DK141882B - CHLORABLE CLEANING AGENT - Google Patents

Description

(11) PUBLICATION NOTICE 1 ^ 1882 \ Yes /

DENMARK (51) lntc '3 c 11 D 7 / BU

UMmviMni \ D 06 L 3/06 '(21) Application No 5230/74 (22) Filed on 4 Oct. 1974 (23) Race day 4 Oct. 1974

(44) The application submitted and Q

the petition is published on 7 · Jul. 1 9 ° 0

DIRECTORATE OF. ", T J

PATENT AND TRADE MARKET <3 °) Wontøt honored from death

Oct 6 1973, 2350295, DE

(71) JOH.A. BENCKISER GMBH, PO Box 21 0167, D-6700 Ludwigshafen / Rhein, DE.

(72) Inventor; Helmut Hartenstein, Gartenstraese 3, D-6729 Ruelzheim, DE.

(74) Plenipotentiary in Suction Treatment:

Plougmann & Vingtof t Patent agency ♦ _____ (54) Chlorine stable detergent.

The present invention relates to alkaline aqueous cleaning agents, especially for service, containing active chlorine scavenging compounds.

For cleaning service in dishwashers, alkaline cleaning agents are usually used, consisting essentially of builders capable of complexing calcium and magnesium ions, alkali silicate and a slightly foaming, nonionic surfactant. To enhance the purifying effect, especially for removing dye stains such as tea, coffee, fruit remnants, etc., additional bleaching agents which release oxygen or preferably chlorine are added to the agents.

141882

These known cleaning agents containing an active chlorine-depleting compound all have the disadvantage that the chlorine content decreases upon storage, thereby reducing the cleaning effect, and this much more, the more water is present in the agents, which water may partly come from crystal water in the raw materials or may be introduced by the preparation of the agents, e.g. by the granulation. Satisfactory storage or storage stacks are only such mixtures for which the preparation is completely anhydrous raw materials.

However, for a rapidly soluble and fully flushable product from the dishwasher dosing device, a certain water content of the raw materials is indispensable, which in turn causes the rapid decomposition of the chlorine components.

Swedish Patent Specification No. 207,649 describes the use of certain definitions as stabilizers for polychlorocyanuric acid-containing agents.

In the case of these olefins, these are difficult to access and expensive substances, which are also most often liquid, and in order to achieve a good distribution they must be sprayed over the other constituents of the agent in a further operation.

New stabilizers are now provided which do not have these drawbacks.

The present invention relates to alkaline particulate aqueous cleaning agents, in particular for service, containing active chlorine scavenging compounds, chlorine stabilizer, silicate, builders of the type capable of complexing calcium and magnesium ions, low foaming nonionic surfactants and water which are peculiar in that they contain 0.05 - 5% of a chlorine stabilizer consisting of a mixture of aluminum salt and zinc salt calculated as alumina and zinc oxide in a ratio of 1:10 - 10: 1.

The stabilizers herein are solid powdered substances which can be easily mixed with the other detergent ingredients.

The content of stabilizer should preferably be 0.4%, based on alumina and zinc oxide.

3 141882

Suitable aluminum salts are: aluminum sulfate, aluminum chloride, aluminates and water-insoluble aluminum compounds such as basic aluminum phosphate, aluminum stearate, aluminum silicate or also double salts such as alkali metal-aluminum silicates, alkali metal-aluminum-aluminum phosphates, and alkaline earth aluminum phosphates.

Zinc salts include: zinc sulfate, zinc chloride, zincates or insoluble zinc compounds such as zinc oxide, zinc stearate, zinc silicate or zinc phosphate.

Preferably, zinc-aluminum double compounds can also be used, e.g. zinc-aluminum-silicate, zinc aluwinate or aluminum-zincate.

Examples of active chloro-splitting compounds are e.g. sodium / potassium salts of di / trichloroisocyanuric acid, sodium / calcium / lithiura salts of chloroacetylation, chlorinated trisodium orthophosphate, trichloromelamine, N-chloroacetylurea and chlorarain. They are added in such amounts that there is 0.5-5%, preferably 1%, active chlorine in the mixture.

