DE1280456B - Powdered cleaning and / or abrasive preparations and process for their manufacture - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

German class

Number:
File number:
Registration date:
Display day:

ClId

C09g
D061

23e-2
22g-14

P 12 80 456.7-41 (U 11904)

July 23, 1965

17th October 1968

The invention relates to powdered detergent and / or abrasive compositions and methods of making them. In particular, the invention relates to powdery cleaning and / or abrasives containing an inorganic per-compound as a bleaching agent and a catalyst to increase the low temperature bleaching ability of per compounds.

Known low-temperature bleaches generally contain a chlorine-releasing compound, z. B. dichlorocyanuric or trichlorocyanuric acid, which has the disadvantage of spreading an unpleasant Smell of chlorine, which persists for some time after use, especially on the Skin, persists, and the further disadvantage of sometimes attacking the fibers of textiles, especially of textiles provided with a finish. Another The disadvantage associated with chlorine bleach is their instability in storage, which leads to leads to a decrease in bleaching power. These disadvantages are not to the same extent with bleaches based on inorganic per compounds such as perborates or persulfates. However, inorganic per compounds are relatively inactive bleaching substances at low temperatures, for example at 20 to 50 C. Their bleaching effect increases with increasing temperature and reaches its maximum when simmering.

Accordingly, the invention consists in a powdery Cleaning and / or abrasive agent which contains an inorganic per compound as a bleaching agent An agent and a catalyst for increasing the low temperature bleaching ability of per compounds contains, characterized by a content of a water-insoluble or sparingly soluble powdery dry inorganic carrier containing less than 15% water on which Metal ions are adsorbed as a catalyst.

The invention also consists in a method for producing this agent, which is characterized in that is that the previously prepared catalyst is the powder as the last ingredient under thorough Mixing is added.

The agents according to the invention are distinguished by the fact that they can even be used to remove adhering Stains, e.g. tea stains, from hard surfaces such as bowls, tiles and the like, are suitable.

Effective bleaching at relatively low temperatures, for example at 20 to 50 ^° C., can be achieved with the agents according to the invention.

Powdered cleaning and / or
Abrasives and Processes
for its manufacture

Applicant:

Unilever N.V., Rotterdam (Netherlands)

Representative:

Dr.-Ing. A. ν. d. Werth and Dr. F. Lederer,

Patent attorneys,

2100 Hamburg 90, Wilstorfer Str. 32

Named as inventor:
Balaram Das, Rotterdam;
Karel Gerhard van Senden,
Schiedam (Netherlands)

Claimed priority:

Great Britain, June 24, 1964 (29 769)

The catalysts which can be used according to the invention are in the form of a dry powder with a water content of less than 15 ° o. preferably 1 to 5%. and contain a metal clay adsorbed on a suitable inorganic support. The metal ions per se in non-adsorbed form may or may not have an effect on the bleaching activity of the inorganic per-compounds. However, when properly adsorbed on suitable supports, these metal ions greatly increase the bleaching activity. It has been found that the metal ions of transition elements of the periodic table, especially those with unpaired electron spinning, such. B. Co ² *, Mn ²⁺ , Ni ² ', Cr ^{3 f} , Mo ²¹ or Cu ² \ are particularly effective. Advantageously usable carriers are any water-insoluble or sparingly soluble compounds of Zn, Cd, Ca, Mg, Al, Sn, Be, Ti, Sb, Bi or SiQ ₂ .

The most active catalysts resulted from these possible combinations when Co ²⁺ on zinc silicate, titanium dioxide or hydroxide, tin dioxide, antimony trioxide, aluminum oxide, or hydroxide

809 627/1407

-silicate, alkaline zinc carbonate, alkaline cadmium carbonate, Cadmium carbonate, silicate or oxide is adsorbed. The metal ion content can be from 1 to 100 mg or more per 1 g of catalyst, and preferably from 20 to 60 mg / g. Of course The catalysts of the invention are also effective in increasing the bleaching capacity of inorganic Per compounds to support colored solutions at low temperatures.

