDO IO

In addition, the granules of the invention can also contain an aminopolycarboxylic acid and / or its alkali metal salts.

Preferred aminopolycarboxylic acids and their alkali salts are nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylletriaminepentaacetic acid. .

The weight ratio of homo- or copolymeric polycarboxylic acid to the aminopolycarboxylic acid and / or its alkali salt can be 9: 1 or 1: 9, preferably 1: 1. The sum of polycarboxylic acid and aminopolycarboxylic acid should be at least 5% by weight.

On water-insoluble, ion-exchanging alkali aluminum silicate All silicates mentioned, for example, in DE-OS 24 12 837 and DE-OS 25 10 741 come into consideration, preferably alkali aluminum silicate like zeolite of type A, X, Y with a water of crystallization content of approx. 22%. The alkali aluminum silicate is advantageous in the form of the commercially available water-containing, With approx. 1 - 2% nonionic stabilized alkali aluminum silicate suspension (aluminosilicate slurry) used, which have a water content (excluding the water of crystallization) of 37 - 45%.

It is of course also possible to use a non-stabilized Use aluminosilicate slurry.

It has been shown that granulates consisting of 70 - 95 .Weight. ' % water-insoluble alkali aluminum silicate and 30 - 5

BATH ORIQINAL.

% By weight of homo- or copolymeric polycarboxylic acids or mixture of homo- or copolymeric polycarboxylic acid "and polyaminocarboxylic acid and / or their alkali salts have very good properties for the purposes of the present invention. . ·

The granules according to the invention are obtained by mixing the alkali aluminum silicate slurry with the polycarboxylic acid according to the invention or the mixture of polycarboxylic acid and aminopolycarboxylic acid and / or their alkali salts and spray-drying. The alkali aluminum silicate slurry is intimately mixed with at least 5% by weight of polycarboxylic acid and / or its alkali salt or a mixture with the aminopolycarboxylic acid (based on the alkali aluminum silicate content). The polycarboxylic acid or the mixture with the aminopolycarboxylic acid is preferably added as a concentrated aqueous solution. The slurry obtained must have a clearly alkaline pH greater than 9. If necessary, the pH value must be readjusted by adding alkali. The slurry is at 50 - 70 ⁰ C is heated and spray dried. Spray drying is carried out in a spray tower with a 1-substance nozzle. It is also possible to carry out the spray drying on a spray tower with an atomizer disc or 2-substance nozzle.

The granules according to the invention have a high abrasion resistance. The advantageous strength is at a residual moisture (excluding crystal water) of no more than Receive 4%. >

Surprisingly, those according to the invention stand out Granules are characterized by the fact that they are dispersed in water

_.__! . :; ___ ·. _.._ "ORIGINAL BATHROOM.. COPY

OO IUO

Easily disintegrate and the alkali aluminum silicate returns to its original fine particles of a size below 25 μ. present. ' An agglomeration of the silicate particles to form irreversible agglomerates occurs in the case of the invention Granules do not take place.

The granules according to the invention are excellent for the Use in detergents, cleaning agents and dishwashing detergents, textile detergents or in washing aids, such as softeners, suitable. You can use the rest of the ingredients in Cleaners can be mixed in without the formation of dust. The funds can be used in simple packaging for longer periods of time Period of time to be stored. The flowability is retained, there is no segregation. A clump in the dosing chamber of the washing machine and dishwasher does not occur and easy rinsing is guaranteed.

The invention is explained in more detail using the following examples:

Example 1-8

An aluminum silicate slurry (. A zeolite content 61%) was well mixed with the polycarboxylic acid or the mixture of polycarboxylic acid and aminopolycarboxylic acid and / or alkali metal salts thereof and at 50 - 70 ⁰ C heated. Approx. 1.00 kg of the slurry were sprayed per hour in an 18 m high spray tower with a diameter of 2.5 m with a 1-substance nozzle under the conditions specified in Table 1 below. /

Tabel 1 3 . . .4. 5 6th 7th 8th example 1 2

Zeolite A slurry. 150 kg 150 kg 150 kg 150 kg 150 kg 150 kg 150 kg 150 kg addition of ■. '

Maleic anhydride / vinyl ethyl ether

- Copolymer j MGW 240,000 12kg j

Maleic anhydride / vinylinethyl ether,

- Copolymer J MGW 500,000 12 kg

Maleic acid / vinylitethyl ether,

Copolymer Na-Salz ^

MGW 68,000. .u>

35% solution 26 kg,

Polyacralic acid

MGW 150,000

40% solution '' 29 kg

Maleic acrylic acid ¹ copolymer

Na-SaIz MGW "70,000." X 20 kg

35% solution '25 kg

Polyacrylate sodium salt
MGW 20,000
. 35% solution ■

Nitrilotriacetate
; (40% solution)

% Proportion of additive (TS or on TS)
pH value slurry

8th 10 9 11th 8th , 5 27 kg 11 5 11th CO .. · "■ '■■ 10.2 11.0 11.3 10.5 11th 10, 7th 10.6 CO cn 9.5 cn 10.9 CO

Table 1 (continued)

Supply air itemp. 280 267 279 280 235 250 269 281 Exhaust air Itenp. 145 141 144 143 125 131 126 143 • Nozzle pre-pressure 8 bar 8 bar · 8 bar 9 bar 8 bar 8 bar 9 bar 8 bar

Bulk density g / 1 580
Residual moisture% 1.2

Product appearance: Examples 1-8: solid grain, free-flowing, not dusty.