In addition to the chlorine stabilizer and the active chlorine-releasing compounds, the compositions of the invention may contain the usual ingredients for cleaning present. However, it is a particular advantage that according to the invention it is not necessary that the raw materials are in anhydrous form, but that it is possible to dispose of crystalline aqueous raw materials without loss of chlorine during storage or storage of the agents.

Thus, a substantial component of the agents is a builder capable of complexing calcium and magnesium ions, preferably the alkaline reacting triphosphate, in amounts of 20 - 80%, preferably 30 - 60%, based on the mixture. The water content for a well-flushable product should be 3-15%, preferably 4-8%. Also the fully hydrated triphosphate as hexahydrate can be used. Also, other builders such as phosphonates or nitrogen-containing organic complexes such as NTA and EDTA or nitrogen-free organic complexes such as polycarboxylic acids may be present in the agents.

141882 4

Furthermore, the agents must contain silicate, preferably sodium silicate. The ratio of Na 2 O to SiO 2 must be between 1: 1 and 1: 3.5.

It is used in an amount of 5 - 70%, preferably 20 - 50%, based on the mixture. The water content may, to prevent discoloration and sticking, be 1 - 10%, preferably 5%. Instead, the pentahydrate with approx. 42% water.

It is also important that a certain relationship between SiO2 and P2O5 is observed, since on the one hand the purifying effect becomes optimal due to synergistic effects and on the other hand the corrosion is reduced to a minimum. The ratio of P2 ° 5: 2 to 2 should be between 1: 0.7 and 1: 2, preferably 1: 1.

As nonionic surfactants, low foaming agents such as lower ethoxylated nonylphenol polyglycol ethers, polypropylene polyethylene block polymers, fatty alcohol ethoxylates with C C-C ^ g and 3-6 moles of ethylene oxide are considered. Further, the mixtures may further contain other usual substances such as dyes, perfumes, etc.

The compositions of the invention are prepared according to conventional methods such as by mixing or granulating. The application is in solid form at usual concentrations.

The compositions according to the invention can be stored or stored for a long time without any significant loss in chlorine and thus in purifying effect. In addition, depending on the water content, the agents are easily soluble and can be flushed well and completely from the dishwasher dispensers.

It has been found that the good chlorine stabilizing effect occurs only with the mixture of aluminum salts and zinc salts used according to the invention, while aluminum salts alone and zinc salts alone have no chlorine stabilizing effect.

According to German Publication No. 2,124,835, mixtures of aluminum salts and boron salts are used for a completely different purpose, namely as glaze preservative. It has been found in tests conducted by the applicants that such a mixture does not have the chlorine stabilizing effect exhibited by the mixture of aluminum salts and zinc salts used according to the invention. This is evident from the following experiments: A Chlorine stability of known cleaning agents (without the addition of a chlorine stabilizer).

Detergents of the composition below are tested to determine chlorine stability. The agents are stored at 40 ° C and the chlorine content is determined after various periods of time.

Example 1.

50% sodium phosphate, anhydrous 40% sodium metasilicate, anhydrous 2% potassium dichloroisocyanurate 2% polypropylene-polyoxyethylene block polymerate 6% sodium carbonate, calc.

Example 2.

50% sodium triphosphate with 5% water 40% sodium metasilicate with 3% water 6% soda 2% fatty alcohol ethoxylate Cg-C-q with 3 moles of ethylene oxide 2% potassium dichloroisocyanurate.

Example 3

36% sodium triphosphate with 3% water 60% sodium metasilicate with 5 moles of water (containing 42% water) 2% nonylphenol ethoxylate with 5 moles of ethylene oxide 2% potassium dichloroisocyanurate.

6 141882

The test of chlorine stability at 40 ° C gave the following results:

Table I

Example I II III

Initial chlorine content 1.2 1.2 1.2 after 1 month 1.1 1.0 1.0 after 3 months 0.8 0.7 0.6 after 6 months 0.7 0.4 0.3 flushing poor good good

This arrangement shows the relatively rapid decrease in the chlorine content and hence the decrease in the cleaning ability, especially towards dye spots such as tea, coffee and fruit residues. The effect is particularly evident in the preparations containing water. On the other hand, precisely the aqueous products can be easily flushed.