The catalysts, the production of which is not _{claimed here t0} , can be produced in the following way:

a) By dry mixing a finely divided powder containing the metal ion Salt, e.g. B. COCI2, with the finely divided carrier in such a way that a homogeneous Mixture is obtained in which both substances are in very good contact.

b) By adding an aqueous solution containing the metal ion, e.g. B. CoCfe solution, to the required amount of finely divided powdery carrier. Water is then added and the whole mixture is stirred until a paste-like mass is obtained. The product is then at temperatures up to about 100 ⁰ C - can be vacuum or can not be used - preferably dried at temperatures of 40 to 60 ° C, at a vacuum of 1 to 15 mm Hg. Much higher temperatures can also be used depending on the type of catalyst, although it is not advisable because it would affect the catalytic activity.

c) By freeze-drying the paste-like masses as described under b) at temperatures from −50 to 0 ^° C. and a vacuum of 0.01 to 1 mm Hg.

The catalysts obtained in this way support the bleaching at temperatures of e.g. B. 20 ⁰ C or at temperatures that are even lower, as well as at higher temperatures with sodium perborate and / or with other inorganic per compounds including per compounds, such as a triple salt, consisting of potassium permonosulfate, potassium hydrogen sulfate, potassium sulfate in an approximate molecular ratio of 2: 1 :1:

It is desirable that the bleaching agent be an alkaline one Solution, preferably one with pH values between 7 and 11, should be given.

It has been found that catalysts prepared by the above procedures for some Time can be saved without losing its activity. You can dry with inorganic per compounds to form low temperature bleaches, preferably in weight ratios of 1: 1 and 1: 8, can be mixed. Such mixtures, when incorporated in normal detergents, enable them to bleach effectively at relatively low temperatures. It was also found that those obtained by the freeze-drying method [method c)] Catalysts, especially those with zinc compounds as supports, are much more active than the catalysts which were prepared from the same compounds according to method a) or b).

However, their activity decreases when stored under normal room conditions to values which are approach those of catalysts made according to the other methods. By a suitable coating of the particles would make it possible to obtain this unusually high level originally To keep activity. Catalysts made with supports with a particle size of 250 to 500 μ, are particularly suitable for wrapping.

The catalysts can according to the invention with the inorganic per compounds, for. B. sodium perborate, mixed to form persistent low temperature bleaches. You can also in cleaning powder mixtures with a per-compound content of up to 30% and also in scouring powder with a per compound content of 1 to 20%, preferably 5 to 15%, of sodium perborate be incorporated. When used in scouring powder formulations, it is preferable to use the catalyst added to the powder as the last ingredient with thorough mixing. Preferably the water content is of detergent or scouring powder is kept as low as possible.

In order to avoid unwanted coloring of the bleaching solution and the goods to be bleached, what by The catalyzed metal ions can cause sequestrants in the bleach be incorporated, e.g. B. sodium hexametaphosphate. Other condensed phosphates, in particular Sodium tripolyphosphate appears to decrease the catalytic activity.

Example!

Catalysts with a cobalt content of about 4% (40 mg / g catalyst) were used in the following Ways made:

a) 100 g of finely powdered zinc silicate (150 μ) and 19 g of COCl2 · 6H2O were put in a mortar mixed together so that a homogeneous mixture was obtained. That was zinc silicate previously dried in an oven at 80 ° C under vacuum for 1 hour.

b) A solution of 38 g of COCl2 · 6H2O in 180 ml of water was added to 200 g of finely powdered zinc silicate (150 μ) and the mixture was stirred so that a homogeneous paste was obtained. Part of the paste was then ^{dried in a vacuum dryer at 40 °} C. and 10 mm Hg for 5 hours. The product obtained by pulverizing the grains in a mortar had a free water content of about 1.5%.

c) The other part of the paste was at a temperature of less than -20 "C and below dried at a pressure of 0.05 mm Hg. The water content was about 1.5%.