570 560 570 590 610 600 610 0.8 1.0 1.7 0.2 1.6 2.1 2.7

331651

were used

Gantrez AN 119:
GAF

Gantrez AN 139:
GAF

Maleic anhydride / vinylitiethyl ether

- copolymer MGW 240,000

Maleic anhydride / vinyl ethyl ether

- Copolymer MGW 500,000

Sokalan CP 2:

Maleic acid / vinyl methyl ether - Na salt copolymer MGW 68,000

Sokalan CP 5:
BASF

Maleic acrylic acid copolymer

Na-SaIz

MGW 70,000

Sokalan PAS:
BASF

Polyacrylic acid MW 150,000

Tamol PA:
BASF

Polyacrylate, sodium salt, MW 20,000

<J I UvJ

The excellent high rate of disintegration of the invention Granules in aqueous liquor are shown in Table 2.

To determine the rate of disintegration, 2 liters of an aqueous wash liquor were prepared, each containing the granulate to be tested in an amount corresponding to 6 g of the alkali aluminum silicate contained therein and 14 g of tripolyphosphate. 500 ml each of this liquor were distributed over 4 launderometer beakers to simulate a washing process, and 490 ml of tap water and 10 ml of 2.5% strength solution of a fatty alcohol ethoxylate with 11 E0 groups were added. The cups were then ^{rotated at 35 °} C. for 15 minutes. The recombined test solution was then poured over pre-weighed test sieves (approx. 200 × 200 mm nylon fabric) stretched in a frame. After rinsing with water and alcohol, the sieves were dried overnight at room temperature and reweighed.

The respective residues are in percent, based on the alkali aluminum silicate (6g) present, in Table 2 specified.

Tabel

% Residue on the sieves 100 μ 63 μ 40 μ 25 μ

Decay rate (less than

Alkali aluminum silicate

98%

example 1 0.3 1.8 1.2 0.7 2 1.2 0.8 0.9 0.7 3 0.9 1.3 1.4 1.0 4th 1.0 0.6 0.4 1.7 5 0.8 1.6 0.8 1.0 6th 0.3 2.0 1.6 0.9 7th 1.5 1.4 1.7 1.0 8th 0.8 1.0 1.2 0.9

96.3

95.4

96.3

95.8

95.2

94.6

96.1

The abrasion resistance of the granules according to the invention is shown in Table 3 shown.

The abrasion resistance is obtained by determining the grain size distribution before and after treatment of the granules with increased mechanical abrasion during the sieving process (Application of freely movable nylon brushes on the individual sieves). .

OO \ Ό Ο ΙΟ

1. Abrasion resistance

I. Examination of the grain size distribution of the granules
by sieve analysis

100 g of the sample were precisely weighed and placed on the sieve with the largest mesh size (1000 μ) a standardized test sieve set DIN 4188 given. After a sieving time of 5 minutes on one. The sieve fractions were vibrated in a beautiful manner (type JEL) with a force-controlled three-dimensional sieve movement balanced. The sample residues on the sieves were weighed cumulatively, i.e. the The respective sieve residue is weighed out only after it has been combined with the following finer residue.

II. Abrasion resistance

After completion of the sieve analysis, the entire sample was again freely movable with the addition of Nylon brushes subjected to sieve analysis on all sieves. The abrasion resistance gives from the direct comparison of the first with the second sieve analysis.

Table 3
Sieve analysis according to DIN 4188 in microns

Examples 1000 500 250 125 80 <80

I II I II I II I II I II I II

I 1 0.3 0.2 3.5 3.2 48.7 48.1 42.0 42.9 5.0 5.0 0.5 0.6

I = 1. Sieve analysis without abrasion resistance

ι II = 2. Sieve analysis with abrasion resistance (nylon brushes).