B Chlorine stability of detergents plus chlorine stabilizer of zinc and aluminum salt (according to the invention) and by comparison chlorine stability of detergents plus addition of aluminum salt alone or zinc salt alone.

Example 4. ·

A detergent of the following composition: 50% sodium triphosphate with 5% water 40% sodium metasilicate with 3% water 2% soda 2% fatty alcohol ethoxylate Cg - C3 with 3 moles of ethylene oxide 2% potassium dichloroisocyanurate is added to one of the following compositions: 7 141882 a) 4% aluminum-zinc silicate with 5% alumina and 8% zinc oxide, corresponding to 0.2% alumina + 0.32% zinc oxide (according to the invention) b) 2.6% zinc silicate, corresponding to 0.53% zinc oxide c) 3.3% aluminum silicate, corresponding to 0.53% alumina d) 1.25% aluminum silicate, corresponding to 0.2% alumina +> 0.32% B203, each time supplemented with Na2SO4 to 100%.

Example 5

33% sodium triphosphate with 3% water 58.6% sodium metasilicate with 5 moles of water (contains 42% water) 2% nonylphenol ethoxylate with 5 moles of ethylene oxide 2% potassium dichloroisocyanurate 4% calcium aluminum silicate, corresponds to 0,2% alumina 0.4 % zinc phosphate, corresponds to 0.2% zinc oxide.

Example 6

60% sodium triphosphate with 5% water 30.5% sodium metasilicate with 5 moles of water (contains 42% water) 2% nonylphenol ethoxylate with 4 moles of ethylene oxide 2% potassium dichloroisocyanurate 5.5% aluminum-zinc silicate corresponds to 0.2% alumina and 0.6% zinc oxide.

The aluminum-zinc silicate is made as follows:

A solution (A) consisting of 680 g of water glass with 9.6% Na2 © + 24.8%

SiO 2, diluted to 2 liters.

8 161882

A solution (B) consisting of 50.3 g of aluminum sulphate and 47.7 g of zinc sulphate is also diluted to 2 liters.

Both solutions are poured at a pH of 7 - 8 at the same time and slowly into 2 liters of water at 80 ° C and maintained at the temperature mentioned.

After complete mixing of the solutions, the precipitate is suctioned, which is washed sulfate-free and dried at 130 ° C. The powdered substance has the following composition: 3.6% alumina 10.8% zinc oxide 5.7% Na 2 O 69.0% SiO 2 Remaining water.

Of the substance prepared, 5.5% is used, corresponding to 0.2% alumina and 0.6% zinc oxide.

Eksempel.7.

The ratio A ^ C ^ iZnO = 1:10.

40% sodium triphosphate with 5% water 53.31% sodium uromethasilicate with 5 moles of water 2% nonylphenol polyglycol ether with 3 moles of ethylene oxide 2% potassium dichloroisocyanurate 0.69% aluminum sulfate with 29% Al2 O3, corresponding to 0.2% Al2 O3 2.0% ZnO.

9 141882

Example 8.

60% sodium triphosphate with 7% water 30.84% sodium metasilicate with 5 moles of water 2% fatty alcohol ethoxylate with 6 moles of ethylene oxide 2% potassium dichloroisocyanurate 0.40% zinc sulphate with 50.3% ZnO, corresponds to 0.2% ZnO 4.76% aluminum phosphate with 42% A ^ O ^, equals 2% A ^ And.

The chlorine stability test when stored at 40 ° C yielded the following results:

Table II

Example Initial 1 month 3 months 6 months chlorine content 4 a) 1.2 1.0 1.0 0.9 4 b) 1.2 1.0 0.65 0.4 4 c) 1.2 1.0 0 , 6 0.3 4 d) 1.2 1.0 0.7 0.5 5 1.2 1.1 1.0 0.9 6 1.2 1.1 1.0 1.0 7 1.2 1.1 1.0 0.9 8 1.2 1.15 1.1 1.0

The comparative tests unequivocally show the excellent chlorine stability exhibited by the compositions of the invention in relation to the compositions of the same composition without the addition of a chlorine stabilizer and in relation to agents containing only aluminum salt or zinc salt only. In addition, the products of the invention can be easily and completely rinsed from the dosing devices.