Example 2

A number of scouring powder formulations were made containing sodium perborate and one prepared according to Example 1 obtained catalyst. For comparison purposes, two remedies were also made, one without a catalyst and the other with a content of metal ions, but without Carrier.

Table I. II. III 9.0 9.0 IV I. Parts by weight 65.5 82.5 15.0 8.5 ^ atrium dodecyl 9.0 benzenesulfonate .. 72.0 4.0 - Mixture III, Silica 8.5 3.0 - to which NaBO _:! -4H ₂ O ... added
becomes 0.16%
Cn- I ik Catalyst with
a salary of 4.0 3.5 - CoCl ₂ without 4% Co ² ' 3.0 carrier Urea" 3.5 Matriumhexameta- phosphate

capacity again in the manner as described in Example 2, measured. The following results show that the agents retained their bleaching activity during storage.

Table III

(Results obtained after storage of
2 months)

These agents were used at room temperature to bleach tea stains on unglazed tiles (Royal Sphinz Maastricht, 15 x 15 cm) by applying it as a paste to the tile surface. The following test procedure was used.

The reflectance of a tea stained tile was measured. 10 g of powder were distilled with 7 ml Mixed water and stirred for 30 seconds. The mixture was poured onto the tile surface. After a contact time of 1 to 2 minutes, the paste was removed from the tile surface with running tap water rinsed off for at least 10 seconds. After standing in the air for about The reflectance of the tile was measured again for 24 hours. The table below shows the increase indicated on the reflectance of the tile surface after treatment. From this table it can be seen that the The type of vehicle used is a major factor.

Table II

40

45

carrier increase in the 2 minutes Reflectance (%) after a 42 middle Zinc silicate Contact time from 29 Cadmium carbonate 1 minute 24 I. Tin oxide 27 30th Antimony oxide 27 30th Zinc silicate *) 20th 42 Zinc silicate 27 11 No catalyst 26th 5 II No carrier 27 III 3 IV 0

50

*) Catalyst prepared by dry mixing. The other catalysts were prepared according to process b).

B e i s ρ i el 3

The first four of the agents mentioned in Table II were taken at room temperature in closed vessels kept for 2 months and their bleaching

55

carrier Increase in the 2 minutes Reflectance (%) after a 39 middle Zinc silicate Contact time from 31 Cadmium carbonate 1 minute 23 I. Tin oxide 26th 28 Antimony oxide 30th 22nd 27

Claims (7)

Patent claims: 1. Powdered cleaning and / or abrasive detergents, which uses an inorganic per compound as a bleaching agent and a catalyst Contains increase in the low-temperature bleaching capacity of per compounds, characterized by a content of one water-insoluble or poorly soluble powdery dry inorganic, less than Support containing 15% water on which metal ions are adsorbed as a catalyst. 2. Means according to claim 1, characterized in that the metal ion from the group of Transitional elements of the periodic table, especially those with an unpaired one Electron spinning, is selected. 3. Agent according to the preceding claims, characterized in that the carrier is a water-insoluble or sparingly soluble compound of Zn, Cd, Ca, Mg, Al, Sn, Be, Ti, Sb, Bi or SiO ₂ . 4. Agent according to the preceding claims, characterized in that the metal ion content is between 1 to 100 mg per 1 g of catalyst. 5. Agent according to the preceding claims, characterized in that the weight ratio between catalyst powder and inorganic Per compound is within the range of 1: 1 to 1: 8. 6. Agent according to the preceding claims, characterized in that the per connection is present in an amount of 1 to 30 percent by weight of the total batch. 7. A method for producing an agent according to the preceding claims, characterized in that that the previously prepared catalyst is added to the powder as the last ingredient with thorough mixing.