; ■. · ■,. oo

.GO

; C ^

: cn

2.1 1.9 6.2 5.8 43.0 43.0 40.7 41.0 6.8 7.0 1.2 1.3 ι 1.1 0.8 3.6 3.0 56.2 55.7 32.1 33.0 5.6 6.1 1.4 1.4 ι 0.2 0.2 5.2 4.6 57.0 56.0 32.0 32.8 3.8 4.3 1.8 1.9 VD
I. 1.9 1.6 4.7 4.0 49.3 48.1 38.2 40.0 4.9 5.6 1.0 1.0 2.3 1.9 5.8 5.1 42.9 41.7 40.1 41.3 7.5 8.3 1.4 1.7 1.2 0.7. 4.0 3.1 50.1 48.9 36.5 37.2 6.7 7.8 1.5 2.3 0.3 0.1 2.9 2.6 45.7 45.1 42.8 43.3 6.9 7.3 1.4 1.6

Claims (1)

1. Free-flowing and abrasion-resistant granules Basis of water-insoluble Alkalxaluminiumsxlikät, characterized in that it is made of water-insoluble Alkali aluminum silicate and at least 5 percent by weight of a homo- or copolymeric polycarboxylic acid and / or their alkali salt. Granules according to Claim 1, characterized in that the homo- or copolymeric polycarboxylic acids Have average molecular weights of 1,000 to 1,500,000 and the general structural formula BAO ORDINAL COPY 3316b13 X
I. C.
I. Z I C-COOH have, ■ in which X, Y and Z: hydrogen, methyl, aryl, Can be carboxyl, hydroxyl or carboxymethyl groups and where the following monomeric units present: OR. I.
C - CH. where R _{1 is} an alkyl group with C ₁ to C ₁₂ or an acyl group with C ₁ to C ₁₂ / optionally hydroxyl-substituted, - CH. R ₂ = H or CH ₃ ^R 2 C - IJ COOR R ₃ = H or C ₁ to C ^ _Q alkyl, where R ₂ and R may be hydroxy-substituted. ₃ 5 -, / I I.
R, ^R 7. COPV where R- to R_ are H or alkyl groups and R ₄ to R ₇ together have 1 to 20 carbon atoms and R ₄ to R ₇ can be hydroxy-substituted. 3. Granules according to claim 1, characterized in that that the polymeric carboxylic acids are copolymers of maleic acid or maleic anhydride with methyl vinyl ether or ethyl vinyl ether or acrylic acid, having an average molecular weight of 12,000 to 500,000. 4. Granules according to claims 1-3, characterized in that they contain mixtures of homo- or copolymeric polycarboxylic acids and / or contain their alkali salts. 5. Granules according to claims 1-4, characterized in that they also contain an aminopolycarboxylic acid and / or contain their alkali salts. 6. Granules according to claims 1-5, characterized in that the aminopolycarboxylic acid nitrilotriacetic acid, Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, H-2 is hydroxyethyl-ethylenediaminetriacetic acid and / or its alkali salt; 7. Granules according to claim 1 - 6, characterized by • a weight ratio of homo- or copolymeric polycarboxylic acid and / or its alkali salt to aminopolycarboxylic acid such as 9: 1 to 1: 9, preferably 1: 1, the sum of aminopolycarboxylic acid is at least 5% by weight. . ■. 8. Granules according to claim 1 - 7, characterized in that they have a residual moisture (exclusively water of crystallization) of not more than 4% by weight. 9. Granules according to claims 1-8, characterized in that •. that they consist of 70-95% by weight of water-insoluble alkali aluminum silicate and 30-5 percent by weight homo- or copolymeric polycarboxylic acid or mixture of Polycarboxylic acid and aminopolycarboxylic acid and / or their alkali salt exist. . 10. Process for the production of granules based on water-insoluble aluminum silicate, thereby characterized in that one alkali metal silicate. Slurry with a polycarboxylic acid or a mixture mixed from homo- or copolymeric carboxylic acid and aminopolycarboxylic acid and / or their alkali salts and spray dried. ■ -:. .; _BA6 ÖF «Ö1HAI COPY. 11. A method for the production of granules according to claim 10, characterized in that one alkali aluminum silicate as a slurry with a moisture content of 37-45% by weight with at least 5% by weight (based on the alkali aluminum silicate content) of a homo- or copolymeric polycarboxylic acid or a mixture of homo- or copolymeric polycarboxylic acid and aminopolycarboxylic acid and / or their. Mixes alkali salts, the mixture is heated to 50 - 70 ° C and spray-dried. 12. A method for producing the granules according to claim 10 • to 11, characterized in that the homo- or copolymeric polycarboxylic acid or the mixture of polycarboxylic acid and aminopolycarboxylic acid and / or its alkali metal salts are used as a concentrated aqueous solution. 13. A method for producing the granules according to claim 10 to 12, characterized in that the slurry mixture if necessary adjusts to a pH value greater than 9 with alkalis. 14. The method according to claim 10 to 13, characterized in that that the spray drying is carried out in a spray tower with a 1-fluid nozzle. 15. Use of granules according to claim 1 - ^ 14, Builder in detergents / cleaning agents, dishwashing detergents ,, Laundry detergents and for water softening.